CS235964B2 - Fungicide agent and method of its effective substances making - Google Patents

Description

235964 2

The present invention relates to novel phenoxyphenyl azolylmethyl ketones and carbinols, a process for their preparation and their use as fungicides and as intermediates for the synthesis of other plant protection agents.

It is already known that phenyl azolylmethyl ketones and carbinols possess fungicidal properties (see DE-OS 24 31 407). The efficacy of these azolylderivatives in numerous areas of indications, particularly when these substances are applied at lower levels and concentrations, is not always satisfactory.

New phenoxyphenyl azolylmethyl ketones and carbinols of the general formula I have now been found

Az (I) in which

Az is 1,2,4-triazol-1-yl or -4-yl or 1-imidazolyl, X is phenyl optionally substituted by one to three halogen atoms and / or alkyl of 1 to 4 carbon atoms, A represents a keto group, a -CH (OH) - or -C (OH) E- group, wherein B is a methyl group, an allyl group, a benzyl group or a chlorobenzyl group, and B 1 is a hydrogen atom, a C 1 -C 12 alkyl group, an alkenyl group C 2 -C 6 alkynyl, C 2 -C 6 alkynyl, C 1 -C 2 alkoxyalkyl, chlorobenzyl, cyclopentyl or cyclohexyl, and acid-addition salts thereof for plants. with metal salts.

The compounds of formula (I) optionally contain two asymmetric carbon atoms and may be present in the form of both geometric isomers (treo- and erythro-form), which may result in different weight ratios. In both of these cases, the disclosed compounds may exist in the form of optical isomers. Furthermore, it has been found that the phenoxyphenyl azolylmethyl ketones and the carbinols of general formula I are obtained by

a) haloketones of formula II x-o

(II) in which

Hal is a halogen atom, preferably chlorine or bromine, and X is as defined above,

are reacted with azoles of the formula III H - Az (III) wherein A z is as defined above, in the presence of a diluent and in the presence of an acid-binding agent, where appropriate 3 235% ¼ b) not the azolyl ketones of the formula Ia X thus obtained -0 co-ch2 —Az (Ia) in which

Az and X are as defined above,

is treated with an alkylating agent of formula IV (IV) wherein R 1 is as defined above and Z is an electron withdrawing group, in the presence of a base and in the presence of an organic diluent, or in an aqueous-organic biphasic system in the presence of a phase transfer catalyst, and optionally (c) processes (a) and (b) obtained by azolyl ketones of general formula (Ib) X-O-O-O-CO-CH-R 1Az (Ib) in which

Az, R 1 and X are as defined above, reduced by reaction with complex hydrides or diluents, or reacted with organometallic compounds

aluminum isopropoxide in the presence of the compounds of formula V

Me-R (V) wherein R is as defined above;

Me represents an alkali metal or a residue

Hal '- Mg where

Hal 'means chloro, bromo or iodo, in the presence of a diluent.

An acid or a metal salt can then optionally be added to the compounds of formula I thus obtained. In many cases, it has proven advantageous to obtain the compounds of the formula (I) in pure form via their salts.

The novel phenoxyphenyl azolylmethyl ketones and the carbinols of formula I have potent fungicidal properties. Surprisingly, the compounds according to the invention exhibit a better fungicidal action from the prior art known as phenyl azolyl methyl ketones o-carbinols, which are related chemically and efficiently.

In addition, the novel phenoxyphenyl azolylmethyl ketones and carbinols of the formula I are interesting intermediates for the production of other plant protection agents. In ketoderivatives, the aceto group can be reduced to the group -CH (OH) -, or -CR (OH) - (see variant c) of method 235964 of the invention). In addition, functional derivatives of keto groups such as oximes, oximeters, hydrazones and ketals can be prepared by appropriate reactions. Carbinol derivatives can be converted to the corresponding ethers on the hydroxyl group in a conventional manner. Further, by reaction with, for example, acyl halides or carbamoyl chlorides, the corresponding acyl derivatives or carbamoyl derivatives of the compounds of formula (I) may be prepared in a manner known per se.

Accordingly, the compounds of the invention represent a valuable enrichment of the prior art. The present invention provides a fungicidal composition comprising at least one phenoxyphenyl azolylmethyl ketone or a carbinol of the above general formula I or an acid addition salt or salt thereof compatible with the above and a process for the preparation of these active compounds.

If, for example, alpha-chloro-4- (4-chlorophenoxy) acetophenone and 1,2,4-triazole are used as starting materials, the reaction scheme a) according to the invention can be described by the following reaction scheme:

For example, 4- (4-chlorophenoxy) -alpha- (1,2,4-triezol-1) is used. -yl) acetophenone and 4-chlorobenzyl chloride can be described by the following reaction scheme as follows:

Cl -CO-ch 2 + CICH 2 - (1 H -Cl 2 - Cl

With the use of, for example, 4- (4-chlorophenoxy) -alpha- (1,2,4-triazol-1-yl) acetophenone, sodium borohydrin, the reaction can be carried out as follows: step c) according to the invention to describe the following reaction scheme:

Cl

O

, "= i —N + IMaBH4-

OH I /

CH- CH 2 -N When used, for example, 1- (4-chlorophenyl) -3- [4- (4-chlorophenoxy) phenyl] -2- (1,2,4-triazol-1-yl) propane-3- and methylmagnesium bromide, the reaction step c) of the present invention can be described by the following reaction scheme:

The halogen ketones required as starting materials in the sense of step a) of the invention are generally defined by the above formula II. However, these haloketones are still known, but can be prepared in a generally known manner such that, for example, the diphenyl ether of formula VI

Wherein K is as defined above, is reacted with chloro (bromo) acetyl chloride (bromide) under Friedel-Crafts acylation conditions (see also Examples).

The azoles used as further starting materials in the process of process a) of the invention are generally defined by the above formula III. These azoles are commonly known in organic chemistry.

The azolyl ketones used as starting materials in process b) of the invention are generally defined by the above formula Ia. The compounds of general formula Ia are within the scope of the invention.

The alkylating agents used in the process of process b) of the process of the invention are generally defined by the above formula IV. in this formula, Z is preferably a leaving group electron, such as a halogen atom, a p-methylphenylsulfonyloxy group, -O-SOg-OR 'group, or -NR8a, and others where R' is an alkyl group of 1 to 4 carbon atoms.

The alkylating agents of general formula (IV) are generally known in organic chemistry.

The azoyl ketones used as starting materials in process c) of the invention are generally defined by the above formula Ib. The compounds of general formula Ib are within the scope of the invention.

The organometallic compounds used as further starting materials in the process c) of the process according to the invention are generally defined by the above formula V. In the general formula, Me is preferably lithium, sodium or the so-called Grignard grouping, i.e. grouping. Hal'-Mg, where Hal 'is chloro, bromo or iodo. The organometallic compounds of formula V are generally known in organic chemistry.

For the purpose of process (a) of the present invention, diluents include inert organic solvents, preferably ketones such as diethyl ketone and in particular acetone and methyl ethyl ketone, nitriles such as propionitrile and especially acetonitrile, alcohols such as ethanol or isopropanol, ethers such as tetrahydrofuran or dioxane, aromatic hydrocarbons such as toluene, benzene or chlorobenzene, formamides such as dimethylformaride, and halogenated hydrocarbons.

The reaction according to process a) of the process according to the invention is carried out in the presence of an acid scavenger. For this purpose, any of the customary inorganic or organic acid acceptors, such as carbonates, alkali metals, for example carbonate, potassium carbonate and sodium bicarbonate, or lower tertiary alkylamines, cycloalkylamines or aralkylamines, for example triethylamine, N, H-dimethylcyclohexylamine, dicyclohexylamine,,, can be used. Β-dimethylbenzylamine, followed by pyridine and diazabicyclooctane. Preferably, an excess of the starting azole is used for this purpose.

The working temperatures of process a) of the process of the invention can be varied within wide limits. In general, the reaction is carried out at a temperature between about 20 ° C and 150 ° C, preferably between 60 ° C and 120 ° C. In the presence of a solvent, it is expedient to work at the boiling point of the solvent. Preferably, 2 to 4 moles of azole and 1 to 4 moles of an acid-binding agent are used per mole of the compound of general formula (II) when working in process a) of the process according to the invention. To isolate the compounds of formula (Ia), the solvent is distilled off and the residue is worked up in a customary manner. 235964 6

As the diluent for the process according to process b) of the process according to the invention come! suitable organic solvents, preferably aromatic hydrocarbons, benzene, toluene or xylene, halogenated hydrocarbons such as methylene chloride, tetrachloromethane, chloroform or chlorobenzene, esters such as ethyl acetate, formamides such as dimethylformamide and dimethylsulfoxide.

The reaction according to process b) of the process according to the invention is carried out in the presence of a base. For this purpose, all customary organic and especially inorganic bases, such as alkali metal hydroxides or alkali metal carbonates, for example sodium hydroxide and potassium hydroxide, can be used.

The working temperatures in process b) of the process according to the invention can be varied within wide limits. Generally, the reaction is carried out at a temperature between 0 ° C and 100 ° C, preferably between 20 ° C and 100 ° C. In the process according to process b) of the process according to the invention, 1 to 1.2 mol of alkylating agent is preferably used per mole of the compound of general formula Ia. The isolation of the resulting product of general formula (Ib) is carried out in a conventional manner.

The reaction according to process b) may also be carried out in a two-phase system, for example aqueous sodium or potassium hydroxide solution - toluene or methylene chloride, optionally adding 0.1 to 1 mole of phase transfer catalyst, for example ammonium or phosphonium compounds, for example benzyldodecyl dimethylammonium chloride or triethyl -benzylammonium chloride.

The reduction according to process c) of the process of the invention is carried out in a conventional manner.

When complex hydrides are used, polar organic solvents, preferably alcohols such as ethylene, ethanol, butanol or isopropanol, and ethers such as diethyl ether or tetrahydrofuran are used as diluents for the process of the invention. to 30 ° C, preferably 0 to 20 ° C. In this case, about 1 reaction equivalent of the complex hydride, such as sodium hydride or lithium aluminate, is used per mole of ketone Ib. To isolate the reduced compounds of general formula (I), the residue is taken up in dilute hydrochloric acid, the mixture is then alkalized and extracted with an organic solvent. Further processing is then carried out in the usual manner. When working with aluminum isopropoxide, diluents suitable for use in the process of the present invention are preferably alcohols such as isopropanol or inert hydrocarbons, such as benzene. Again, the reaction temperatures can be varied within a wide range. Generally, it operates at a temperature between 20 and 120 ° C, preferably at 50 to 100 ° C. To perform the reaction, about 1 to 2 moles of isopropoxide aluminum are added to 1 mole of the ketone of the formula Ib. To isolate the reduced compounds of formula I, excess solvent is distilled off in vacuo and the resulting aluminum compound is decomposed with dilute sulfuric acid or sodium hydroxide solution. Further processing is then carried out in the usual manner.

When working with organometallic compounds, diluents which are preferably employed are anhydrous ethers such as diethyl ether, dibutyl ether or tetrahydrofuran. The reaction is generally carried out at a temperature of 0 to 80 ° C, preferably at the boiling point of the solvent used. In this reaction, about 1 to about 3 moles of the organometallic compound of formula (V) are employed per mole of the compound of formula (Ib). The reaction of the organometallic reagent is carried out in a manner known per se. In order to prepare the physiologically tolerable dispensing salts of the compounds of formula I with acids preferably the following acids are suitable: hydrohalic acids, such as hydrochloric acid and hydrobromic acid, especially hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, one and dibasic 7 235964 carboxylic and hydroxycarboxylic acids such as acetic acid, malic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid, and sulfonic acids such as acid p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid.

Acid addition salts of compounds of Formula I can be prepared in a simple manner by conventional salt preparation methods, for example, by dissolving Compound X in a suitable inert solvent and adding an acid such as hydrochloric acid. The salts formed can be isolated in a known manner, for example by filtration, and optionally purified by washing with an inert organic solvent. In order to prepare complexes of the compounds of the formula I with metal salts, preference is given to metal salts IX. to IV. main groups and X, to XI. as well as VI. to VI, subgroups of the Periodic Table, examples of which are 5, zinc, manganese, magnesium, tin, iron, and nickel.

Suitable salt anions are those derived preferably from the following acids: hydrohalic acids, such as hydrochloric acid and hydrobromic acid, phosphoric acid, nitric acid and sulfuric acid.

The metal salt complexes of the formula I can be prepared in a simple manner by conventional means, for example by dissolving the metal salt in an alcohol such as ethanol and adding the compound of the formula X. The metal salt complexes can be isolated in a known manner, for example by filtration, and optionally purified by recrystallization. The active compounds according to the invention show a strong microbicidal action and can be used in practice to combat undesirable microorganisms. The active ingredients described are suitable for use as plant protection agents.

Fungicidal compositions are used in plant protection to combat fungi from the classes Plasmo-diophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes Deuteromycetes.

Bactericidal agents are used in plant protection to combat bacteria from the Pseudomonadaceae, Hhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomyceraceae families.

Since the active compound plants of the present invention are well tolerated at the concentrations required to combat plant diseases, these compounds can be used to treat over-plant parts of plants, seedlings and seeds, as well as to treat the soil.

As plant protection agents, the active compounds according to the invention can be used particularly well for combating Erysiphe species, for example barley powders or cereals (Erysiphe graminis - powdery mildew), for controlling Venturia species, for example against Venturia inaequalis ) or to combat rice diseases such as Pyricularia oryzae and Pellicularia sesakii. It is preferred that the compounds of the invention also exhibit good bactericidal activity. The active ingredients can be converted into conventional formulations, such as solutions, emulsions, spray powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension and emulsion concentrates, powdered seed dressings, impregnated natural asynthetic agents. active ingredient, small particles coated with polymeric substances of the coating material for the seed, as well as with flammable additives such as smoke supports, smoke containers, smoke spirals and the like, as well as compositions in the form of a cold or hot mist spray concentrate. 235964 8

These compositions are prepared in a manner known per se, for example by mixing the active ingredient with fillers, i.e. liquid solvents, liquefied gases under pressure or / and carriers, optionally using surfactants, i.e. emulsifiers or dispersants and / or foaming agents. In the case of using water as a filler, for example, such organic solvents may be used as co-solvents. Basically suitable liquids are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol, as well as ethers and esters thereof, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide as well as water.

By liquefied gaseous fillers or carriers are meant liquids which are gaseous at normal temperature and normal pressure, for example aerosol propellants, as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: stone additions such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or silica, and synthetic stone flours, such as highly disperse silicic acid, alumina and siliceous.

Suitable solid carriers for granules are crushed and fractionated natural stone materials such as limestone, marble, pumice, sepiollt and dolomite, as well as synthetic granules of inorganic and organic flours and granulates, of organic material, such as sawdust, coconut shells. Suitable emulsifiers and / or foaming agents are non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. dispersants such as lignin, sulfite waste liquors and methylcellulose.

The compositions of the invention may contain adhesives such as carboxymethylcellulose, natural and synthetic powder, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate. In addition, the compositions may contain coloring agents such as inorganic pigments, for example ferric, titanium dioxide and ferrocyanide blue, and organic dyes such as alizarin dyes, azo dyes phthalocyanine dyes, and trace elements such as iron, manganese, boron, copper, cobalt, molybdenum salts and zinc.

The concentrates generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight, of the active ingredient. The active compounds according to the invention may be present in the formulations in admixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematocides, herbicides, bird-curing agents, growth substances, plant nutrients and soil improvers. The active compounds according to the invention can be applied as such, in the form of concentrates or by further dilution of the prepared dosage forms, as directly usable solutions, emulsions, suspensions, powders, pastes and granules. The application is carried out in the customary manner, for example by means of a dipping, dipping, spraying, fogging, evaporation, injection, coating, dusting, tumbling, dry pickling, wet or wet pickling, or pickling. When using the active ingredients for the treatment of above-ground plants, their concentrations in the applicable compositions can be varied within wide limits. These concentrations generally lie between 1 and 0.000 1% by weight, preferably between 0.5 and 0.001% by weight. In the treatment of seed, 0.001 to 50 g of active ingredient, preferably 0.01 to 10 g of active ingredient are generally required per kilogram of seed. Depending on the nature of the action, the active substances are required to be used in the soil treatment at a concentration of from 0.000 to 0.1% by weight, preferably from 0.000 to 0.02% by weight.

The following examples illustrate the preparation of the active compounds according to the invention. Example 1

variant A)

Mixture of 100 g (0.36 mol) of i-chloro-4- (4'-chlorophenoxy) acetophenone, 31 1 g (0.45 mol) of 1,2,4-triazole and 124 g (0.9 mol) ground potassium carbonate was heated to reflux for 20 hours. The reaction mixture was allowed to cool, the inorganic salt was filtered off with suction and the filtrate was evaporated. The residue is stirred with methylene chloride and dilute hydrochloric acid is added. The resulting hydrochloride was separated, washed with methylene chloride and converted to the base by addition of an alkaline reagent followed by extraction. 41.5 g (36.8% of theory) of 4- (4 ' -chlorophenoxy) -N- (1,2,4-triazol-1-yl) -acetophenone are obtained, m.p. 148-150 ° C. Preparation of starting material 'ClO > -O <

CO-CH 2 Cl 2 To 150 g (0.73 mol) of 4-chlorobiphenyl ether and 117 g (0.88 mol) of aluminum chloride in 1000 ml of methylene chloride, 86.6 g (0.77 mol) of chloroacetyl chloride are added dropwise at room temperature. The solution is stirred for 1 hour and then poured into 3 liters of ice-water. The organic phase is separated, washed with water, dried over sodium sulfate and evaporated. The residue is triturated with petroleum ether, the solid product is filtered off with suction and dried. 168.7 g (82.3% of theory) of ω-chloro-4- (4-chlorophenoxy) acetophenone of melting point 59 DEG-61 DEG C. are obtained. Example 2

Qi- O 7 ~ 0- O / -co-ck-ch2- / O

Cl variant b) 31.4 g (0.1 mol) of 4- (4-chlorophenoxy) -ω- (1,2,4-triazol-1-yl) acetophenone (see Example 1), 16.1 g 4- of chlorobenzyl chloride and 5.6 g (0.1 mol) of potassium hydroxide in 200 ml of dimethyl sulfoxide was stirred at 40 ° C for 20 hours. The reaction mixture was added to 700 mM water and extracted with ethyl acetate. The organic phase is washed with water, dried over sodium sulfate and evaporated. The residue is boiled with isopropyl ether for purification. 26.1 g (59.6% of theory) of 1- (4-chloro-phenyl) -3- [4- (4-chlorophenoxy) -phenyl] -2- (1,2,4-triazol-1-yl) ) propan-3-one, m.p. 132 ° C. 235964 Example 3 10 Variant c)

OH

7 g (0.016 mol) of 1- (4-chlorophenyl) -3- 4- (4'-chlorophenoxy) phenyl-2 (1,2,4-triazol-1-yl) propan-3-one (via Example 2) ) and 4.8 g (0.04 mol) of methylmagnesium bromide, dissolved in 50 ml of ether, was stirred at reflux for 1 hour in THF (100 ml). The reaction mixture was allowed to cool and dilute hydrochloric acid was added. The organic phase was separated, washed with water, dried over sodium sulfate and evaporated. The residue is stirred with diisopropyl ether, filtered off with suction and dried. 5.3 g (73% of theory) of 1- (4-chlorophenyl) -3- [4- (4-chlorophenoyl) phenyl] -2- (1,2,4-triazol-1-yl) butane are obtained. 159 DEG C. 3-ol. Example 4

Cl variant c)

OH

O

To 14 g (0.032 mol) of 1- (4-chlorophenyl) -3- [4- (4'-chlorophenoxy) phenyl] -2- (1,2,4-triazol-1-yl) propan-3-one (see example 2) 0.38 g (0.01 mol) of sodium borohydride dissolved in 10 ml of water is added in 400 ml of methanol. The reaction mixture was stirred at 25 ° C for 2 hours and adjusted to pH 6-7 by the addition of dilute hydrochloric acid. The reaction solution was evaporated and the residue was taken up in methylene chloride and water. The organic phase is separated off after drying over sodium sulfate and evaporated. The solid residue after recrystallization from diisopropylether gave 10.5 g (75% of theory) of 1- (4-chlorophenyl) -3- [4- (4'-chlorophenoxy) phenyl] -2- (1,2,4- triazol-1-yl) propan-3-ol, m.p. 12 ° C.

In an analogous manner, the compounds of the following formula (IA) are prepared according to the process of the invention

A-CH-R

Az (Ia)

X '1 1 235964 Example number 5 6 7 8 9 1 o 1! 12 13 14 15 16 17 18 19 20

Η H

4-C1 H

4-C1 H

Η H

4-C1 H

4-C1 H

4-C1 H

4-C1 H

4-C1 H

4-C1 H

4-C1. H

4-C1 H

4-C1 H

4-C1 H

4-C1 H 2-Cl 4-C 1 H -CO- H -CO- H -CO- H -CO- H -CO- H -CO- H -CO-

H -CO H -CO- H -CO- H -CO- H -CO- H -CO- H -CO- H -CO-

Az / "= 1

U zN = l

-N I

N -N 1 N 2 N = 1

Λ I ζνί

-N I

= N N = i

-N | = N

zN = 1-N I -a

N =, - N I

= N

-N

= N

-N = ll -c -a -o -Π

= A r 'Melting point (° C) or "20 C 3 H 7 - n 66 to 68 -C 1 H y-n 64 to 66 -C 2 H 5 91 to 92 -C 2 H 5 62 to 63 -CH 2, 606 1 -C 4 H 9 -n 88

-CH2CH = CHCH3 83 -CH2CH2OCH3 1,594O -CH = CHC3H7 1.5840 -C1H2-n106 235964 12 Example X1 X2 X3 AA z r 'Melting point (° C) or • n20 D 21 2-CH3 6-C1 H -CO- -QH 93 8Ϊ 97 22 2-C1 4-C1 H -co- -QH ioo 23 4 -Br HH -co- -a H 1 50 24 4-C1 HH -co- -a -c2h5 1, 609 2 25 4-C1 HH -co- -a -Ο ^ Ηγ-η 1,604 0 26 4-C1 HH -co- -a -ch3 1,599 0 27 4-C1 HH -co- nH = N -C4Hg-n 1,595 9 28 4-C1 HH -co- -a-C3H7-i 114 to 116 29 4-C1 HH-CO- and H 212 (xCuClg) 30 4-ClHH-CH (OH) / N = | - (I -c2h5) oil (A-form) 31 4-C1 HH -CH (OH) - -C2H5 161 to 162 (B-form) 32 4-C1 HH -CH (OH) - -C (N-150) ( A-form 33 4-C 1 HH -CH (OH) - / N = 1N | -CjH ^ -n 106 to 107 (B-form) 34 4-C1 HH -CH (OH) - Nji -C4H9-n 90 (A-form) 35 4-C1 HH -ch (ohJ--0 -C4H9-n 116 (B-form) 13 235964

Example x 'X2 X3 A Number

Az R

Melting point (° C) or ni 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51

4-Cl Η H

Η Η H

Η Η H

Η Η H

Η Η H

4-Cl Η H

Η Η H

Η Η H

4-Cl Η H

4-C1 Η H

4-Cl Η H

4-Cl Η H

4-Cl Η H

4-Cl Η H

4-Cl Η H

4-C1-H -CH (OH) -CH (OH) -CH (OH) -CH (OH) -CH (OH) -CH (OH) -CH (OH) -CH ( OH) -CH (OH) -CH (OH) -CH (OH) -CH (OH) -CH (OH) -CH (OH) -CH (OH) -CH (OH) -

/ -Η-N I

= N / N = j-N | / "-N |."

N / N =

-N

= IM zN = | / N =

"IN

= M / N =, ΜC 5 H 11 -n -O---Wi-C 4 H 9 -Cl 4 H 9 -C 1 H 4 -G 1 -O-ί 90- 100 1,584 2 96 (A-form), 02 ( B-form 1,4 to 17 158 121 (A-form) 120 (B-form) 84 (A-form) 102 (B-form) 161 to 163 (A-form) 74 to 76 (B-form) 1.10-114.107 (A-forma) 151 (B-form), 60-162

235964 14 Example K1 number X1 X2 X3 A Az -CH (OH) - / N =, 52 4-C1 H H - N I -CHOC = CH = N 2 53 4-C1 H H -CH (OH) - / N = | -N -CH_CH = CH- = N 2 2 / N = | 54 4-C1 H H -CH (OH) - -NJ 'U7H15-n 55 4-C1 H H -CH (OH) - -n | -CH.CH = CHCH. = N 2 56 4-C 1 H -CH (OH) - -N 1 - = N -CH 3 CHC 1 H? , N = i 57 4-Cl HH -CH (OH) - - <Ί = N -CH 2 CH 2 OCH 3 zN = i 58 2-Cl 4 -C 1 H -CH (OH) - —NM -CjHy-n 59 2-Cl 4-Cl and -CH (OH) - ZN = - N -CH, = N 3 ch2- (o), N = i 60 4-C1 HH - 0 (ΟΗ) - ~ - <_ Ί = N -C ^ -n / N = i 61 4-C1 HH -C (OH) CH3 Mi - ^ -Y-η / ΝΊ 62 4-C1 HH -C (OH) CH, -N-ch3 3 CH, -Yo-Cl, N = 63 4-C1 HH -C ( OH) - - (I -CH 3 CH 2 -CH-CH 2 'n-N 1 N 64 4-C 1 HH 1 -C (OH) - / N = 1 65 2 -CH 6 -C 1 H -CH (OH) - - N | H 3 66 2-Cl 4 -ClH-CH (OH) - / N 1 —NH Mi

Melting point (° C) or n £ ° 90 107 74 109 1.560 8 95 to 100 Viscous oil 200 (x HCl) Oil 145 128 142 128 125 to 126 Viscous oil 15 235964 Example Number x 'X2 X3 A Az H1 Melting temperature ( ° C) or n ^ ° 67 4-C 1 HH -CH (OH) - -HH 114 68 4-Br HH -CH (OH) - / N = jN I = NH 106 69 HHH -CH (OH) - -a -Ο ^ Ηγ-η 1, 560 0 70 HHH -CH (OH) - -a-C ^-i, 28 71 4-Cl HH -CH (OH) - -NO = N -C 2 H 5 48 to 52 72 4-C1 HH -CH (OH) - -Ό N -CH3 viscous oil 73 • 4-C1 HH -CH (OH) - -a -C4H9-n 120 to 130 74 4-C1 HH -BH (OH) - -a -C3Vi 50 to 55 75 4-C1 HH -CH (OH) - -G-ΟΟ -G-η 44 to 48

Legend: A-form and B-form represent both possible geometric isomers 235964 16

The following examples illustrate the fungicidal activity of the compounds of the invention.

Example A

Venturia inaequalis test (apple scab) protective effect 1-solvent: 4.7 parts by weight of acetone emulsifier: 0.3 part by weight of alkylaryl polyglycol ether 1 part by weight of the active ingredient is mixed with the indicated amount of solvent and emulsifier and concentrate to prepare a suitable active ingredient is diluted with water to the desired concentration. To determine the protective activity, young apple plants are sprayed with a ready-to-use active agent until dripping. After the spray coating has dried, the plants are inoculated with an aqueous suspension of conidia of the apple scab (Venturia inaequalis) and kept in an incubation chamber at 20 ° C and 100% relative humidity for 1 day.

The plants are then placed in a greenhouse at 20 ° C and about 70% relative humidity.

The experiment is evaluated from i2 days after inoculation. The active ingredients, active compound concentrations and results are shown in the table below.

Table A

Ventiria inaequalis test (protective effect) Active substance (Example No.) Infection in% at active substance concentration 0.01% 0.002 5%

Q-CO-ch 2 (A) (Known) 91

CH

(B) (Known) 54

CF (C) (known) 79 17 235964

Table A Continuation Active Substance (Example No.) Invasion in% at an Effect Concentration of 0.01% 0.002% 5% Cl2-Q2-O-O-O-CO-CH-Ch3 (9) Cl2-Cl2. o — 0-C ° -CH -c4h9 [f ^ n— 0 (10) ci - @> - 0 - / oV- £ h- CH- <j7j A N -! «· 4 (4) / o \ t 0- (0) -CO-CH-F-n O 29 (5} Cl - <GV oVdWcn-c ^ '-' '-' zN-s i-J 10 (7) CI-ZoV-O <O> CO - CH - C ^ 7 - N - N - O (6) @> - 0 -ζθ / -00 - CH - CgHg if N - N '6 (8) O - (o "3 ^ -7 ^ CH3 (40) N- c.- <O> o-XO> -Co-ch-c <CH3-CH3 | 5 — U 16 16 (13) 35 235964 18

ExampleB

Barley / protective Erysiphe graminis test: solvent: 100 parts by weight of dimethylformamide emulsifier: 0.25 parts by weight of alkyleryl polyglycol ether To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent and emulsifier and the concentrate is diluted with water to desired concentration. To determine the protective activity, young barley plants are sprayed with an effective formulation until wetted. After the spray coating has dried on, the plants are sprayed with Erysiphe graminis f. Sp. hordei. To ensure favorable conditions for the development of powdery mildew, plants are placed in the greenhouse at a temperature of about 20 ° C and 80% relative humidity.

7 days after inoculation, the assay is evaluated. The active ingredients, active compound concentrations and results are shown in the table below.

Table B

Erysiphe graminis barley test (protective effect) Active substance (Example No.)

Effect Concentration in Spray (% w / w)

Invading% oprotineoStreated Control Spaces

OH N c 1-6 -CH 2 -CH 2 - (D) (known) 0.025 100.0 µ-O / -O-O 2 -CH 2 -CH-CH 3 H 7 (69) CI-θθ-Ο-ζθ ^ - co-ch -ch3 fj N-11 (9) ·

ci-ZoV-o VoVco-CH-C 4 H 9 '- 7' - 7 L

N 0.025 0.025 (10) 0.025 17.5 15.0 15.0 19 235964 Active Substance (Example No.) Concentration Influence of active substance in% compared to non-sprayed (% w / w) control plants

0.025 0.025 0.025 0.025 0.025 0.025 0.025 0.025 15.0 15.0 15.0 8.8 '7.5 17.5' 7.5 12.5 235964 20 Active substance (Example no.) ) Invading% of the anti-obstructed control areas

0.025 15.0 03),

-CO-CH-CH 1 (ι

N-U 'CH 3 CH, 0.025 15.0

Example C

Pyricularium oryzae Test (Rice) Protective Effect Solvent: 12.5 parts by weight of acetone emulsifier: 0.3 part by weight of alkylaryl polyglycol ether 1 part by weight of the alkylaryl polyglycol ether is mixed. and the concentrate is diluted with water and said amount of emulsifier to the desired concentration. To determine protective activity, young rice plants are sprayed with a ready-to-use active agent until dripping. After the spray coating has dried on, an aqueous suspension of Pyricularia oryzae spores is planted, and then placed in a greenhouse at 100% relative humidity and 25 ° C.

4 days after inoculation, the extent of the disease is evaluated. The active ingredients, active compound concentrations and the results obtained are listed in the table below. 21 235964

Table C

Test for Pyricularia oryzae (rice) / protective effect Active substance (Example No.) Concentration of the active substance («) Invading in% oprotineoControlled CO -ch2-0 CF3 (A) (known) 0.025 100 ° H / = Nci- <O> ch- ch2-NJ (D) (known) 0.025 100 OH α ^ Ο> οΗ @> - 0Η-ch -ch3 / N t 5 * N-11 (36) 0.025 25 C. ^ - oVoVcO-CH-C ^ O (7) 0.025 0 OH ci- / oVo - ^ o -CH -CH -ch (ch3) 2 ó (74) 0.025 13 235964

Example D 22

Pellicularia saaekll (rice) Solvent: 12.5 parts by weight acetone emulsifier: 0.3 part by weight of alkylaryl polyglycol ether To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent and the concentrate is diluted with water and said amount of emulsifier desired concentration. To determine the efficacy, young 3 to 4 leaf rice plants are sprayed with the prepared active agent and condensed to dry in the greenhouse. The plants are then inoculated with Pellicularia sasakii and further stored at 25 ° C and 100 $ relative air humidity.

The extent of the disease is evaluated 5 to 8 days after inoculation. The active ingredients, active compound concentrations and results are shown in the table below.

Table D

Test for Pellicularia sasakii (rice) Active substance (example no.)

Effective Concentration («)

Invading% oprotineoStreated Control Plants (Oy-CO-CH2-CF, 0.025 100 (A) (known)

(D) (known) 0.025 100

OH-C 1 -C 10 -O-O 2 -OH-CH-CH 3 (36) n-a 0.025 0

(7) 0.025

Claims (2)

23 235964 Active Substance (Example No.) Active Substance Concentration (%) Invaded in 56 OprotinStreated Control Plants (74) 0,025 OBJECT OF THE INVENTION What is claimed is: 1. A fungicidal composition comprising at least one phenoxyphenyl azolylmethyl ketone or carbinol of formula I as active ingredient. Az (I) wherein Az is 1,2,4-triazol-1-yl or 4-yl or 1-imidazolyl, X is phenyl, optionally substituted with one to three halogen atoms or / and alkyl with 1 or 2 groups. to 4 carbon atoms, A is keto, -CH (OH) - or -C (OH) R-, wherein R is methyl, allyl, benzyl or chlorobenzyl and R 1 (II) is hydrogen, alkyl C 1 -C 12, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 2 alkoxyalkyl, chlorobenzyl, cyclopentyl or a cyclohexyl group, or an acid addition salt thereof compatible with the plant or a metal salt complex. 2. A process for the preparation of the active compounds of the formula I according to claim 1, characterized in that the halo ketones of the formula II are x-o (II) wherein Hal is a halogen atom, preferably chlorine or bromine, and X is as defined above, reacted with azoles of the formula III H - Az (III) wherein Az is as defined above, 235964 24 in the presence of a diluent and in the presence of an acid-binding agent, optionally adding azolyl ketones of the formula Ia -Az (Ia) in which Az and X are as defined above are treated with an alkylating agent of the general formula IV E1-Z (IV) in which R1 has and Z represents electrons attracting a scavenging group, in the presence of a base and in the presence of an organic diluent, or in an aqueous-organic two-phase system in the presence of a phase transfer catalyst, and optionally the azolyl ketones of the formula Ib as described above -R1 (Ib) wherein Az, X 1 and r 'are as defined above, reduced by reaction with complex hydrides, optionally with aluminum isopropoxide in the presence of a diluent, or reacted with organometallic compounds of formula V Me - E (V) wherein R is as defined above and Me represents an alkali metal or a residue Hal - Mg where Hal 'is chlorine, bromine or iodine, in the presence of a diluent and the compound of formula I thus obtained is optionally treated with an acid or a metal salt. Severografia, n. P „MOST Price 2.40 Kcs