CS259870B2 - A fungicidal agent and method for producing the active ingredient - Google Patents

Abstract

The fungicidal plant protection agent contains as active ingredient α-aryl- -1H-azole-1-ethanol derivatives of the formula I, where R represents hydrogen, halogen, C1-5alkyl, phenyl, optionally substituted by halogen, C1-3alkoxy or nitro group, Ri represents C1-8alkyl, C1-alkenyl, C3...6cycloalkyl, C3-6cycloalkylC1-3alkylene, Az represents 1,2,4-triazol-1-yl or imidazol-1-yl and Z represents hydrogen or C1-5alkyl. The compounds of the formula I are produced by reacting an oxirane of the formula II or its halohydrin with 1,2,4-triazole or imidazole. The fungicidal agent serves to protect plants against pathogenic fungi.

Description

The invention relates to a fungicidal composition for protecting plants against pathogenic fungi and a method for producing its active substance. It contains as active substance derivatives of α-aryl-1H-azole-1-ethanol of the general formula I.

According to the invention, alpha-substituted alpha-ethynyl substituted phenyl)-1H-azole-1-ethanols are prepared, wherein the azole group is 1,2,4-triazol-1-yl or imidazol-1-yl, the ethynyl group is unsubstituted or substituted, and ethers of such ethanol compounds.

The fungicidal composition according to the invention contains as active ingredient α-aryl-1H-azole-1-ethanol derivatives of the general formula I

OZ

AND

R1 (O) where R represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 5 carbon atoms, a phenyl group optionally substituted with halogen, an alkoxy group with 1 to 5 carbon atoms or a nitro group,

R1 is an alkyl group with 3 to 8 carbon atoms, an alkenyl group with 2 to 8 carbon atoms, a cycloalkyl group with 3 to 6 carbon atoms or a cycloalkylalkylene group with 3 to 6 carbon atoms in the cycloalkyl moiety and 1 to 3 carbon atoms in the alkylene moiety,

Az 1,2,4-triazol-1-yl group or imidazol-1-yl group and

Z represents a hydrogen atom or an alkyl group with up to 5 carbon atoms, in free form or in the form of acid addition salts.

The compounds prepared according to the invention contain one or more chiral centers; such compounds are generally obtained in the form of racemic or diastereomeric mixtures. Such and similar mixtures, however, can optionally be separated either completely or partially into the individual isomers or into the desired mixtures of isomers by methods known per se.

If the symbol R represents a halogen atom, it is, for example, a chlorine, bromine or iodine atom.

If the symbol R1 comprises an alkylene moiety with 1 to 3 carbon atoms, this moiety is, for example, a methylene group (CH2) or a methylmethylene group (CH3).

When the symbol R1 represents an alkyl group having 1 to 8 carbon atoms, it is preferably an isopropyl group or a tert-butyl group.

When R1 is a halogen-substituted alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkynyl group having 2 to 8 carbon atoms, the halogen substituent may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

When R1 represents or includes a cycloalkyl moiety having 3 to 6 carbon atoms, such cycloalkyl moiety is preferably a cyclopropyl group or cyclopropyl moiety. The ethynyl substituent is generally in the meta or para position of the phenyl group, preferably in the para position.

If the ethanolic hydroxyl group of the compounds prepared by the process according to the invention is etherified, such ethers are, for example, alkyl ethers having 1 to 5 carbon atoms, such as methyl ethers.

The compounds according to the invention are prepared by reacting 2-(ethynyl substituted phenyl)-2-hydrocarbyloxirane, wherein the ethynyl group may be substituted or a reactive derivative thereof, with 1,2,4-triazole or with amidazole, followed by optional substitution of the ethyl moiety, if unsubstituted, with a halogen atom and/or etherification of the ethanol compound thus obtained.

That is, the active substances of general formula I are prepared by reacting oxirane of general formula II

R-C

where R and R1 are as defined above, or a halohydrin derivative thereof, with a heterocyclic compound selected from the group consisting of 1,2,4-triazole or imidazole. Optionally, in the compound of formula I, where R1 and Az are as defined above and R and Z are hydrogen, the hydrogen atom of the ethynyl group is replaced by a halogen atom. The obtained ethanol compound of formula I, where R, R1 and Az are as defined above and Z is hydrogen, is optionally etherified by reaction with an alkyl halide having 1 to 5 carbon atoms. This gives the compound of formula I in free form or in the form of an acid addition salt.

The entire procedure is clearly described in the following text.

Compounds of general formula 1 are therefore prepared by reacting oxirane of general formula II

239870

R-

(Η) where R, Ri and X have the above meaning, or a functional derivative thereof, with 1,2,4-triazole or imidazole and optionally etherifying the ethanol compound thus obtained, or

b) for the preparation of a compound of general formula Ib

C~C

OlH,// í·' i

X fy (lb) where Ri, X and Az have the above meaning and where Y represents a halogen atom, the hydrogen of the ethynyl group in the compound of general formula lc ?:c is replaced

OH fy/

R<1 (ic) where Ri, X and Az have the above-mentioned meaning, with a group Y (halogen atom) and optionally etherification of the ethanol compound thus obtained is carried out.

The method according to paragraph a) is a reaction known per se for the preparation of azole-1-ethanols by reacting oxirane with azole. The reaction can be carried out under conditions similar to those known per se: it is advantageous to use the azole in the form of a salt (for example, an alkali metal salt, such as the sodium or potassium salt), in the trialkylsilyl form (for example, in the trimethylsilyl form) or to carry out the reaction in the presence of an acid-binding agent.

The reaction with oxirane according to paragraph a) is usually carried out in a solvent inert under the reaction conditions, such as, for example, dimethylformamide. A suitable reaction temperature is between room temperature and the reflux temperature of the reaction mixture; if the azole is in the trialkylsilyl form, the temperature is usually higher than room temperature, for example 70 to 90 °C. If a trialkylsilylazole is reacted, the reaction is usually carried out in the presence of a base, for example in the presence of sodium hydride.

The term "reactive functional derivative" used in connection with 2-aryl-2-R1-oxiranes, as compounds of general formula II, includes any oxirane derivatives from which the ethanol compound of the invention is obtained by reaction with an azole. Various examples of such reactive derivatives are known to those skilled in the art. Suitable examples include the corresponding halohydrins, wherein the halogen atom is, for example, a chlorine atom or a bromine atom.

The conditions under which azoles can react with reactive functional derivatives of the above-defined 2-aryl-2-R1-oxiranes are known per se. The reaction of the azole with the halohydrin derivative of the compound of general formula II can be carried out under conditions known for the reaction with oxirane compounds, but is usually carried out in the presence of an additional equivalent of base.

The replacement of the ethynyl hydrogen atom in the compound of formula Ic by a halogen atom is also carried out in a manner known per se for this type of substitution reaction. It can be carried out either directly or by reacting the compound of formula Ic with a halogen cation donor such as an alkali metal hypochlorite, for example sodium hypochlorite or potassium hypochlorite, N-chlorosuccinimide or N-bromosuccinimide or carbon tetrachloride (in the case of carbon tetrachloride in a strongly alkaline medium) or via a di-Y-addition product with subsequent cleavage of the HY group from the addition product.

The ether derivatives of the ethanol compounds according to the invention can be obtained by esterifications known per se from the corresponding ethanols. Suitable O-alkylating agents are, for example, the corresponding halides, for example iodides, such as methyl iodide.

The compounds prepared by the process according to the invention are isolated from the reaction mixture in which they are formed by known methods. They are obtained in free form or in the form of a salt or in the form of a metal complex, for example as an addition salt with an organic or inorganic acid, for example as hydrochlorides, or they are obtained in the form of an alcoholate, for example sodium ethanolate, or in the form of a complex with a metal, for example copper or zinc, and with anions from the group consisting of chloride, sulfate and nitrate.

Unless the method of preparation of any starting material is specifically described, these compounds are known or can be prepared and purified by methods known per se or by methods analogous to those described or known per se.

The compounds of formula I, prepared by the process of the invention, in free form or in the form of agriculturally acceptable salts or complexes, are useful fungicides for the control of phytopathogenic fungi. Their advantageous fungicidal activity has been determined in in vivo tests at a concentration of about 0.0008 to 0.05% against Uromyces appendiculatus. rust affecting legumes, against other rust-causing fungi (such as Hemikne, Puccinia) on coffee, wheat, geraniums, against powdery mildew Erysiphe cichoracearum affecting cucumbers and against other fungi known as powdery mildew (grass powdery mildew Erysiphe graminis affecting wheat, Erysiphe graminis affecting barley, apple powdery mildew Podosphaera leucotricha, grape powdery mildew Uncinula necator] on wheat, barley, apple and grapevines. Further interesting efficacy is observed, for example, in vitro against corn blight Ustilago maydis and in vivo against potato root rot Rhizoctonia solani. Many of the compounds of general formula 1 are tolerated by plants in an excellent manner, and these compounds have good systemic action. The compounds of general formula 1, prepared by the method according to the invention, are therefore used for treating plants, seeds and soil to combat phytopathogenic fungi, for example basidiomycetes Basidiomycetes rust species Uredinales, such as Puccinia spp, Hemileia spp, Uromyces spp, Ascomycetes fungi of the powdery mildew species Erysiphales, such as Erysiphe spp. powdery mildew Podosphaera spp. and powdery mildew Uncinula spp. as well as flax wilt fungi Phoma, potato flaking Rhizoctonia, fungi Hehninthosporium, Pyricularia, Pellicularia (= Corticium], Thielaviapsis and Stersum spp.

The amount in which the compound of general formula I is used depends on various factors, such as the type of compound used, the subject treated (plant, soil, seeds), the type of treatment (dipping, sprinkling, spraying, dusting, pickling), the purpose of the treatment (prophylactic or therapeutic treatment), the type of fungus to be destroyed, the application time. In general, satisfactory results are achieved if the compound of the general formula I is used in an amount of 0.005 to 2.0, preferably about 0.01 to 1 kg/ha, in the case of plant or soil treatment: for example, 0.04 to 0.125 kg of active ingredient per hectare is used in the case of cultivated plants such as cereals, or in a concentration of 1 to 5 g of active ingredient per hectare in the case of fruit, grapes and vegetables (at application volumes of 300 to 1,000 l/ha depending on the size or volume of the leaves of the plants, which corresponds to a dose of about 10 to 50 g/ha. The treatment can optionally be repeated, for example at intervals of 8 to 30 days.

When the compounds of formula I are used for seed treatment, generally satisfactory results are obtained when the compounds are used in an amount of approximately 0.05 to 0.5, preferably 0.1 to 0.3 g/kg of seed.

The term soil here refers to any living environment for plants, whether natural or artificial.

The compounds of general formula I, prepared by the method according to the invention, can be used for the treatment of a large number of crop plants, such as soybeans, coffee plants, ornamental flowers (for example, pelargonium and rose, vegetables (for example, legumes, cucumbers, celery, tomatoes, berry plants), sugar beet, sugar cane, cotton, flax, corn, grapevines, pome fruits and stone fruits (for example, apples, plums, pears) and cereals (for example, wheat, oats, barley, rice).

In view of the good tolerability of numerous compounds of the general formula I prepared by the process according to the invention, these compounds are particularly suitable for fungicidal treatment in cases where such good tolerability is desired or necessary, for example in the case of fruits such as apples. Various compounds of the general formula I, such as the compounds according to Example 2.33, also have a favorable curative effect.

Particularly favorable results are achieved, for example, with compounds of general formula I which have at least one of the following characteristics:

X represents a hydrogen atom, the C~OR group is in the para position,

R represents a hydrogen atom, a chlorine or bromine atom, a methyl group, a butyl group (for example, an n-butyl group or a tert-butyl group), or a phenyl group, unsubstituted or substituted, in particular a phenyl group substituted or unsubstituted by a bromine atom, especially an unsubstituted phenyl group,

R1 is an iso-propyl group, a tert-butyl group, a cycloalkyl group with 3 to 6 carbon atoms, especially a cyclopropyl group, or a cycloalkylalkylene group with 3 to 6 carbon atoms in the cycloalkyl moiety and about 3 carbon atoms in the alkylene moiety, especially a cyclopropylalkylene group with 1 to 3 carbon atoms in the alkylene moiety, especially a cyclopropyl--CH(CH3)),

And a 1,2,4-triazol-1-yl group.

The invention also relates to fungicidal compositions which contain as fungicidally active substance a compound of the general formula I, prepared by the process according to the invention, in free form or in the form of a fungicidally suitable salt or in the form of a complex together with a fungicidally suitable diluent (hereinafter referred to simply as diluent). They are obtained by methods known per se by mixing the active substance of the general formula I with the diluent and optionally with additional components such as surfactants.

The term "thinner" used here always refers to liquid or solid fungicidal substances that can be added to

5 9 ?. 7 0 active ingredient of the general formula I, in order to convert this active ingredient into a more easily and better usable form, or to dilute the active ingredient of the general formula I to a usable or desired level of effectiveness. Examples of such diluents include talc, kaolin, diatomaceous earth, xylene or water.

In particular, the compositions are used in the form of sprays, as water-dispersible concentrates or wettable powders, which may contain surface-active substances such as wetting agents and dispersants, for example condensation products of formaldehyde and phthalatesulphonate, alkylarylsulphonate, ligninsulphonate, fatty alkyl sulfate, ethoxylated alkylphenol and ethoxylated fatty alcohol.

In general, the compositions contain from 0.01 to 90% by weight of active ingredient, from 0 to 20% of a fungicidally suitable surfactant and from 10 to 99.99% of at least one diluent. Concentrated forms of fungicidal compositions, for example emulsion concentrates, generally contain from 2 to 90%, preferably from 5 to 70% by weight of active ingredient. Application forms of fungicidal compositions according to the invention generally contain from 0.0005 to 10% by weight of active ingredient of the general formula 1. Typical suspensions for application by spraying contain from 0.0005 to 0.05%, preferably from 0.001 to 0.02% by weight, for example from 0.001, 0.002 or 0.005% by weight of active ingredient of the general formula I.

In addition to the usual diluents and surfactants, the fungicidal compositions according to the invention may contain further special additives with special tasks, such as, for example, stabilizers, deactivators (for solid compositions or surface-active carriers), plant adhesion promoters, corrosion inhibitors, antifoaming agents and dyes. In addition, such fungicidal compositions according to the invention may contain further fungicidally active substances with similar or additional fungicidal action, such as, for example, sulfur, chlorothalonil, dithiocarbamates such as mancozeb, maneb, zineb, propleneb, trichloromethanesulfenylphthalaminides and their analogues such as, for example, captan, captafol and foipet, benzimidazoles such as benomyl or other beneficial agents such as, for example, insecticides. The fungicidal compositions according to the invention may have the following forms: aj Wettable powders

10 parts of the compound of general formula I are mixed with 4 parts of synthetic fine silica, 3 parts of sodium lauryl sulfate, 7 parts of sodium ligninsulfonate and 68 parts of finely divided kaolin and 10 parts of diatomaceous earth and ground to a mean particle diameter of approximately 5 microns. The resulting wettable powder is diluted with water before use as a spray liquid, which can be applied to the leaves and roots.

bj Granules

0.5 parts by weight of a binder (nonionic surfactant J) is sprayed onto 94.5 parts by weight of quartz sand in a drum mixer and mixed thoroughly. Then 5 parts by weight of a compound of the general formula I are added and thorough mixing is continued until a granular composition with a particle diameter of 0.3 to 0.7 mm is obtained. The granules can be applied by introducing them into the soil around the plant to be treated.

c) Emulsion concentrate

25 parts of the active ingredient of the general formula 1 are mixed with 10 parts by weight of emulsifier and 65 parts by weight of xylene. The concentrate is diluted with water to the desired concentration.

d) Seed dressing

45 parts of the compound of general formula I are mixed with 1.5 parts of diamylphenoldecaglycol etherethylene oxide addition product, 2 parts by weight of spindle oil, 51 parts by weight of fine talc and 0.5 part by weight of the dye rhodanine B. The mixture is ground in a cotrapex mill at a speed of 10,000 rpm until a mean particle diameter of less than 20 microns is achieved. The resulting dry powder has good adhesion and can be applied to seeds, for example by mixing for 2 to 5 minutes in a slowly rotating container.

The invention is further illustrated by the following examples, which are not intended to limit it in any way. Temperatures are given in °C. R _f values obtained on silica gel (thin layer chromatography j.

Example 1

Method for preparing 2-(4-ethynylphenyl)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol

At room temperature, 17.2 g of dodecyldimethylsulfonylpyrrolidinyl sulfate are added to a solution of 6.5 g of 1-(4-ethynylphenyl)-2,2-dimethylpropan-1-one in 80 ml of absolute toluene. The mixture is stirred for 15 minutes, then 3.8 g of powdered potassium hydroxide are added and the mixture is stirred for 22 hours at 35°C. The reaction mixture is poured onto ice, the pH is adjusted to 7 with 6 N sulfuric acid and extracted with diethyl ether. The organic phase is washed with water, dried (sodium sulfate) and evaporated in vacuo. The residue, containing 2-(4-ethynylphenyl)-2-(1,1-dimethylethyl)oxirane, is used for the next reaction without purification.

The residue is added dropwise over 10 minutes at 90 ^° C to a suspension of 4 g of 1,2,4-triazole and 14.5 g of potassium carbonate in 80 ml of absolute dimethylformamide and stirred for 4 hours at 90°C. The reaction mixture is then cooled, poured onto ice and extracted with diethyl ether. The ether solution is washed with water, dried and concentrated in vacuo. The residue is stirred with hexane, the insoluble solid product is filtered off and recrystallized from hexane/toluene. The compound prepared is obtained in the form of colorless crystals with a melting point of 101°C (R _f = 0.35 ethyl acetate/hexane in a ratio of 6:4).

Example 2

Analogously to Example 1, the following compounds, listed in Table I, of general formula I, where X represents a hydrogen atom and the group R—C=C— is in the para position, unless otherwise stated, are prepared, starting from the corresponding ketones of general formula IV and the compounds of general formula I are prepared via oxiranes of general formula II.

The notes in the table have the following meaning:

⁽¹⁾ means 1,2,4-triazol-1-yl ⁽²⁾ means imidazol-1-yl ⁽³ > means ethyl acetate/hexane system in the ratio 8:4 ⁽⁴⁾ means ethyl acetate/ethanol system in the ratio 40:1 ⁽⁵⁾ means C3H5 = cyclopropyl ^(sl means diastereomeric mixture separated by thin layer chromatography: diastereomer A has diastereomer A: _Rf = 0.3 (symer A has diastereomer B: Rf = 0.4 (ethyl acetate/hexane system in the ratio 6:4).

Diastereomer B can be recrystallized and has a melting point of 91-92°C.

TABLE I

Example R Ri From R _f , tt °C 2.1 H 1-C3H7 Tr' ⁴ ' 121 2.2 CHs 1-C3H7 Tr 98 to 99 2.3 CH3 1-C3H7 I ⁽²⁾ 180 2.4 G&H5 1-C3H7 Tr 71 2.5 C6H5 1-C3H7 Im 188 2.6 CeHs t-CáHg Tr R _f = 0.35' ³ ' 2.7 C6H5 t-CáHg Im _Rf = 0.35 ⁽⁴⁾ 2.8 CHs t-CáHg Tr 99 2.9 CH3 t-CáHg Im 2.10 n-C<H9 t-CáHg Tr 77 to 78 2.11 n-CáHg t-CáHg Im 2.12 n-CáH9 1-C3H7 Tr 65 2.13 n-C4H9 1-C3H7 Im 2.14 4-C1—CeHa t-CáHg Tr 125 to 127 2.15 4-C1—CeHa t-CáHg Im 158 2.16 4-F-C6H4 1-C3H7 Tr 150 2.17 4-F—CeHa 1-C3H7 Im 2.18 4-CH ₃ O—CeHa 1-C3H7 Tr 132 to 133 2.19 4-CH3O—CeHα 1-C3H7 Im 175 to 176 2.20 4-CH3O—CeHα t-CáHg Tr 140 2.21 4-CH3O—CeHα t-CáHg Im 142 to 143 2.22 4-C1—CeHa 1-C3H7 Tr 129 2.23 CeHs CH2—CH(CHs)2 Tr 119 2.24 C6H5 CH(CH3)_CH(CH3)2 Tr 97 2.25 CeHs C(CH3)2—CH(CH3)2 Tr 2.26 CH3 CH—CH(CH3)2 Tr 2.27 CH3 CH(CH3)—CH(CH3]?, Tr 117 2.28 CH3 C(CH3]2—CH(CH3)2 Tr 2.29 t-CáHg 1-C3H7 Tr 198 2.30 t-CáHg t-CáHg Tr 268 to 269 2.31 n-CáH9 CH2—CH(CH3)2 Tr 66 2.32 4-NO2—CeHa t-CáHg Tr 227 2.33 CeHs CH(CH3)— C3H5 ⁽⁵⁾ Tr (6) 2.34 CeHs Í-C3H7 Tr 83 to 84 (R—C=C in the m position] 2.35 CeHs CHfCHsj—C3H5 Im 139 (diastereomeric mixture] 2.36 4-F—CeHa t-CáHg Tr 122 2.37 CeHs cyclopropyl Tr 126 2.38 H cyclopropyl Tr 88 2.39 n-CáH9 cyclopropyl Tr R ₍ = 0.35 (ethyl acetate/hexane 6 : 4) 2.40 CeHs C(CH3)2CH2CH=CH2 Tr R _f = 0.45 (toluene/ethyl acetate

: 4), mp 58 to 60

Example 3

Method for preparing 2-(4-bromoethynylphenyl)-3,3-dimethyl-1-(III-1,2,4-triazol-1-yl)butan-2-ol

2 g of bromine are added to 10 ml of 2.5 N aqueous sodium hydroxide solution and then a solution of 2.7 g of 2-(4-ethynylphenyl)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol in 20 ml of dioxane is added dropwise with stirring over 15 minutes. The reaction mixture is kept at room temperature for three hours, then diluted with 100 ml of water and extracted with diethyl ether. The ether solution is washed with water, dried and the solvent is evaporated. The residue is recrystallized from the hexane-toluene system, thereby obtaining colorless crystals with a melting point of 138 ^C C (R _f = 0.4, ethyl acetate/hexane system in the ratio 6:4). Example 4

Similarly to example 2, the following compounds of general formula I are obtained, where X represents a hydrogen atom and the group R—C=C— is in parapologue from the corresponding compounds of general formula Ic.

Example R

4.1** Cl 4.2 Cl 4.3 J 4.4 Br

Ri From R _f , tt °C t-CíHg Tr 45 to 46 Í-C3H7 Tr Í-C3H7 Tr 122 Í-C3H7 Tr 197

Tr means 1,2,4-triazol-1-yl ** means contaminated with 30% perchlorate

Example 5

Process for preparing 2-(4-chloroethynylphenyl)-3-methyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol

To a stirred mixture of 12 g of 2-(4-ethyl)-3-methyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol in 50 ml of hexamethylphosphoric acid in the form of triamod is added 24.8 g of N-chlorosuccinimide in portions over 15 minutes. The reaction is slightly exothermic (the reaction temperature increases from 20 to 30 °C). The reaction mixture is cooled slightly, maintaining the temperature of the reaction mixture at 25 to 30 °C, and stirred for one hour.

The bright yellow reaction solution is poured into 1000 ml of water and extracted with diethyl ether. The diethyl ether phase is washed once with water, dried and the solvent is evaporated. The oily residue is chromatographed on a silica gel column using the toluene/ethyl acetate system in a ratio of 3:7, thereby obtaining the prepared compound in impure form (R _f = 0.35).

Example 6

Method for preparing 2-(4-iodoethynylphenyl)-3-methyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol

To a solution of 5.1 g of (2-(4-ethynylphenyl)-3-methyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol in 100 ml of absolute methanol, 2.6 g of iodine and 10 ml of 30% sodium hydroxide solution are simultaneously added with stirring at a temperature of 20 to 25 °C. The reaction mixture is kept at room temperature for 24 hours with stirring, then poured into 500 ml of water and extracted with dichloromethane. The organic phase is washed, dried and evaporated. The residue is stirred in the hexane fraction and left undisturbed for 16 hours. The precipitate is filtered off with suction and dried, thereby obtaining the compound being prepared with a melting point of 122 C in the form of colorless crystals.

Example 7

Method for preparing 2-[4-(phenyl)thynyl]phenyl]-3-methyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol methyl ether

Sodium hydride (1.6 g, 80%) was stirred in 60 ml of absolute dimethylformamide and then added dropwise over 60 minutes to a solution of compound 2.4 (16.6 g) in 60 ml of dimethylformamide at room temperature; the mixture was stirred for 30 minutes. Methyl iodide (7.4 g) was added to the mixture. The mixture was stirred for 15 hours at room temperature and then diluted with water; the solid precipitate was filtered off with suction, washed with water and dried to give 2-[4-(phenylethynyl)phenyl]-3-methyl-1-(1H-1,2,4-triazol-1-yl}butan-2-ol methyl ether, melting point 181 °C (petroleum ether; colorless crystals), R ₍ = 0.6 (95:5 trichloromethane/methanol system).

Example 8

Fungicidal action

8.1 Wheat powdery mildew control

Wheat infected with powdery mildew Erysiphe graminis is treated with a spray liquid containing the compound according to Example 2.4 as active ingredient in a concentration of 300 mg/l of spray liquid. The spray is applied at a rate of 500 l/ha. The treatment achieves a significant reduction in powdery mildew infestation.

8.2 Wheat rust control

Wheat infected with yellow rust Puccinia striformis is treated with a spray liquid containing the compound according to Example 2.4 in a concentration of active substance of 100 mg/l spray liquid. The spray is applied at a rate of 1,000 l/ha. The treatment achieves a significant reduction in rust infestation.

Claims (4)

Subject Fungicidal plant protection product, characterized in that it contains, as active substance, α-aryl-1H-azole-1-ethanol derivatives of the general formula I R-C = C oz C-CH,> ~ Az i ⁴ r ₄ (where R O represents hydrogen, halogen, alkyl of 1-5 carbon atoms, phenyl popříp. Substituted by halogen, alkoxy having 1 to 5 carbon atoms or nitro; R 1 is C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkylalkylene in the cycloalkyl moiety and C 1 -C 3 alkylene, Az 1,2,4-triazol-1-yl or imidazol-1-yl a Z is hydrogen or alkyl of 1 to 5 carbon atoms, in free form or in the form of acid addition salts. 2. A fungicidal composition according to claim 1, wherein the active ingredient is a compound of formula (I) wherein R, R1 and Az are as defined in (1), Z is hydrogen in free form or in acid addition salts. 3. A process for the preparation of an active ingredient according to claim 1, which comprises reacting an oxirane of formula II of the invention wherein R and R1 are as defined in claim 1 or a halohydrin derivative thereof, with a heterocyclic compound selected from the group consisting of 1,2, 4-triazole or imidazole, optionally in a compound of formula I wherein R 1 and Az are as defined in 1 and R and Z are hydrogen, replace the hydrogen atom of the ethynyl group with a halogen atom, and optionally obtain the ethanol compound of formula I, wherein R, Rt and Az are as defined in 1 and Z is hydrogen, etherified by reaction with a C 1 -C 5 alkyl halide to give a compound of formula I in free form or in acid addition salt form. 4. A process for the preparation of an active compound according to claim 3, which comprises reacting an oxirane of the formula II wherein R and Rt are as defined in item 1 or a halohydrin derivative thereof with a heterocyclic compound selected from the group consisting of 1,2,4 -trtazole or imidazole, optionally in a compound of formula I wherein R 1 and Az are as defined in 1 and R and Z are hydrogen, replace the hydrogen atom of the ethynyl group with a halogen atom to form a compound of formula I wherein R, R 1 and Az is as defined in item 1, Z is hydrogen, in free form or in acid addition salt form. Severography, n. Race 7, Most Price 2,40 Kčs