HU185917B - Fungicide composition and process for preparing the active substance - Google Patents

Abstract

Compounds of the formula <IMAGE> wherein R<o> is C1 to 12 alkyl, C3 to 8 cycloalkyl or C4 to 11 cycloalkylalkyl in which the cycloalkyl portion is of 3 to 8 carbon atoms and the alkyl portion of 1 to 3 carbon atoms, said cycloalkyl and cycloalkylalkyl groups being optionally substituted by one or C1 to 3 two alkyl groups, R is hydrogen, F, Cl or Br, C1 to 4 alkyl, mono-, di or tri-halo-C1 to 4 alkyl in which the halo is F, Cl, or Br, C1 to 4 alkoxy, C1 to 4 alkylthio or nitro, and R' is hydrogen, F, Cl, Br or I, C1 to 4 alkyl, mono-, di or tri-halo-C1 to 4 alkyl in which the halo is F, Cl or Br, C1 to 4 alkoxy, mono, di- or tri-halo-C1 to 4 alkoxy in which the halo is F, Cl or Br, C1 to 4 alkylthio, nitro, -CN, -COOR'', <IMAGE> R'' is hydrogen, C1 to 4 alkyl, R''' is hydrogen, F or Cl or C1-2 alkyl, Z is oxygen or sulfur, or R and R' together represent alkylenedioxy of 1 or 2 carbon atoms substituted onto adjacent carbon atoms of the phenyl Ring A, and Y<o> and Y are independently hydrogen, F, Cl or Sr, C1 to 4 alkyl or C1 to 4 alkoxy, their preparation and their use as agricultural fungicides.

Description

FIELD OF THE INVENTION The present invention relates to fungicides containing alpha-aryl-1H-1,2,4-triazol-1-yl-ethanols, in particular a-alkyl-a-phenyl-1H-1,2,4-triazol-1,1-yl-ethanol, and relates to a process for the preparation of active ingredients.

The fungicides according to the invention contain 0.0005-90% by weight of the compounds of the formula I in which R 0 is propyl, tert-butyl, branched pentyl, C 3 -C 8 cycloalkyl, in the cycloalkyl part 3 the alkyl moiety represents a C 1-3 cycloalkylalkyl group having a total of 4 to 11 carbon atoms and said cycloalkyl and cycloalkylalkyl optionally substituted with a C 1-3 alkyl group;

R is hydrogen, 9 to 35 halogen, C1-C4 alkyl, trifluoromethyl, C1-C4 alkoxy, or nitro;

R 'is hydrogen, 9 to 53 halogen atoms, C 1-4 alkyl, trifluoromethyl, C 1-4 alkoxy, trifluoromethoxy, nitro, cyano, phenyl or phenoxy;

R 'is hydrogen or methyl, with the proviso that at least one of R, R' and R 'is other than hydrogen.

Halogen atoms from 9 to 53 are fluorine, chlorine, bromine and iodine, and halogen from 9 to 35 are fluorine, chlorine and bromine.

The compounds of formula (I) may be prepared by the following process.

A compound of formula II, wherein R 0, R, R 'and R' are as defined above, is reacted with a compound of formula III, wherein X is an alkali metal atom in the presence of an inert organic solvent.

The process may conveniently be carried out at 0 to 180 ° C, preferably 40 to 120 ° C, in the presence of a conventional inert organic solvent such as an amide of an organic carboxylic acid such as dimethylformamide. The compound of formula (III) is prepared in a conventional manner, but preferably in a reaction with a strong base such as an alkali metal hydride, such as sodium hydride, in an inert organic solvent, preferably as employed in the process of the invention.

The compounds of the present invention can be isolated from the reaction mixture for their preparation by known methods. The compounds of formula I can be prepared and used in the form of their acid addition salts.

The compounds of formula (I) are ethanol derivatives, therefore, in free form and in alternating forms such as the ethanolate salt, e.g., sodium ethanolate, and in the form of a metal complex, e.g., lb, IIa, IIb, VIb, VIIIb and VIII of the Periodic Table. and anion such as chloride, sulfate, nitrate, carbonate, acetate, citrate, dimethyldithiocarbamate, and the like. in the form of a complex.

Preferably, any salt of the compounds of formula I is an agriculturally acceptable salt.

The acid addition salts, ethanolate salts and metal complexes can be prepared from the corresponding free compound in a known manner and vice versa.

The starting compounds of formula (V) may be prepared by reacting a compound of formula (V), wherein R 0, R, R 'and R' have the meanings given above, with a strong base and trimethylsulfonium iodide; Reaction with a reagent of formula VI in the presence of an inert organic solvent. This process is a known reaction for the preparation of epoxy derivatives from ketones.

Most of the starting compounds of formula (V) are known and those which are not known can be prepared from known starting materials by analogous methods to the preparation of known compounds. The vast majority of the compounds of formula II are also known.

The compounds of formula (I) may be used as active ingredients in agents effective against plant pathogenic fungi, in particular powdery mildew and rust fungi, as further demonstrated by conventional in vivo and in vitro assays. The fungicides containing the compounds of the formula I can be used in the treatment of plants, seeds and soil. The effective amount of the active ingredient containing the active ingredient of formula (I) will depend on known factors, such as the nature of the active ingredient, the preventive or curative treatment, the mode of application, i.e. spraying the leaves, treating the soil or seed dressing. may vary depending on the species of fungus in question and the time of treatment. Generally, a satisfactory result is obtained when the plants, either the plants themselves or the soil, are treated with 0.005 to 2, preferably 0.01 to 1 kg / ha of active compound. If necessary, the treatment may be repeated, for example at intervals of 8-30 days. If the seeds are dressed, a satisfactory result is obtained in an amount of 0.05-0.5, preferably 0.1-0.3 g / kg of active ingredient.

The term soil designation used herein includes any conventional medium of natural or artificial origin.

The fungicides according to the invention contain 0.0005-90%, preferably 0.1-60% by weight of the active ingredient. The agents may be diluted concentrates prior to use or may be directly diluted. For example, typical representatives <

Examples include wettable powders, emulsion concentrates, dusts, sprays, granules, and sustained release formulations containing conventional carriers and other diluents and / or additives which are acceptable in agriculture. Generally, the agents for direct use contain from 0.0005 to 10% by weight of the active compound of formula (I).

Typical spray suspensions may contain, for example, 0.0005-0.05% by weight, preferably 0.001-0.02% by weight of the active ingredient. The concentrated agents generally contain from 2 to 90% by weight, preferably from 5 to 70% by weight, of the active ingredient of the formula (I). The active ingredient content of emulsion concentrates is generally

185,917

It may be from 10 to 70%, preferably from 20 to 60%. Solid granular agents are preferred.

The spraying is particularly suitable compositions comprise a surfactant additive, such as liquid polyglycol ethers, fatty alcohol sulphate or lignin sulfonate ^5.

In addition to conventional carriers and surfactant additives, the agents of the present invention may also contain other special purpose additives, such as stabilizers, deactivators (in solid compositions containing active surfactant ¹⁰ ), anti-caking agents, corrosion inhibitors, antifoams and colorants.

Agents of the present invention further pesticides, such as fungicides, insecticides and bacteria ¹⁵ umölőszerek active ingredients may also be added.

The following describes the composition and preparation of some typical fungicides.

a) Wettable powder sr. An active ingredient of the formula I, for example, α-tert-butyl-α- (p-methylphenyl) -1 -1-1,2,4-triazole-1 to ²⁵ ethanol, is added in 2 volumes. with lauryl sulfate, 3 sr. sodium lignin sulfonate and 45 sr. powdered kaolin until the average particle size is less than 5 μ. The resulting powder can be prepared by dilution with water permedé used for spraying the leaves and roots ³⁰ of the treatment.

(b) Granules

In the mixer 94.5 sr. for quartz sand 0.5 sr. isoctylphenyl octaglycol ether is sprayed and mixed thoroughly. To the mixture, 5 sr. The active ingredient of formula (I), such as powdered α-tert-butyl-α (p-methylphenyl) -1H-1,2,4-triazol-1-yl-ethanol, is added 40 and stirred until 0.3- A granule size of 0.7 mm is obtained. The granulate can be applied to the soil surrounding the plants to be treated.

c) Emulsion concentrate sr. The active ingredient of the formula (1), for example, α-tert-butyl-α- (p-methylphenyl) -1Η-1,2,4-triazol-1-ethanol, is mixed with 30 µl. isooctylphenol octaglycol 50, and 45 sr. 210-280 ° C boiling petroleum fraction (D ₂₀ = 0.92). The resulting concentrate may be diluted with water to the desired concentration before use.

d) Dressing agent sr. An active ingredient of the formula (1), such as α-tert-butyl-α- (p-methylphenyl) -1H-1,2,4-triazol-1-yl-60 ethanol, is mixed with 1.5 sr. diamylphenol decaglycol ether and ethylene oxide addition product, 2 sr. with spindle oil, 51 sr. powdered talc and 0.5 sr. dye (rhodamine B). Grind the mixture in a mill at 10,000 rpm until the average particle size is less than 20 μ. The resulting dry powder dressing adheres well and can be used for seed dressing, for example, in a slow rotating roller for 2-5 minutes.

e) Wettable powder sr. The active ingredient of Example 2A was treated with 9 sr. with silica and 1 sr. dispersing agent (sodium lignin sulfonate) until a powder having an average particle size of less than 5 microns is obtained. The resulting wettable powder can be diluted with water before use.

The fungicides containing the active compounds of the formula I are of particular importance, for example, in controlling the following fungi:

(A) Basidiomycetes,.

A) 1) Uredinales, such as the genus Uromyces on plants, such as Uromyces appendiculatus beans and Uromyces dianthi on ornamental plants; plants of the genus Hemileia, such as coffee, Hemileia vastatrix; cereals such as wheat, barley and rye such as Puccinia graminis, Puccinia recondita and Puccinia striiformis; ornamental plants such as Puccinia pelargoniizonalis and Pucc. antirrhini; plants of the genus Phakopsora, such as Phakopsora pachyrhizi soya; plants of the genus Melampsora, such as flax Melampsora lini; plums of the genus Tranzschelia, such as Tranzschelia pruni;

(2) those of the order Ustilaginales, such as those of the genus Ustilago, such as barley, wheat, maize and sugar cane such as U. maydis maize and U. nuda barley, and

3) the genus Stereum on small fruits and stone fruits such as Stereum purpureum apples and plums.

B) Ascomycetes,

B 1) Erysiphales, such as Erysiphe graminis on plants such as cucumbers, barley, wheat and sugar beet, such as Erysiphe graminis f. sp. tritici on wheat and Erysiphe cichoraceareum on cucumber; Spohaerotheca on cucumbers and roses such as Spohaerotheca pannosa; apples, pears and plums of the genus Podosphaera, such as apples of Podosphaera leucotricha; plants of the genus Uncinula, such as grapes such as Uncinula necator grapes; members of the genus Oidium on many plants; Leveillula on plants such as cotton and other Malvaceae such as Leveillula taurica.

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C) Oomycetes,

C 1) Phytophthora spp. genomes such as Ph. cactorum, Ph. parasitica and Ph. cinamomi on susceptible plants;

C 2) plants of the genus Aphanomyces, such as peas and sugar beets such as Aphanomyces euteiches, and

D) Deuteromycetes,

D 1) plants of the genus Helminthosporium such as barley and maize, for example Helm. sativum;

D 2) plants of the genus Septoria such as wheat, tomatoes and celery, e.g. tritici on wheat, tomato and celery;

D 3) plants of the genus Rhizoctonia such as cotton and potatoes such as Rhis. solani on cotton;

D 4) Fusarium spp. , such as F. oxysporum f. sp. lycopersici tomato, F. oxysporum f. sp. vasinfectum cotton, F oxysporum f. sp. cubense on bananas, F. solani on vegetables, F. culmorum on cereals and F. graminearum on cereals;

D 5) Thielaviopsis on plants such as cotton, tobacco, etc., such as Thielaviopsis basicola;

D 6) plants of the genus Phoma, such as sugar beet, rape, etc., such as Phoma betae sugar beet;

D 7) Piricularia spp. gender, for example

P. oryzae on rice and

D 8) Colletotrichum pp. , such as C. lindemuthianum beans.

The following conventional methods illustrate assays for determining the antifungal activity of agents containing the active compounds of formula (I).

A) Method

In vivo determination of the activity against bean rust (Uromyces appendiculatus) Bean plant (Phaseolus vulgaris) was grown for 9 days in a plastic container of cm diameter in a mixture of peat and sand. The plants were then sprayed with a spray containing 0.0008-0.05% (e.g. 0.0008%, 0.0003%, 0012% and 0.05%) of active ingredient. During the treatment, the leaves of the plants were sprayed dropwise or the soil was soaked (28 ml of spray per dish). After spray drying, the plants were inoculated with a spore suspension spray (500,000-700,000 spores / ml) and incubated for 7 days at 100% relative humidity and 21 ° C. The efficacy of the treatment with the agent was determined by comparing the number of leaf spots per leaf on the treated plants with that of the leaves of untreated, similarly infected plants. The active compounds of formula (I) were used in the form of a wettable powder containing 26% by weight of active ingredient, s% of kaolin, 2% by weight of diatomaceous earth, 3% by weight of sodium lauryl sulfate and 5% by weight of sodium lignin sulfate. Before use, it was diluted with water to the desired concentration. Significant fungicidal activity was observed.

Analogous studies were performed with similar results on the following crop and fungus assemblies:

coffee: leaf rust (Hemileia vastatrix), wheat: black rust (Puccinia graminis), wheat: brown leaf rust (Puccinia recondita), wheat: marigold (Puccinia striiformis), flax: linden (Melamspora lini), nutmeg (pelargonium), nutmeg : succulent rust (Puccinia antirrhini).

B) Method

In vivo determination of the activity against cucumber powdery mildew (Erisiphe cichoracearum).

Cucumbers (Cucumos sativus) were grown for 7 days in plastic pots filled with a mixture of peat and sand for 6 days. The plants were then sprayed with a spray containing 0.0008-0.05% (e.g. 0.0008%, 0.003%, 0.012%, and 0.05%) of active ingredient. During spraying, the leaves were sprayed dropwise or the soil was soaked (28 ml of spray juice per dish). After spray drying, the plants were inoculated with freshly collected conidia and kept for 7 days in an incubation chamber at 60-80% RH and 25-30 ° C. The efficacy of the agent was determined by comparing the degree of fungal infection with that of untreated, similarly infected plants. The compounds of formula (I), when used in the form of a sprayable wettable powder as described in method (A), have a significant antifungal activity.

Analogous tests were carried out on method B) with similar results on the following plants and fungi:

wheat: powdery mildew (Erys. gram. f. sp. tritici), barley: powdery mildew (Ery. gram. f. sp. hordei), apple: powdery mildew (Podos. leucotricha), grape: powdery mildew (Uncinula necator).

The test according to Method B was repeated with the active ingredient according to Example 1 on cucumber powdery mildew (leaves and soil were treated), but the concentration of the active ingredient was only 0.0002 s% and 0.00005 s%, however, it was 100% fungicidal. an effect which further underlines the outstanding efficacy of the agent of the invention. In the same study, spray rates of 0.000012% and 0.000003% were found to have a 70% and 50% fungicidal activity, respectively, and a 90% and 70% fungicidal activity, respectively, when soil was applied. A spray of 0.0002% and 0.00005% by weight of barley powdery mildew according to Method B was found to have a 70% and 55% fungicidal activity and 80% and 70% fungicidal activity on the soil. %. In the method B test against wheat powdery mildew 0.0002 s% and 0.00005 s% -41

Using a spray of 185,917 we found an 80% and 60% fungicidal effect and 90% and 70% fungicidal effects on the soil.

C) Method

In vitro study against Ustilago maydis

Malt agar plates were made at concentrations of 0.8-200 ppm (e.g. 10 0.8, 3.2, 12.5, 50 and 200 ppm). The plates were then infected by spraying with a spore suspension of U. maydis or by inserting a piece of agar containing the fungus into the center of the plate. The plates were incubated at room temperature for ¹ 5 2-5 days. The efficacy of the treatment was determined by comparing fungal development on untreated, similarly infected plates. The active compounds of formula (I) exhibited moderate to good activity in the test according to method (C). For example, the active compounds of Examples 1 and 2A showed good activity at both low and high concentrations in the assay according to Method C.

Fungi of the sexes mentioned above cause significant damage in 25 agriculture and are difficult to prevent or prevent. The compounds containing the compounds of the formula I as active ingredients, in addition to their good fungicidal activity, have no phytotoxic effect on plants which are treated with an effective dose and are of particular importance in the systemic action of fungi such as bean Uromyces appendiculatus. .

In a further 35 studies analogous to Method C, the active ingredient of Example 1 exhibited 100% fungicidal activity at 13 and 200 ppm in at least one dose, unless stated numerically, in the following fungi: Phytophthora cactorum (up to 4C 45%) Phytophthora cinamomi (up to 65% effect), Aphanomyces euteiches, Stereum purpureum, Thielaviopsis basicola, Piricularia oryzae, Colletotrichum lindemuthianum (up to 90% effect). 45

In tests analogous to Methods A and B, the active ingredient of Example 1 was 32,

Applied as a spray at a concentration of 125 and 500 ppm barley exerted 75%, 95% and 100% action against Helminthosporium, and Na was 20% phytotoxicity _5Q The larger portion.

D) Method

In vivo activity against Rhizoctonia solani _5t;

The fungus was grown in a sterile mixture of Zonolite and maize flour in a 10: 1 weight ratio to which water was added in a 1: 1 weight ratio; the culture time was 25 days at 25 ° C. The fungus was then mixed with a semi-sterile mixture of peat and sand, and the mixture was treated with an agent containing the active ingredient (composition according to Method A) and at concentrations ranging from 10 to 160 ppm (e.g. 10, 40 and 160 ppm) per substrate volume. we created.

The substrate was filled into pots of 5 cm diameter and planted with cotton shoots (cotyledon). The inoculated pots were kept in an incubation chamber for 14 days at 24 ° C and 60-70% relative humidity, and the fungal infection rate of the roots and stems was compared to untreated, similarly infected plants. The active compounds of formula (I) showed good activity in the test according to Method D. For example, the wettable powder containing the active ingredient of Example 1 exhibited 100% fungicidal activity and, at lower concentrations, was phytotoxic.

The fungicidal efficacy of the agents containing the active compounds of the formula I in tests A and B is summarized in the following table.

Fungicide - Efficacy of formula (1)

R ° R, R ', R Erysiphe Uromyces

125 125 ppm / 500 ppm / 500 ppm_ppm

n-propyl 4-methyl 10 10 9 10 tert-butyl 4-methyl 10 10 10 10 tert-butyl 4-chloro 5 6 10 10 tert-butyl 4-fluoro 10 10 10 10 tert-butyl 4-methoxy 10 10 10 10 tert-butyl 4-phenyl 10 10 10 10 tert-butyl 4-phenoxy 8 10 10 10 tert-butyl 4-trifluoro- methoxy 10 10 10 10 tert-butyl 4-cyano 10 10 10 10 tert-butyl 4iodo 10 10 10 10 tert-butyl 4-bromo 10 10 10 10 tert-butyl 3-trifluoromethyl methyl 10 10 10 10 tert-butyl 3-methyl 10 10 10 10 tert-butyl 2-methyl 10 10 10 10 tert-butyl 2,4-dichloro 10 10 6 10 tert-butyl 3-fluoro-4- methyl 10 10 9 10 tert-butyl 3-chloro-4-methyl 10 10 10 10 tert-butyl 3,5-dimethyl 10 10 10 10 tert-butyl 3-nitro-4- methyl 3,5-dinitro-4- 10 10 3 4 tert-butyl methyl 8 8 2 2 2-pentyl 4-methyl 10 10 10 10 3-pentyl 4-methyl 10 10 10 10 cyclopropyl 4-chloro 10 10 10 10 1-methyl- cyclopropyl 4-methyl 10 10 10 10 cyclohexyl 4-methyl 10 10 10 10 cyclopropyl methyl 4-methyl 10 10 10 10 cyclohexyl- methyl 4-methyl 10 10 10 10

= 100% antifungal effect = no effect

The fungicidal activity of the agent containing the compound of Example 2A is known from 1- (4-chlorophenoxy)-)-51 (1 51-1,2,4-triazol-1-yl) -3,3-dimethyl-2-butanone. (triadimefon), to determine the concentration (in ppm) that produces a 90% fungicidal effect (EC 90).

The results are shown in the following table.

EC 90 Example 2A tridimefon Erysiphe on cucumber 1 <2 barley 5 8 wheat 6 5 Podosphaera on apple <2 <2 Uncinula on grapes 5 5 Uromyces bean 4 38

From these test results, it will be apparent to those skilled in the art that the agents of the present invention are particularly valuable in controlling important soil fungi and seed fungi such as Helminthosporium, Phoma, Rhizoctonia and Thielaviopsis, apart from their significant and outstanding value against powdery mildew and rust fungi.

The particular value and benefits of the agents of the invention are demonstrated and / or better supported by

Containing the active ingredient of Example 1. more detailed test results with which we have identified the following outstanding and in some cases significant properties of the eyes: (1) prolonged action, which was evident from the 100% effect of treatment with beans at 0.012 s% 8 days prior to infection Uromyces app. in case of; (2) stability of the aqueous spray suspension, which was excellent 3 days after preparation of the 0.012 s% suspension in beans Uromyces app. 100% of the effect of treatment against; (3) rapid and sustained penetration into the leaves of the plants, as evidenced by the 100% effect achieved with 0.012 s% agent (a) if the bean leaves were washed 10 minutes after treatment for 10 minutes and then infected with Uromyces app, (b) the leaves - grapes - were washed for 2 hours 15 minutes after treatment and then infected with Uncinula, (c) if coffee leaves were soaked in artificial rain at 50 mm / hour for 15 minutes after treatment with the agent, then dried and soaked again for 15 minutes, dried again, finally watered for a third time for 15 minutes, finally infected with Hemileia vastatrix, and (d) if the leaves of the bean plant were soaked in artificial rain at 50 mm / h for 10 minutes after treatment with the agent, then dried again. It was watered for 10 minutes, dried again, watered for another 10 minutes, and then the bean leaves were infected with Uromyces app. (4) excellent systemic effect in the transport of grapes from the upper and lower parts of the leaves to other untreated parts, whereby uncinated upper and lower leaves showed 70% and 75% eradication of Uncinula, that untreated leaves reach both the acropetal and the basal petals. Further testing of the active ingredient of Example 1 showed a 100% antifungal activity compared to the untreated control when treated with an agent containing 0.012% active ingredient in bean plants6 Uromyces app. 3 days after infection with fungi.

If your treatment is already Uromyces app. bean plants containing sprouted specimens were sprayed with 0.05% by weight sprays, the visible signs of infection were reduced by 60% compared to untreated control 10 days after treatment and only reduced by 50% 3 days after treatment. The results of further tests with the agent containing the active ingredient of Example 1, therefore, indicate that the agent has a satisfactory curative effect and at least a partial destruction effect.

For example, the fungicidal activity of the active ingredient of Example 2A is at least equivalent to that of the active ingredient of Example 1A.

Preferred compounds of formula (I) fulfill at least one, but preferably all, of the following conditions: a) R 0 is propyl, tert-butyl, branched pentyl, C 3-6 cycloalkyl or C 3-6 cycloalkylmethyl in the cycloalkyl moiety; -group; b) R is hydrogen, fluoro, chloro or bromo, trifluoromethyl or C 1-4 alkyl; c) R 'is hydrogen, fluoro, chloro or bromo, C 1-4 alkyl, C 1-4 alkoxy, or cyano, or phenyl or phenoxy, and in each of these groups Y 0 and Y are as defined above;

d) R 'is hydrogen.

Of the preferred compounds of formula (I), those which satisfy at least one of the following conditions are particularly preferred:

a) R 0 is C 3 -C 4 alkyl or C 3 -C 6 cycloalkyl, such as cyclopropyl and cyclopentyl;

b) R is hydrogen, fluorine, chlorine or bromine, trifluoromethyl or C 1-2 alkyl; and

c) R 'is hydrogen, fluoro, chloro, cyano, C 1-2 alkyl or C 1-2 alkoxy; or

d) R is hydrogen and R 'is phenyl or phenoxy in the para position of ring A.

Particularly preferred are compounds of formula I wherein R 0 is -propyl, isopropyl and tert-butyl, in particular tert-butyl. C5-branched alkyl, such as isopentyl and neopentyl, are also preferred. Also preferred are compounds wherein R 0 is cyclopropyl, cyclopentyl or cyclohexyl.

The following Examples illustrate in detail the preparation of compounds of formula (I).

Example 1 α-tert-Butyl-α- (p-methylphenyl) -1 H -1,2,4-triazole-ethanol

A solution of 61.4% sodium hydride (0.62 g) was washed 3 times with petroleum ether and 10 ml of dimethylformamide was added with stirring. To the resulting suspension is slowly added 1.1 g of triazole in 10 ml of dimethylformamide with stirring, and the mixture is stirred at 20 [deg.] C. until gas evolution ceases.

185917th

Juk. Next, 3.0 g of 2- (tert-butyl) -2- (4-methylphenyl) oxirane was added and the mixture was stirred at 90 ° C for 6 hours. The reaction mixture was poured into water, extracted with ethyl acetate, dried and chromatographed on silica gel, eluting with 50:50 hexane / chloroform. A yellow oil is obtained which crystallizes to a solid upon recrystallization from ethanol to give α-tert-butyl (p-methylphenyl) -1 -1-1,2,4-triazol-1-ethanol; m.p. 69-71 ° C. The corresponding hydrogen oxalate (Example IA) has a melting point of 147-150 ° C; p-methylbenzene sulfonate (Example IB) mp 215-220 'Con and hydrochloride (Example IC) mp 247-250' C; the title compound sodium ethanolate (Example 1D) melts above 250 ° C.

Example 2

By following the procedure described in Example 1, the following compounds were prepared:

A) α-tert-Butyl-α- (p-chlorophenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 114-115'C;

B) α-tert-butyl-α- (o, p-dichlorophenyl) -1H-1,2,4-triazol-1-ethanol, m.p. 63-64 'C;

C) α-tert-butyl-α- (m, p-dichlorophenyl) -1Η-1,2,4-triazole-1-ethanol, m.p. 156-157 ° C;

D) α-tert-butyl-α-phenyl-1β-1,2,4-triazole-1-ethanol, m.p. 84-86 'C;

E) α-tert-butyl-α- (p-fluorophenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 104-106 'C;

F) α-tert-butyl-α- (p-methoxyphenyl) -1 -1-1,2,4-triazole-1-ethanol, m.p. 76-79 'C;

G) α-tert-butyl-α- (p-biphenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 117-118 'C;

H) α-tert-Butyl-α- (m-cyanophenyl) -1Η-1,2,4-triazole-1-ethanol, m.p. 123-124 'C;

I) α-tert-butyl-α- (p-phenoxyphenyl) -1Η-1,2,4-triazole-1-ethanol, m.p. 112-113 'C;

J) α-n-Propyl-α-phenyl-1Η-1,2,4-triazole-1-ethanol, m.p. 81-83 'C;

K) α-Isopentyl-α-phenyl-1β-1,2,4-triazole-1-ethanol, m.p. 78-80 'C,

L) α-n-propyl-α- (p-methylphenyl) -1 -1-1,2,4-triazole-1-ethanol, m.p. 86-88 ° C;

M) α-n-Pentyl-α-phenyl-1β-1,2,4-triazole-1-ethanol, m.p. 89-90 'C;

N)? -Isopropyl-? -Phenyl-1? -1,2,4-triazole-1-ethanol, m.p. 71-73 'C;

O) α-tert-butyl-α- (m-trifluoromethylphenyl) -1H1,2,4-triazole-1-ethanol, m.p. 120-122 ° C;

P) α-tert-butyl-α- (m -methylphenyl) -1Η-1,2,4-triazole-1-ethanol, m.p. 93-94 'C;

Q) α-tert-butyl-α- (o-methylphenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 98-100 ° C;

R) α-tert-butyl-α- (p-tert-butylphenyl) -1Η-1,2,4-triazole-1-ethanol, m.p. 108-110 ° C;

S) α-tert-butyl-α- (p-ethylphenyl) -1Η-1,2,4-triazole-1 ethanol, m.p. 91-94 'C;

T) α-tert-butyl-α- (m-phenoxyphenyl) -1Η-1,2,4-triazole-1-ethanol, m.p. 133-135 ° C;

U) α-tert-butyl-α- (m-methoxyphenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 59-61 'C;

V) α-tert-Butyl-α- (p-trifluoromethoxyphenyl) -1H1,2,4-triazole-1-ethanol, m.p. 80-83 'C;

W) α-cyclohexyl-α- (p-methylphenyl) -1Η-1,2,4-triazole-1-ethanol, m.p. 102-103 'C;

X) α-tert-butyl-α- (p-bromophenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 124-125 ° C;

Y) α-cyclohexylmethyl-α- (p-methylphenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 79-81 'C;

Z) α-cyclopentylmethyl-α- (p-methylphenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 74-76 'C;

Z-1) α- (1-ethyl-propyl) -α- (p-methyl-phenyl) -1 -1-1,2,4-triazole-1-ethanol, m.p. 87-89 'C;

Z-2) α- (1-methylbutyl) -α- (p-methylphenyl) -1Η-1,2,4-triazole-1-ethanol, m.p. 89-91 ° C;

Z-3) α-tert-butyl-α- (m -bromo-p-methylphenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 155-158 ° C;

Z-4) α-tert-butyl-α- (m-fluoro-p-methylphenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 102-104 'C;

Z-5) α-tert-butyl-α- (m-chloro-p-methylphenyl) -1H1,2,4-triazole-1-ethanol, m.p. 144-147 ° C;

Z-6) α-cyclopropyl-α- (p-chlorophenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 91-93 'C;

Z-7) u-Cyclobutyl-α- (p-fluorophenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 83-84 'C;

Z-8) α-tert-butyl-α- (m, p-dimethylphenyl) -1Η, 2,4-triazole-1-ethanol, m.p. 120-122 ° C;

Z-9) α-tert-butyl-α- (m''-dichlorophenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 145-147 'C;

Z-10) u-tert-butyl-α- (m-chlorophenyl) -1Η-1,2,4-triazole-1-ethanol, m.p. 126-127 'C;

Z-11) α-tert-butyl-α- (p-cyanophenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 105-107 'C;

Z-12)? -Cyclopentyl-α- (p-methylphenyl) -1? -1,2,4-triazole-1-ethanol;

Z-13) α- (1-methylcyclopropyl) -α- (p-methylphenyl) -1 1-1,2,4-triazole-1-ethanol, m.p. 126-128 ° C;

Z-14) α-tert-butyl-α- (p-iodophenyl) -1Η -1,2,4-triazole-1-ethanol, m.p. 78-80 'C;

Z-15) α- (2-pentyl) -α- (p-methylphenyl) -1Η-1,2,4-triazole-1-ethanol, m.p. 89-9! 'C;

Z-16) α- (tert-butyl) -α- (m, m'-dimethylphenyl) -1H1,4-triazole-1-ethanol, m.p. 128-130 ° C;

Z-17) α-tert-butyl-α- (3-nitro-4-methylphenyl) -1H-2,4-triazole-1-ethanol, m.p. 160-161 ° C;

Z-18) u-tert-Butyl-α- (3,5-dinitro-4-methylphenyl) 1H-1,2,4-triazole-1-ethanol, m.p. 194-196 'C.

Example 3

2- (tert-Butyl) -2- (4-methylphenyl) -oxirane

A solution of 61.4% sodium hydride (2.2 g) was washed 3 times with petroleum ether, 70 ml dimethylsulfoxide was added and the reaction mixture was heated to 70 ° C with stirring and then allowed to warm to 85 ° C. and then stirred for 40 minutes at 75 ° C. The resulting reaction mixture was cooled to 0 'C in a brine bath and treated dropwise with a solution of trimethylsulfonium iodide (7.0 g) in dimethylsulfoxide (50 ml) and tetrahydrofuran (20 ml) while maintaining the temperature below 18 ° C. A solution of tert-butyl p-methylphenyl ketone (3.0 g) in THF (30 mL) was added to the reaction mixture under stirring, while maintaining the temperature below 10 ° C. The reaction mixture was stirred at 0 ° C for 30 minutes and then at room temperature for 2 hours. The reaction mixture was poured into water (400 mL), extracted with methylene chloride, and the organic phase was washed with water and brine, dried and evaporated to give 2- (tert-butyl) -2- (4-methylphenyl) oxirane as a yellow oil.

Claims (15)

A fungicide, characterized in that the active ingredient is 0.0005-90% by weight of a- ^10- aryl-1H-1,2,4-triazol-1-yl-ethanol of the formula (I): R 0 is propyl, tert-butyl, branched pentyl, C 3 -C 8 cycloalkyl, or C 3 -C 8 cycloalkyl in the cycloalkyl moiety and C 4 -C 11 total cycloalkylalkyl in the alkyl moiety, and cycloalkyl- and cycloalkylalkyl optionally substituted with C 1-3 alkyl; R is hydrogen, 9 to 35 halogen, C 1 -C 4 alkyl, trifluoromethyl, C 1 -C 4 alkoxy, or nitro; R 'is hydrogen, halogen atoms from 9 to 53, C 1-4 alkyl, trifluoromethyl, C 1-4 alkoxy, trifluoromethoxy, nitro, cyano, phenyl or phenoxy; R is hydrogen or methyl, with the proviso that at least 30 of R, R 'and R' are other than hydrogen, containing a carrier or diluent, preferably a natural or synthetic mineral, aliphatic, aromatic or cyclic hydrocarbon, and a surfactant, preferably an ionic or non-ionic dispersant, an emulsifier, or a wetting agent, at least one. (Priority 11/11/1980) Fungicide according to claim 1, characterized in that it contains an active ingredient of the formula I in which R 0 is propyl, 40 tert-butyl or branched pentyl, R, R 'and R' are as defined in claim 1. (Priority: November 13, 1979) 3. The fungicidal composition according to claim 2 wherein (I) active agent of formula ₄₅ wherein R @ t-butyl group, R ', R and R' are as defined in claim 1. (Priority: November 13, 1979) 4. The fungicidal composition according to claim 3, characterized in that a (1) active substance ₅₀ comprising formula wherein R 'is fluorine, chlorine, bromine, iodine, methoxy, phenyl, trifluoromethoxy, methyl or ethyl, R and R 'are hydrogen. (Priority: November 13, 1979) The fungicide according to claim 3, characterized in that it contains an active ingredient of the formula I in which R 2 is chlorine, R 14 is chlorine and R 'is hydrogen. (Priority: November 13, 1979) The fungicide according to claim 1, characterized in that it contains an active ingredient of the formula I in which R 0 is a C 3 -C 8 cycloalkyl group or a (C 3 -C 8 cycloalkyl) C 1 -C 3 alkyl group, which is unsubstituted or monosubstituted with C 1-3 alkyl. (Priority: July 14, 1980) The fungicide according to claim 6, characterized in that it contains an active ingredient of the formula I in which R 'is hydrogen, R is hydrogen and R' is chloro, bromo, iodo, methoxy, phenyl, trifluoromethoxy. , methyl or ethyl, or R 2 -chlorine and R '4 -chlorine. (Priority: July 14, 1980) Fungicide according to claim 7, characterized in that it contains an active ingredient of the formula I in which R 0 is cyclopropyl. (Priority: July 14, 1980) Fungicide according to claim 7, characterized in that it contains an active ingredient of the formula I in which R 0 is (C 3 -C 8 cycloalkyl) - (C 1 -C 3) alkyl. (Priority: July 14, 1980) 10. A process for the preparation of a-aryl-1H-1,2,4-triazol-1-yl-ethanols of the formula I and their salts, wherein R 0, R, R 'and R' are as defined in claim 1. by reacting a compound of formula II, R 0, R, R ', and R with an alkali metal X of formula III, as defined above, and then converting the resulting compound into a salt thereof, if desired. (Priority 11/11/1980) 11. A process according to claim 10 for the preparation of compounds of formula I wherein R 0 is propyl, tert-butyl or branched pentyl, wherein a compound of formula II is reacted wherein R 0 is as defined in the claim. (Priority: November 13, 1979) 12. A process according to claim 11 for the preparation of a compound of formula I wherein R 0 is a tert-butyl group, comprising reacting a compound of formula II wherein R 0 is a tert-butyl group. (Priority: November 13, 1979) 13. A process according to claim 10 for the preparation of compounds of formula I wherein R 0 is C 3 -C 8 cycloalkyl or C 3 -C 8 cycloalkyl-C 1 -C 3 alkyl which is unsubstituted or 1-C 1 -C 3 alkyl. Monosubstituted with C3 alkyl, characterized in that a compound of formula II is reacted wherein R0 is as defined in this claim. (Priority: July 14, 1980) 14. A process according to claim 13 for the preparation of a compound of formula I wherein R 0 is cyclopropyl, which comprises reacting a compound of formula II wherein R 0 is cyclopropyl. (Priority: July 14, 1980) A process for the preparation of a compound of formula (I) according to claim 13 wherein R 0 is (C 3 -C 8) cycloalkyl (C 1 -C 3) alkyl, characterized in that wherein R 0 is (C 3 -C 8) cycloalkyl (C 1 -C 3) alkyl. (Priority: July 14, 1980)