NL8006170A - METHODS FOR PREPARING AND USING ORGANIC COMPOUND - Google Patents

Description

* '♦

Methods for preparing and using organic compounds.

The invention relates to x-aryl-1H-1,2, h-triazole-1-ethanols, in particular α-alkyl-α-phenyl-1H-1,2, - triazole-1-ethanols, and to methods of preparing these ethanols and their use as fungicides and of preparations intended for agricultural purposes to facilitate such use.

In particular, the invention provides compounds of formula 1, wherein R ° is an alkyl group having up to 12 carbon atoms, a cycloalkyl group having 3-8 carbon atoms, or a cycloalkylalkyl group having U-11 carbon atoms, wherein the cycloalkyl portion is 3-8 carbon atoms and the alkyl portion 1 -3 carbon atoms, which cycloalkyl and cycloalkylalkyl groups are optionally substituted by one or two alkyl groups of 1-3 carbon atoms, R a hydrogen atom, a halogen-15 atom with a sequence number of 9 to 35, an alkyl group with 1- U carbon atoms, a mono-, di- or tri-haloalkyl group with 1-k carbon atoms, in which the halogen atoms, independently of each other, have a sequence number from 9 to 35, an alkoxy group with 1-h carbon atoms, an alkylthio group with 1- k carbon-20 atoms or the nitro group, R 'a hydrogen atom, a halogen atom with a sequence number of 9-53, an alkyl group with 1-U carbon atoms, a mono-, di- or tri-haloalkyl group with 1-h carbon atoms, wherein the halogen atoms, independently of each other, are halogen atoms with a sequence number of 9-35, an alkoxy group with 1-U carbon atoms, a mono-, di- or tri-haloalkoxy group with 1-U carbon atoms, wherein the halogen atoms, independently of each other, have a sequence number from 9 to 35, an alkylthio group with 1-h carbon atoms, a nitro, -CN or -C00R "group, a group of formula 7 or 8, R", a hydrogen atom or an alkyl group with 1- h carbon atoms, R '*' a hydrogen atom, a halogen atom with a sequence number of 9-17 80 06 17 0 2 \ or an alkyl group with 1 or 2 carbon atoms and Z represent an oxygen or sulfur atom, or in which R and R 'together form a alkylene-dioxy group with 1 or 2 carbon atoms, the carbon atoms of which are adjacent to the phenyl ring A, are substituted and 5 Y ° and Y, independently of each other, are a hydrogen atom, a halogen atom with a sequence number of 9-35 », an alkyl group with 1-1 * carbon atoms or an alkoxy group with 1-1 * carbon atoms for set.

Examples of halogen atoms with a sequence number 10 of 9-53 are fluorine, chlorine, bromine and iodine, with a sequence number of 9-35 fluorine, chlorine and bromine and those with a sequence number of 9-17 fluorine and chlorine.

One of the substituents R or R 'represents a mono-, di- or tri-haloalkyl group or contains such a group, for example this is the trifluoromethyl group.

The invention also relates to processes for preparing the compounds of the formula I according to the invention, by a) a compound of the formula 2, in which R °, R, 20 R 'and R, M have the meanings indicated above in a inert organic solvent to react with a compound of formula 3, wherein X represents an alkali metal, b) preparation of a compound of formula 1a, wherein R 2 and R have the meanings indicated above, by oxidation of the CH 2 group of a compound of formula 1b, in which R ° and R have the above meanings, or c) preparation of a compound of formula 1c, wherein R and R ° have the above meanings and alk is an alkyl group with 1 to mb carbon atoms by esterifying a compound of formula 1a with an alcohol of formula bt wherein alk has the meaning indicated above, or a reactive functional derivative thereof.

Process a) can be carried out at a temperature between, for example, 0 and 180 ° C, preferably between 1 * 0 and 120 ° C, in a conventional inert, organic solvent, for example an 8 0 06 1 7 0 «3 amide of an organic carboxylic acid, such as dimethylformamide,; are carried out. As usual, the compound of formula 3 is preferably obtained by reaction of triazole with a strong base, such as an alkali metal hydride, eg sodium hydride, in an inert organic solvent which is suitably the same solvent as that used in process a).

The oxidation according to method b) can be carried out using an oxidizing agent capable of oxidizing a methyl group to a carboxyl group. Examples of suitable oxidizing agents are potassium permanganate, manganese dioxide and corresponding oxidizing agents, preferably potassium permanganate. The reaction is suitably carried out in an aqueous solution. Suitable reaction temperatures for process b) 15 are between 20 and 150 ° C, preferably between 60 and 120 ° C.

The compounds of formula 1a are obtained in free form or in salt form (replacing the hydrogen of the carboxyl group with a cation), depending on the reaction conditions used and the manner in which the recovery is carried out. The free forms of compounds of formula 1a can be converted into salts thereof in the usual manner and vice versa. Preferably, the cation of the salt form of compounds of formula Ia is an agriculture acceptable cation such as 11a, K and NH 2.

Method c) can be carried out according to known esterification methods for compounds containing a reactive hydroxyl group. Esterification with an alcohol of formula IV is suitably carried out at a reaction temperature between 30 and 80 ° C, especially under anhydrous conditions and in the presence of an acid, such as hydrogen chloride. Examples of suitable solvents for this reaction are inert organic solvents or an excess of an alcohol of the formula k. Examples of suitable, reactive, functional derivatives of an alcohol of formula 1+ are the corresponding diazo-alkane, for example a diazoalkane with 1-3 carbon atoms, or 8 0 06 1 7 0 1+ or an alkyl halide, in particular a chloride , bromide or iodide. The reaction with a diazoalkane is suitably carried out under anhydrous conditions in an inert organic solvent. A suitable reaction temperature is then between 5 -20 and + 0 ° C, usually between -5 and + 20 ° C. For the reaction with an alkyl halide, the compounds of the formula Ia are preferably used in salt form, for example as an alkali metal or silver salt. Such a reaction is conveniently carried out in an inert organic solvent and at a temperature between 0 and 100 ° C, usually between 100 and 90 ° C.

The reaction product of processes a), b) and c) can be recovered from the reaction mixture in which it is formed by conventional methods.

The compounds of formula 1 of the invention wherein R 'has a meaning other than the carboxyl group can be prepared and used in the form of acid addition salts. The compounds of the formula I are ethanol derivatives and can therefore be in the free form as well as in other forms, such as an ethanolate salt form, for example a sodium ethanolate form and in the form of a metal complex, for example of metals of the groups Ib, Ha, Ilb, Vlb, Vllb and VIII of the Periodic Table, such as copper and zinc and with anions, such as chloride, sulfate, nitrate, carbonate, acetate, citrate, dimethyl dithiocarbonate, etc. exist. Optional salt forms of compounds of formula 1 are preferably salt forms acceptable in the agricultural field.

The acid addition salts, the ethanolate salt forms and the metal complexes can be prepared from the corresponding free form in a conventional manner and vice versa.

Compounds of formula 2 can be obtained by reacting a compound of formula 5, in which R ° R, R 'and R, M have the meanings indicated above, with the reaction product of a strong base and trimethylsulfonium iodide, which provides a reagent which is formula 6 can be proposed. This process is performed in an inert 8006170 organic solvent. It is a known type of reaction for preparing epoxy derivatives from ketones.

Many compounds of formula 5 are known and those which are not known per se can be obtained by analogous methods to those known for preparing known compounds from known materials. Many compounds of formula II are also known.

The compounds of the invention of the formula (I) are useful as fungicides for controlling phytopathogenic fungi, including in particular powdery mildews and rust fungi, as evidenced by standard fivn and in vitro experiments of the type described below. For such an application, the compounds of the formula 1 according to the invention can be applied to plants, seeds or the earth in a conventional manner for the use of fungicides. As will be appreciated, the amount of the compound of formula 1 to be used will depend on known factors, such as the specially employed compound, whether the treatment is prophylactic or therapeutic, whether the compound will be used for foliar spraying, soil treatment or of the seeds, the fungus type to be controlled and the time of application. In general, however, satisfactory results are obtained when the compound is applied to a washed, washed or soil soil in an amount between about 0.005 to 2, preferably about 0.01 to 1 kg (active ingredient) per hectare. If desired, the treatment can be repeated, for example, at intervals of 8 to 30 days. If the preparation is used for treating seeds, satisfactory results are obtained if the active compound (s) is used in an amount between about 0.05 to 0.5, preferably about 0.1 to 0.3, gram / kg of seed.

The term "soil" as used herein includes any conventional growth medium, both natural and artificial.

8006170 β

Another aspect of the invention relates to a process for the preparation of a composition having a fungicidal action comprising as fungicidal at least one compound according to the invention of the formula 1 in free form and / or 5 in the form of an agriculture-acceptable salt and des optionally contains an inert carrier or diluent. Generally, such compositions will contain from about 0.0005 to 90, preferably from about 0.1 to 60, weight percent active material. They can be in a concentrated form, which must be diluted before use, or in a dilute form ready for use. Examples of special preparation forms are wettable powders, concentrated emulsions, sprayable preparations, sprayable preparations, granules and preparations from which the active ingredient is slowly released, in which conventional carriers and the like other diluents and / or additives that are acceptable in the agricultural field can be present to be. Uses of these preparations will generally contain between about 0.0005 and 10% by weight of one or more of the compounds of the invention of Formula 1 as active ingredient. Examples of sprayable suspensions may contain, for example, between 0.0005 and 0.05% by weight, preferably between 0.001 and 0.02% by weight, of the active ingredient. Concentrated fungicidal formulations will generally contain between about 2 and 90 wt%, preferably between about 5 and 70 wt%, of one or more compounds of formula 1 as active ingredient. Concentrated emulsion forms will generally contain between 10 and 70 wt / s, preferably about 20 to 60 wt, active ingredient. Preferred, however, are solid, particulate preparations.

Preparations primarily for spraying preferably contain a surfactant such as a liquid polyglycol ether, a higher alkyl sulfate or a lignin sulfonate.

In addition to the usual carriers and surface-active agents, the compositions according to the invention can also contain other additives for special purposes, such as, for example, stabilizers, deactivators (for solid preparations on carriers with an active surface), agents for -5 improve adhesion to plants, anti-corrosion agents, anti-foaming agents and dyes.

In addition, other fungicides, bactericides and other beneficial materials, such as insecticides, may be present in the compositions of the invention and are also within the scope of the invention.

Examples For preparing preparations having a fungicidal action are: a) A wettable, powdered preparation

50 parts of a compound of formula 1, for example ot, butyl-α- (p-methylphenyl) -1H-1,2, U-triazole-1-ethanol, were ground with 2 parts of Jauryl sulfate, 3 parts of sodium lignin sulfonate and k5 parts of finely divided kaolinite until the average particle size was less than 5 microns. The resulting sprayable liquid can be used both for spraying foliage and for watering roots.

b) Granular preparation.

0.5 parts by weight of binder (nonionic surfactant) was sprayed on 9.5 parts by weight of quartz sand in a tumbler mixer and the whole was intimately mixed.

Then 5 parts by weight of a compound of formula 1, for example, powdered α-t-butyl-α- (p-methylphenyl) -1H-1,2, U-triazole-1-ethanol, were added and mixing was continued continue until a granular preparation with a particle size between 0.3 and 0.7 mm was obtained. This granular preparation can be used by incorporation into the soil next to the plants to be treated.

c) Concentrated emulsion.

25 parts by weight of a compound of the formula 1, for example α-t-butyl-α- (p-methylphenyl) -1H-1,2, U-35 triazole-1-ethanol, was mixed with 30 parts by weight of iso- octylphenyl octaglycol-8006170 ether ether and b5 parts by weight of a petroleum fraction with a boiling range of 210-280 ° C (D20: 0.92). Finally, the concentrated preparation was diluted with water to the desired concentration.

d) Preparation for treating seeds.

U5 parts by weight of a compound according to the invention of the formula 1, for example at, butyl-α- (p-methyl-phenyl) -1H-1 * 2, H-triazole-1-ethanol, were mixed with 1.5 parts of diamylphenol decaglycol ether ethylene oxide adduct, 2 parts by weight of thin liquid lubricating oils, 51 parts of fine talc and 0.5 parts of rhodamine B colorant. This mixture was ground at 10,000 rpm.

in a contraplex grinder until an average particle size of less than 20 microns was obtained. The resulting dry powder for seed treatment has good adhesion and can be applied to the seeds, for example, by mixing in a slowly rotating vessel for 2-5 minutes.

Examples of fungi against which the compounds of the formula I of the invention are particularly indicated are: A) Basidiomycetes, including 20 A. 1) Those of the class Uredinales. such as those of the genus Uromyces, in plants, such as beans, e.g. Uromyces annendiculatus and ornamental plants, e.g. Uromyces dianthi, those of the genus Hemileia, in plants such as coffee, e.g. Hemileia vastatrix, those of the genus Puccinia 25 in plants, such as cereals ( for example wheat, oats and barley), for example Puccinia graminis, Puccinia recondita and Puccinia striiformis, or ornamental plants, for example Puccinia pelargoniizonalis and Pucc. antirrhini. that of the genus Phakopsora in plants, such as soy, for example Phakonsora pachyrhizi.

Those of the genus Melampsora, in plants, such as flax, for example Melampsora lini, and those of the genus Tranzschelia, eg Tranzschelia pruni in plums, A. 2) those of the class Ustilaginales, such as those of the genus Ustilago, in plants, such as gers, wheat, corn and sugar cane, for example U, maydis on corn and U, nuda on barley and 8 0 06 1 7 0 9

• V

A. 3) that of the genus Stereum in trees with kernels containing fruits and stone fruits, for example Stereum purpureum in apples and plums.

B) Ascomycetes, including 5 B. 1) those of the Erysiphales class, such as those of the genus Erysiphe, in plants, such as cucumber, barley, wheat and sugar beets, for example Erysiphe graminis f. sp. tritici on wheat and Erysiphe cichoraceareum on cucumbers, those of the genus Spohaerotheca on cucumbers and roses, for example, Spohaerotheca pannosa on roses, those of the genus Podosphaera in apples, pears and plums, for example Podosphaera leucotricha on apples, those of the genus Uncinula on plants, such as grapes, for example Uncinula necator cp vines, those of the genus Oidium on a wide variety of plants and those of the genus Leveillula in plants, such as cotton and other Malvaceae, e.g.

Leveillula taurica on cotton.

C) Oomycetes, including C. 1) those of the genus Phytophthora spp., E.g.

Ph. cactorum, Ph. parasitics and Ph. cinamomi on sensitive plants and C. 2) those of the genus Aphanomyces in plants, such as beans and sugar beets, for example Aphanomyces euteiches in sugar beets, and D) Deuteromycetes, including 25 D. 1) those of the genus Helminthosporium in plants, such as barley and corn, for example Helm. Sativum, D. 2) that of the genus Septoria in plants such as wheat, tomatoes and selerie, e.g. Sept. tririci in wheat, tomatoes and selerie, for example Sept. tritici in wheat, D. 3) those of the genus Rhizoctonia in plants, such as cotton and potatoes, for example Rhiz. solani in cotton, D. k) that of the genus Fusarium spp., e.g.

F. oxysporum f. sp. lycopersici in tomatoes, F, oxysporum f. sp, 35 vas infect urn in cotton, F. oxysporum f. sp. cubense in bananas, an Ofi 17 n 10 F. solani in vegetables, F. culmorum in cereals and F. graminearum in cereals, D. 5) those of the genus Thielaviopsis in plants, such as cotton, tobacco, etc., for example Thielaviopsis basicola 5 in cotton, D. 6) that of the genus Phoma in plants, such as sugar beet, swede, etc., for example, Phoma betae in sugar beet, D. 7) that of the genus Piricularia spp., e.g.

10 P. oryzae on rice and D. 8) those of the genus Colletotrichum spp .. eg.

C. lindemuthianum in beans.

The following conventional tests illustrate the manner in which the fungicidal activity of the compounds of the formula I of the invention can be demonstrated.

Test Method A: In vivo using bean rust (üromyces appendiculatus). Phaseolus vulgaris (French bean plants) was cultivated in a mixture of peat and sand in plastic pots with a diameter of 6 cm for 9 days. Thereafter, these plants were sprayed with a spray liquid containing 0.0008 to 0.05 w / w (eg 0.0008, 0.003, 0.012% and 0.05%) active ingredient. According to this treatment, the foliage was sprayed until the liquid almost dripped from the leaves or the soil was watered (28 ml of liquid per pot). After drying, the plants were inoculated with a spray of a spore suspension (500,000 to 700,000 spores / ml) and incubated in an incubation chamber with a relative humidity of 100% and a temperature of 21 ° C for 7 days. The efficiency of the treatment with active material was determined by comparing the number of rats per 30 leaves to that of untreated, correspondingly inoculated, control plants.

The compounds of formula 1, in particular the compounds of the following front beds, for example the compounds of examples 1, 1A, 1B, 1C, 2A, 2B, 2D, 2F, 2G, 2H, 2L, 2N, 2P, 2Z-1, 2Z-3, 2Z-U, 2Z-7, 2Z-8, 2Z-9, 2Z-11, 2Z-13, 8 0 06 17 0 11 2Z-14, 2Z-15, 2Z-2i +, 2Z-27, 2Z-28, 2Z-32, 2Z-33, 2Z-Ul to 2Z-U and 3 used hereinafter in the wettable powder formulation described above exhibit a remarkable degree of fungicidal activity in the test described above »Both by contact and by a root systemic action.

Corresponding tests carried out on * following combination of crop fungi gave corresponding results, coffee: coffee leaf rust (Hemileia vastatrix) wheat: black stem rust (Puccinia graminis) 1 o wheat: brown leaf rust (Puccinia recondita) wheat: yellow or stripe rust (Puccinia striiformis) flax : Flax rust (Melamsnora Lini) Pelargonium: Pelargonium rust (Puccinia pelargoniizonalis) Snapdragon: Snapdragon (Puccinia antirrhini) 15 Test method B: In vivo, using cucumber powdery mildew (Erysiphe cichoracearum).

Cucumis sativus (cucumber) was grown for 7 days in a mixture of peat and sand in plastic pots with a diameter of 6 cm. The plants were then sprayed with a spray liquid containing 0.0008 to 0.05% by weight (eg 0.0008%, 0.003%, 0.012% and 0.05%) active ingredient. Treatment included spraying the foliage until the liquid almost ran out or watering earth (28 ml spray liquid per jar). After drying, the plants were seeded by dusting them with freshly collected conidia and then incubated for 7 days in an incubation chamber with a relative humidity of 60-80% and a temperature between 25 and 30 ° C. The activity of the active ingredient was determined by comparing the degree of fungal attack with that on untreated, correspondingly grafted, control plants.

The compounds of formula 1, in particular the compounds of the following examples, for example the compounds of examples 1, 2A, 2B, 2G, 2D, 2F, 2G, 2H, 2L, 2u, 2P, 2Q, 2R, 2S , 2T, 2U, 2V, 2Z-1, 2Z-3, 2Z-H, 2Z-9, 2Z-11, 2Z-13 -35 2Z-15, 2Z-2U, 2Z-26, 2Z-27, 2Z- 28, 2Z-35, 2Z-U0 - 2Z-7, 1A, 1B, 8 0 06 1 7 0 12 1C and Example III hereinafter used in the aforementioned wettable powder formulation exhibit a significant degree of fungicidal activity, both by contact as a systemic action through the roots.

5 Tests according to test method B were carried out with the same results on the following combinations of crops and fungi: wheat: powdered powdery mildew (Erys. Gram, f. Sp, tritici) barley: barley powdered powdery mildew (Erys. Gram, f. Sp. Hordei) 10 apple: apple powdery mildew (Podos leucotricha) grapes: vine powdery mildew (Uncinula necator)

The above-described test method B was repeated with the cucumber powdery mildew and the recommended compound of Example 1 below (both by spraying the foliage and watering the soil), but now at lower concentrations of 0.0002 wt% and 0.00005 wt%. A further 100% control of the fungi was obtained, which further indicates the remarkable activity obtained with the compounds according to the invention. At concentrations of 0.000012 wt% and 0.000003 wt., In the same experiment, when applied by spraying, a control of resp. 70% and 50% and when administered via watering the earth a control of resp. 90% and 70% are obtained. Repeating Test Method B, at concentrations of 0.0002 wt% and 0.00005 wt% against barley powdery mildew when applied by spraying, a control of resp. 70% and 55% and when applied via watering the earth a control of resp. 80% and 70% are obtained. According to test method B, in concentrations of 0.0002 wt.% And 0.00005 wt.%, A control against wheat powdery mildew was applied when sprayed by spraying resp. 80% and 60% and when administered via earth a control of resp. 90% and 70% are obtained.

Research Method C: In vitro test using Ustilago maydis (corn fire).

Different concentrations of the 8 0 06 1 7 0 13 active ingredient were incorporated in malt agar plates, whereby concentrations of 0.8 to 200 ppm ai (eg at 0.8, 3.2, 12.5, 50 and 200 ppm) were ) obtained. The plates were then seeded by spraying a spore suspension of U. maydis on it or by placing a piece of agar containing the fungis in the center of the plate. The plates were then incubated at room temperature for 2 to 5 days. The effect of the treatment with the active ingredient was determined by comparing the growth of the fungis with those on untreated, correspondingly grafted plates. The compounds of formula 1 give moderate to good control according to research method C. For example, the compounds of Examples 1, 2A and 2Z-1 below give good control in both the low and high concentrations of Test Method C. According to a corresponding test on Fusarium oxysnorum f. sp. the compounds of formula 1, for example the compounds of Examples 2A, 2B, 2D, 2P, 2R, 2S, 2Z-32, 2Z-3, and 2Z-1 * 6 below, give moderate to good control.

Fungi of the above-mentioned genera cause considerable damage in the agricultural field and are difficult to destroy or combat. In addition to the compounds of the formula I of the invention controlling such fungi, their effective doses on plants that do not lead to such fungi are phytotoxic, and these compounds further appear to be of particular interest because they also combat fungi via systemic action, such as for example, was determined in the control of Uromyces appendiculatus on beans.

Additional tests, analogous to Test Method C, at 13, 50, and 200 ppm ai, except where otherwise indicated, show 100% control using the compound of Example 1 below in at least one dose tested at the following fungi: Phytophthora cactorum (maximum control ^ 5%) \ Phytophthora cinamomi (maximum control 65%) \ Aphanomyces euteiches; Stereum purpureum; 35 Thielaviopsis basicola; Piricularia oryzae; and Colletotrichum 8 0 06 1 7 0

1U

lindemuthianum (maximum control 90%).

Additional tests analogous to Test Methods A and B give doses of 32, 125 and 500 ppm a.i. performed with the compound of Example 1 below, applied by spraying, a control of resp. 75 95% and 100% of Helminthosporium. with 20% phytotoxicity at the highest dose.

Test Method D: In vivo, using Rhizoctonia solani.

The fungus was grown in a sterile mixture of Zonolite and corn meal (10: 1 w / w), to which water in an amount of about 1: 1 (w / w) was added. Cultivated for 1U days at 25 ° C. Then the fungus was mixed with a semi-sterile peat and sand mixture, which was then treated with a suspension containing the active ingredient in the form of a preparation to give concentrations of 10 to 160 ppm (e.g. 10, Uo and 160 ppm) calculated per volume of substrate. The substrate was then transferred to 5 cm diameter pots planted with cotton-20 seedlings (at the seed stage). The pots with plants were incubated after 1¾ days in an incubation chamber at a temperature of 2 ° C and a relative humidity between βθ and 70%, after which the disease attack was determined by comparing the damage of the roots and hypocotyl by the fungus 25 with those of untreated control plants inoculated in a corresponding manner. It has been found that the compounds of formula 1 in this test D give a good control. For example, the compound of Example 1 below, used in the wettable powder formulation described above, provides a control of 100 JS, without phytotoxicity at the lowest dose.

According to a test analogous to test method D conducted with Phoma betae on sugar beets, the compounds of formula 1, for example the compounds 1, 1A, 1B, 1C, 35 2A, 2B, 2D, 2N, 2P, 2R, 2T, 2Y, 2Z , 2Z-1, 2Z-4, 2Z-7, 2Z-8, 2Z-11, 2Z-15, 2Z-32, 2Z-33, 2Z ~ 3k and 2Z-U1 8006170 15 good combat.

From the foregoing it appears that the compounds according to the invention are also of particular importance for combating important fungi developed in soil and seeds, for example Helminthosporium, Phoma. Rhizoctonia and

Thielaviopsis. this in addition to their considerable value and importance for controlling powdery mildews and rusting.

The particularity and advantages of the invention are confirmed and / or further demonstrated by more detailed evaluations of the compound of Example 1, which compound has the following extraordinary and sometimes remarkable properties: 1) a sustained action that is still 100% combat Uromyces app. on stake beans in spray concentrations of 0.012% t where the preparation was applied 8 days before inoculation gives 2) good stability of aqueous sprayable suspensions as evidenced by the 100% control of

Uromyces app. on beans, whereby the preparation was applied 3 days after preparation of the suspension (concentration 0.012%), 3) a rapid and continuous penetration of the active ingredient into the leaves of the plants to be protected, as evidenced by the 100% control at a concentration of 0.012% after a) washing the leaves of the stake beans for 10 min, only 10 min after applying the active ingredient, followed by contamination with Uromyces app., b) washing the leaves of vine for 15 min., 2 hours after application of the active ingredient, followed by infection with Uncinula. c) a simulated rain washing treatment of the leaves of coffee plants at a rain rate of 50 MM / hour, first 2 hours after applying the active ingredient for 15 minutes followed by drying and a second rain treatment for 15 minutes, again followed by drying and then a third rain treatment 8006170 16 for 15 min., followed by infection of the coffee plants with Bemileia vastatrix and d) a simulated rain fall treatment of the leaves of stake beans at a rain rate of 50 MM / hour, first 2 hours after application of the active component-5 for 10 minutes and followed by drying, then a second rain treatment for 10 minutes, followed by drying and then a third rain treatment for 10 minutes, followed by infection of the stake bean plants with Uromyces app. and 10 U) excellent systemic distortion which causes transport, after incorporation through the leaves of the upper or lower parts of the vine, to the other part that has not been treated, resulting in a 70% and 75% control of Uncinula in resp. the untreated top and bottom leaves are observed, indicating that such transport to the untreated leaves occurs both to the top and bottom leaves.

In a still further study of the compound of Example 1 below, a fungicidal activity of 100 compared to an untreated standard, observed upon application of the active ingredient, at a concentration of 0.012 3 days (before spore formation) was observed. stake beans with Uromyces ann. were infected,

When applied at a concentration of 0.05% on 25 stake bean plants that already have spore eats of Uromyces app.

showed a 60 # control of the visible disease symptoms, compared to an untreated control, was observed 10 days after application, while a 50% control was observed as early as just 3 days after application.

The foregoing further properties of the compound of Example 1 indicate the desirable properties of a medicinal activity and an at least partial extermination activity.

Other compounds of formula 1, especially the compounds of examples 2A, 2B, 2D, 2F, 2G, 8006 170 17

2H, 2L, 2Ï, 2P, 2Z-1, 2Z-3, 2Z-1 *, 2Z-7 to 2Z-9, 2Z-11, 2Z-13 to 2Z-15, 2Z-21 *, 2Z-32, 2Z-33, 2Z-1 + 3 to 2Z-5 and 3 also show very good to excellent fungicidal activity according to the test methods described above. For example, the fungicidal activity of the compound of Example 2A is

at least equal to the activity of the compound of Example 1 and also the compound of Example 2Z-33 has the same degree of fungicidal activity as that of Example 1.

Recommended compounds of formula 1 have one or more and preferably all of the following characteristics: a) R ° is an alkyl group with 2-10 carbon atoms, in particular an alkyl group with 3-10 carbon atoms and especially an alkyl group with 3-6 carbon atoms, a cycloalkyl group with 3-6 carbon atoms or a cycloalkylmethyl group, wherein the cycloalkyl moiety has 3-6 carbon atoms, b) R represents a hydrogen, fluorine, chlorine or bromine atom, the trifluoromethyl group or an alkyl group with at most h carbon atoms for, c) R 'is a hydrogen, fluorine, chlorine or bromine atom, an alkyl group with at most U carbon atoms, an alkoxy group with also at most U carbon atoms, an alkylthio group with at most b carbon atoms, a CIT group, a group of formula 7 or 9 »in which Y ° and Y have the meanings indicated above and d) R, M represents a hydrogen atom. The especially recommended compounds of the aforementioned recommended compounds of formula 1 satisfy one or a number, preferably all, of the above-mentioned properties: a) R ° is an alkyl group with 3-6 carbon atoms or a cycloalkyl group with 3-6 carbon atoms, such as the cyclopropyl or cyclopentyl group, b) R represents a hydrogen or fluorine, chlorine or bromine atom, a trifluoromethyl group or an alkyl group of 1 or 2 carbon atoms and c) R * represents a hydrogen, fluorine - or chlorine- 80 06 17 0 * 18 atom, a CN group, an alkyl group with 1 or 2 carbon atoms or an alkoxy group with 1 or 2 carbon atoms for, or d) R is a hydrogen atom and R 'gives a group of formula 7 or 9, placed in the para-position of ring A, 5, particularly wherein Y ° and Y are hydrogen atoms.

Especially recommended compounds of formula 1 are those in which R ° has a propyl or butyl group, for example the n-propyl, isopropyl, n-butyl, sec.butyl, i-butyl and t-butyl group, in the especially the n.propyl, isopropyl, the branched butyl groups and especially the t-butyl group. Other branched alkyl groups of 5 or 6 carbon atoms, for example the iso-pentyl and neopentyl group, are also of particular interest.

This is also the case with those compounds in which R ° is the cyclopropyl, cyclopentyl or cyclohexyl group.

Example 1; α-t.butyl-a - (p-methylphenyl) -1H-1,2, k-triazole-1-ethanol.

A portion of 61% sodium hydride weighing 0.62 g was washed three times with petroleum ether and then 10 ml of dimethylformamide was added while stirring.

To the suspension thus obtained, 1.1 g of triazole in 10 ml of dimethylformamide was slowly added with stirring, followed by stirring at 20 ° C until bubbling ceased. Then 3.0 g of 2- (t-butyl) -2-25 (4-methylphenyl) -oxiran were added to the resulting solution and the resulting mixture was heated at 90 ° C with stirring for 6 hours. The resulting reaction mixture was then poured onto water, extracted with ethyl acetate, dried and chromatographed on silica gel, followed by elution with a mixture and equal parts of hexane and chloroform to yield a yellow oil which crystallized on standing. from which at-butyl-α- (p-methylphenyl) -1H-1,2, U-triazole-1-ethanol, mp: 69-71 ° C, was obtained from recrystallization from ethanol. The corresponding hydrogen oxalate (example 1A) has a melting point of 1U7-150 ° C, the p-methylbenzene sulfonate (example 1B) a melting point of 19 215-220 ° C and the hydrogen chloride (example 1C) a melting point of 2U7-250 ° C. The sodium ethanolate of the title compound has a melting point above 250 ° C (Example 1D).

Example 2

The following compounds according to the invention are also obtained according to the procedure of example 1: A) at-butyl-α- (p-chlorophenyl) -1H-1,2,4-triazole-1-ethanol, m.p .: 11 h -115 ° B) at-butyl-a ** (o, p-dichlorophenyl) -1H-1,2tk-triazole-1-ethanol, mp .: 63-6U °.

C) o-t-butyl-a- (m, p-dichlorophenyl) -1H-1,2 + triazole-1-ethanol, mp .: 156-157 °.

D) α-t-butyl-α-phenyl-1H-1,2,4-triazole-1-ethanol, m.p .: 8U-86 °.

E) α-n-decyl-ct- (p-methylphenyl) -1H-1,2, -triazole-1-ethanol.

F) α -t. butyl-α - (p-fluorophenyl) -1H-1,2,1; -tri azole-1-ethanol, m.p .: 10 ^ -106 ° G) α-t.butyl-a- (p-methoxyphenyl) - 1H-1,2, U-triazole-1-ethanol, m.p .: 76-79 °.

H) a-n-butyl-a- (o, p-dichlorophenyl) -1H-1,2, U-triazole-1-ethanol, m.p .: 109-110 °.

I) a-n-propyl-a- (p-chlorophenyl) -1H-1,2, -triazole-1-ethanol.

J) a - i-butyl-a- (p-chlorophenyl) -1 H-1,2, U-triazole-1-ethanol.

K) α-methyl-α- (p-chlorophenyl) -1H-1,2, U-triazole-1-ethanol.

L) α-t.butyl-a- (p-biphenylyl} -1H-1,2, + triazole-1-ethanol, mp: 117-118 °.

M) a-t-butyl-a- (m, p-methylenedioxyphenyl) -1H-1,2, U-triazole-1-ethanol.

N) a-t-butyl-a- (m-cyanophenyl) -1H-1,2, -triazole-8006170 20-ethanol, mp .: 123-12U °.

O) ce-t. butyl-α - (m-nitrophenyl) -1H-1,2, - triazole-1-ethanol.

P) α-t.butyl-α- (p-phenoxyphenyl) -1H-1,2, U-triazole-1-ethanol, mp .: 112-113 °.

Q) α-methyl-α- (m, p-dichlorophenyl) -1H-1,2, U-triazole-1-ethanol, m.p. 97-99 °.

R) α-n-propyl-α-phenyl-1H-1,2, H-triazole-1-ethanol, m.p .: 81-83 °.

S) α-ethyl-α- (p-chlorophenyl) -1H-1,2, -triazole-1-ethanol, mp .: 108-109 °.

T) α-n-hutyl-α-phenyl-1H-1,2,1 + triazole-1-ethanol, m.p. 67-68 °.

tl) α-isopentyl-α-phenyl-1H-1,2, U-triazole-1-ethanol, m.p .: 78-80 °.

V) α-η-propyl-ot- (p-methylphenyl) -1H-1,2, - triazole-1-ethanol, mp .: 86-88 °.

W) α-methyl-α- (p-methylphenyl) -1H-1,2, U-triazole-1-ethanol, m.p. 78-80 °.

X) α-n-pentyl-α-phenyl-1H-1,2, U-triazole-1-ethanol, m.p .: 89-90 °.

Y) α-isopropyl-α-phenyl-1H-1,2, U-triazole-1-ethanol, m.p. 71-73 °.

Z) a-n-butyl-a- (p-c-chlorophenyl) -1H-1,2, l-triazole-1-ethanol, m.p. 108-109 °.

Z-1) a-n-butyl-a- (p-methylphenyl) -1H-1,2, U-triazole-1-ethanol, mp .: 79-80 °.

Z-2) α-methyl-α- (m-trifluoromethylphenyl) -1H-1,2, It-triazole-1-ethanol, as oil.

Z-3) α-t-butyl-a- (m-trifluoromethylphenyl) -1H- 1,2, U-triazole-1-ethanol, mp: 120-122 °.

Z-U) α-t-butyl-α- (m-methylphenyl) -1 Η 1,2,1 + -triazole-1-ethanol, m.p .: 93-9%.

Z-5) α-t-butyl-o- (o-methylphenyl) -1H-1,2, H-triazole-1-ethanol.

8006170 21 Ζ-6) α-t.butyl-α- (p-t-butylphenyl) -1H-1,2, U-triazole-1-ethanol, m.p .: 108-110 °.

Z-T) a-t-butyl-a- (p-ethylphenyl) -1H-1,2,1 + triazole-1-ethanol, mp .: 91-9 ^.

Z-8) α-t-butyl- (m-phenoxyphenyl) -1H-1,2, U-triazole-1-ethanol, mp .: 133-135 °.

Z-9) a -t-butyl-a - (m-methoxyphenyl) -1H-1,2,1 + -triazole-1-ethanol, mp: 59-61 °.

Z-10) o-t-butyl-a- (p-trifluoromethoxyphenyl) -1H-10 1,2,1-triazole-1-ethanol.

Z-11) α-cyclohexyl-α - (p-methylphenyl) -1H-1,2, U-triazole-1-ethanol, mp .: 102-103 °.

Z-12) α-hexyl-o (p-methylphenyl) -1H-1,2,4-triazole-1-ethanol.

Z-13) α-octyl- (p-methylphenyl) -1H-1,2, U-triazole-1-ethanol, mp: 79-81 °.

Z-1U) α-dodecyl-a- (p-methylphenyl) -1H-1,2, U-triazole-1-ethanol, mp .: 78-79 °.

Z-15) a-t-butyl-cu (p-bromophenyl) -1H-1,2, U-20 triazole-1-ethanol, mp: 12U-125 °.

Z-16) cueopentyl-cu (p-methylphenyl) -1H-1,2, -triazole-1-ethanol.

Z-17) <* - sec. -butyl-cu (p-methylphenyl) -1H-1,2, U-triazole-1-ethanol, 25 Z-18) cu (1,1-dimethylpropyl) - a- (p-methylphenyl) - 1H-1 , 2, k-triazole-1-ethanol.

Z-19) out-butyl-cu (m, m-dibromophenyl) -1,1-1,2, U-triazole-1-ethanol.

Z-2 O) cucyclopropyl-ou (p-methylphenyl) -11I-1,2,1 + -30 triazole-1-ethanol.

Z-21) ou (2-methylcyclopropyl) -a- (p-methylphenyl) -1H-1,2, -triazole-1-ethanol.

Z-22) oucyclohexylmethyl-α- (p-methylphenyl) -1H-1,2,1-triazole-1-ethanol, m.p. 79-81 °, 35 Z-23) α-cyclopentylmethyl-α- (p-methylphenyl) -1H-8 0 06 1 7 0 22 1.2, k-triazole-1-ethanol, m.p. 7 ^ -76 °.

Z-2k) a- (1-ethylpropyl) -cr (p-methylphenyl) -1H-1.2, U-triazole-1-ethanol, mp .: 87-89 °.

Z-25) - ((1-methylbutyl) -a - (p-with methylphenyl) -1H-5 1,2, triazole-1-ethanol).

Z-26) α-t-butyl-a- (m-bromo-p-methylphenyl) -1H-1.2, U-triazole-1-ethanol, mp .: 155-158 °.

Z-27) a -t-butyl-a - (m-fluoro-p-methylphenyl) -1H-1,2, -triazole-1-ethanol, mp .: 102-10h °.

10 Z-28) at-butyl-a- (m-chloro-p-methylphenyl) -1H-1,2-triazole-1-ethanol, m.p .: 1UU-1 Vf °, Z-29) at-butyl- a - (m-chloro-m-methoxyphenyl) -1H-1.2, U-triazole-1-ethanol.

Z-3 O) a-t-butyl-a- (p-trifluoromethyl-m-chlorophenyl) -15 1H-1,2, H-triazole-1-ethanol.

Z-31) α-t-butyl-α - (m-chloro-m-phenoxyphenyl) -1H-1.2, lt-triazole-1-ethanol.

Z-32) α-cyclopentyl-α-phenyl-1H-1,2, Wtriazole-1-ethanol, as oil.

Z-33) α-eyelopropyl-α- (p-c-chlorophenyl) -1H-1,2, U-triazole-1-ethanol, as oil.

Z-3h) α-cyclobutyl-α- (p-fluorophenyl) -1H-1,2, U-triazole-1-ethanol, m.p .: 83-8U0.

Z-35) a-t-butyl-a- (m, p-dimethylphenyl) -1H-1,2, U-25 triazole-1-ethanol, mp: 120-122 °.

Z-3e) α-t-butyl-a. (O-methoxy-m-methylphenyl) -1H-1.2, U-triazole-1-ethanol.

Z-37) a-t-butyl-a- (o-methyl-p-methylthiophenyl) -1H-1,2, U-triazole-1-ethanol.

Z-38) α-t-butyl-a- (m-methyl-p-phenoxyphenyl) -1H-1.2, U-triazole-1-ethanol.

Z-39) α-t-butyl-a- (o-methyl-m-nitrophenyl) -1H-1.2, U-triazole-1-ethanol.

Z-1 + O) α-cyclobutyl-α-phenyl-1H-1,2, U-triazole-1 -35 ethanol, as oil.

80 06 17 0 23 Z-41) α-sec. -butyl-ct- (p-chlorophenyl) -1H-1,2,4-triazole-1-ethanol, as oil.

Z-42, ct-t, butyl-α-phimethyl-dichlorophenyl) -1H-1,2,4-triazole-1-ethanol, mp: 145-147 °.

Z-43) α-t-butyl-α- (m -chlorophenyl) -1H-1,2,4-triazo-1-ethanol-mp: 126-127 °.

Z-44) a-t-butyl-a- (p-cyano-enyl) -1H-1,2,4-triazole-3-ethanol, mp: 105-107 °.

Z "45) α-cyclopetyl-α- (p-methylphenyl) -1H-1,2,4-triazol-1-ethano1.

Z-46) α-isobutyl-α-phenyl-1H-1,2,4-triazole-1-ethanol. Z-47) a- (1-methylcyclopropyl) -a-p-methylphenyl-1H-1,2,4-triazole-1-ethanol, mp: 126-128 °.

Z-48) α-methyl-α- (p-diphenylyl) -1H-1,2,4-triazole-1-ethanol, mp .: 115-120 ° C.

Z-49) a-tert-butyl-a (p-iodophenyl) -1H-1,2,4-triazole-1-ethanol, mp .: 78-80 ° C.

Z-50) a- (3-heptyl) -a- (p-methylphenyl) -1H-1,2,4-triazole-1-ethanol, oil.

Z-51) a- (2-pentyl) -a- (p-methylphenyl) -1H-1,2,4-triazole-1-ethanol, mp .: 89 - 91 ° C

Z-52) a- (t-butyl) -a- (m.m'-dimethylphenyl) -1H-1,2,4-triazole-1-ethanol, mp .: 128-180 ° C.

Z-53) a- (t-butyl) -a- (3-nitro-4-methylphenyl) -1H- 1.2.4-triazole-1-ethanol, m.p .: 160 - 161 (dec.) Z-54) ct- (t-butyl) -a- (3,5-dinitro-4-methylphenyl) -1H-1,2,4-triazole-1-ethanol, m.p .: 194 - 196 (dec.)

Example 3: ct-t.butyl-a- (p-carboxyphenyl) -1H-1,2,4-triazole-1-ethanol and its potassium salt.

A mixture of 1.3 g at-butyl-a- (p-methylphenyl) -1H-1, 2,4-triazole-1-ethanol, 1.89 g potassium permanganate and 19 ml water 1 was boiled with stirring under reflux for hours. The resulting reaction mixture was then filtered while it was still hot, the resulting residue was washed with 10 ml of hot water, the filtrate was treated with charcoal and concentrated under reduced pressure to a small volume (4ml) which was dried under high vacuum, 8006170 2k to give the potassium salt of at.-butyl-a- (p-carboxyphenyl) -1H-1,2, U-triazole-1-ethanol, mp: 19 ° C (dec.).

This reaction was repeated using three times the amounts of the above materials except that the filtrate was now washed with diethyl ether, the ether solid was solid with water, the combined vats were acidified with concentrated hydrochloric acid with stirring until no additional precipitate was formed. and filtered the precipitate, washed several times with diethyl ether and dried under high vacuum to give at-butyl-α- (p-carboxyphenyl) -1H-1,2, 1-triazole-1-ethanol, m.p .: 2U8- 250 ° C, obtained.

Example 2- (t-butyl) -2- (U-methylphenyl) oxiran

A 2.2 g portion of 61 U% sodium 15 hydride was washed three times with petroleum ether, then 10 ml of dimethyl sulfoxide was added and the resulting mixture was heated to 70 ° C with stirring, after which the temperature rose to 85 by the exothermic reaction. ° C, after which the mixture was heated at 75 ° C for a further 0 min. The resulting mixture was then cooled in a mixture of ice and salt to 0 ° C and a solution of 7.0 g of trimethylsulfonium iodide in 50 ml of dimethyl sulfoxide and 20 ml of tetrahydrofuran was added dropwise in a nitrogen atmosphere. 18 ° C. Then, a solution of 3.0 g of t-butyl-p-methylphenyl ketone in 30 ml of tetrahydrofuran was added to the resulting mixture, with stirring and in a nitrogen atmosphere, while keeping the temperature below 10 ° C. The resulting mixture was then stirred for an additional 30 minutes at 0 ° C and then for 2 hours at room temperature. The resulting reaction mixture was then poured onto 100 ml of water, extracted with methylene chloride, the organic phases were washed with water and then with a solution of sodium chloride in water, dried and evaporated to dryness, giving a yellow oil of 2- (t-butyl). -2- (k-methylphenyl) oxiran.

8 0 06 17 0 25

Example 5 α- (t.butyl) -α- (p-methoxycarbonylphenyl) -1H-1,2, triazole-1-ethanol

It was added dropwise to a flask containing a solution of CH 2 in diethyl ether, prepared in a conventional manner from 3.39 g of N-methyl-N-nitroso-p-toluenesulfonamide, at 0 ° C, while the flask was ice bath continued to cool, adding a solution of 1.5 g of a- (t-butyl) -a- (p-carboxyphenyl) -1H-1,2, k-triazole-1-ethanol in 85 ml of dry tetrahydrofuran. The resulting mixture was then allowed to stand under ice-cooling until thin-layer chromatography revealed that the triazole starting material was virtually absent. A few drops of acetic acid were then added to decompose the excess diazomethane, the mixture was concentrated to remove tetrahydrofiran, the extracted product obtained was extracted with diethyl ether and washed with a 2N sodium hydroxide solution. After drying, white crystals formed on standing.

These crystals were filtered off and recrystallized from a mixture of CHgClg and diethyl ether to give the title compound, m.p. 152 DEG-15 DEG.

80 06 17 0

Claims (18)

1. Compounds of formula 1, wherein R ° is an alkyl group of at most 12 carbon atoms, a cycloalkyl group of 3-8 carbon atoms or a cycloalkylalkyl group of 5 U to 11 carbon atoms, wherein the cycloalkyl portion contains 3 to 8 carbon atoms and the alkyl portion 1 to 3 contains carbon atoms, which eyeloalkyl and cycloalkylalkyl groups are optionally substituted by 1 or 2 alkyl groups with 1-3 carbon atoms, R a hydrogen atom, a halogen atom with a sequence no. 10 from 9 to 35, an alkyl group with at most 4 carbon atoms, a mono-, di- or trihaloalkyl group with at most b carbon atoms, in which the halogen atoms independently have a sequence of 9 to 35, a alkoxy group with at most carbon atoms, an alkylthio group with at most b carbon-15 atoms or a nitro group, R 'a hydrogen atom, a halogen atom with a sequence no. from 9 to 53, an alkyl group with at most U carbon atoms, a mono-, di- or tri-haloalkyl group with at most b carbon atoms, in which the halogen atoms, independently of each other, are sequential. from 9 to 35 ", have an alkoxy group with at most b carbon atoms, a mono-, di- or tri-haloalkoxy group with at most U carbon atoms, in which the halogen atoms, independently of each other, have a sequence of 9 to 35, an alkylthio group with at most U carbon atoms, a nitro group, -CN group, -C00R "group, a group 25 of formula 7 or 8, R" have a hydrogen atom or an alkyl group with at most b carbon atoms, R'11 a hydrogen atom a halogen atom with a sequence of 9 to 17 or an alkyl group of 1 or 2 carbon atoms and Z represent an oxygen or sulfur atom, or wherein R and R 'together represent an alkylenedioxy group 30 having 1 or 2 carbon atoms, the carbon atoms of which adjoin substituted on the phenyl ring A are and Y ° and Y, independently of each other, are a hydrogen atom, a halogen atom with a sequence of 9 to 35, an alkyl group with at most b carbon atoms or an alkoxy group with also at most 35 b carbon atoms 8 0 06 17 0 Compounds according to claim 1, wherein R is a hydrogen atom, a halogen atom with a sequence no. from 9 to 35, a trifluoromethyl group or an alkyl group with at most H carbon atoms, R 'a hydrogen atom, a halogen atom with a sequence no. from 9 to 35, an alkyl group with at most b carbon atoms, an alkoxy group with at most H carbon atoms or an alkylthio group with also at most b carbon atoms, a CN group, a group of formula 7 or 9, wherein Y ° and Y have the meanings indicated in claim 1 and R '' represents a hydrogen atom. Compounds according to claim 2, wherein R is a hydrogen atom, a fluorine, chlorine or bromine atom, a trifluoromethyl group or an alkyl group with at most b carbon atoms and R 'a hydrogen, fluorine or chlorine atom, a 15 represent the CN group, an alkyl group with 1 or 2 carbon atoms or an alkoxy group with also 1 or 2 carbon atoms. b. Compounds according to claim 2 wherein R represents a hydrogen atom and Rr represents a group of formula 7 or 9 placed para to ring A and wherein Y ° and Y 20 have the meanings set out in claim 1. Compounds according to claim H, wherein Y ° and Y each represent a hydrogen atom. 6. Compounds according to claims 1-5, wherein R ° represents an alkyl group with 2 to 10 carbon atoms or an cycloalkyl group with 3-6 carbon atoms. Compounds according to claim 6, wherein R ° represents an alkyl group with 3 to 6 carbon atoms or a cycloalkyl group also with 3 to 6 carbon atoms. Compounds according to claim 7, wherein R 30 represents a butyl or propyl group. Compounds according to claim 7, wherein R ° represents a t-butyl group. Compounds according to claim 7, wherein R ° represents a cyclopropyl group. Compounds according to claim 7, wherein R ° represents a cyclopentyl group. 12.ot-t.butyl-a- (p-methylphenyl) -1H-1,2, U-triazole-1-ethanol 13.α-t.butyl-a- (p-chloropheny 1) -1H -1.2, U-5 triazole-1-ethanol. 1k. o-t, butyl-a- (o, p-dichlorophenyl) -1H-1,2, U-triazole-1-ethanol. 15. α-t-butyl-α-phenyl-1H-1,2, U-triazole-1-ethanol. 16. a-n-butyl-a- (o, p-dichlorophenyl) -1H-1,2, U-1-triazole-1-ethanol. 1T. α-t, butyl-α- (p-phenoxyphenyl) -1H-1,2,1 + -triazole-1-ethanol. 18. a-n-butyl-a- (p-methylphenyl) -1H-1,2,1 + triazole-1-ethanol. 15 19. at-butyl-a- (m-trifluoromethylphenyl) -1H-1,2, H-triazole-1-ethanol, 20. at-butyl-a- (m-methylphenyl) -1H-1,2, h triazole-1-ethanol. 21. α-cyclopentyl-α-phenyl-1H-1,2, U-triazole-1-20 ethanol. 22. α-cyclopropyl-α- (p-chlorophenyl) -1-1,2,1,1-triazole-1-ethanol. 23. a-t-butyl-a- (m, m-di-chlorophenyl) -1,2-1,2, U-tr i-azole-1-ethanol. 2k, a-t-butyl-a- (m -chlorophenyl) -1H-1,2,4-triazole-1-ethanol. 25. a-t-butyl-a- (p-cyanophenyl) -1H-1,2,1 + triazole-1-ethanol. 26. α-cyclopentyl-α- (p-methylphenyl) -1H-1,2,1 + -3Q triazole-1-ethanol. 27. a-t-butyl-a- (p-fluorophenyl) -1H-1,2, H-triazole-1-ethanol. 28. α-t-butyl-α- (p-methoxyphenyl) -1H-1,2,1 + triazole-1-ethanol. 29. a-t-butyl-a- (p-biphenylyl) -1H-1,2,1 + -triazole- 8 0 06 1 7 0 1 -ethanol. 30. α-t-butyl-α- (m-cyanophenyl) -1H-1,2,4-triazole-1-ethanol. 31. α-t.butyl-a- (p-ethylphenyl) -1H-1,2,4-triazole-5-ethanol. 32. α -t.buty1-a- (m-phenoxyphenyl) -1H-1,2,4-triazole-1-ethanol. 3 3. α-t-buty1-a- (m-methoxyphenyl) -1H-1,2,4-triazole-1-ethanol. 34. ct-cyelohexyl-α- (p-methylphenyl) -1H-1,2,4-triazole-1-ethanol. 35. α-octyl-α- (p-methylphenyl) -1H-1,2,4-triazole-1-ethanol. 36. α-dodecyl-α- (p-methylphenyl) -1H-1,2,4-tri-5-azole-1-ethanol. 37. α-t.buty1-α- (p-bromophenyl) -1H-1,2,4-triazole-1-ethanol. 38. a- (1-ethyl-propyl) -a- (p-methylphenyl) -1H- 1,2,4-triazole-1-ethanol. Compounds according to any of the preceding claims in free form. Compounds according to any of claims 1-38 in salt form or metal comolex form. 41. A method for controlling phyto-pathogenic fungi in plants, seeds or soil, characterized in that these plants, seeds or soil are treated with one or more compounds according to claim 1-10, in free form, and / or in an agribly acceptable salt and / or metal complex form. 3® 1 + 2. Method according to claim 41, characterized in that phytopathogenic fungi in plants or soil are controlled by applying 0.005-2 kg per hectare of one or more compounds according to claims 1-40. 43. Process according to claim 42, characterized in that 0.01 - 1 kg per hectare of one or 80 06 17 0 a number of compounds according to claims 1-Uo are used. HU. Method according to any one of the preceding claims for controlling phytopathogenic fungi in seeds, characterized in that these seeds are treated with 0.05-0.5 g per kg of seed of one or more compounds according to claims 1-Πθ. U5. Process according to claim, characterized in that 0.1-0.3 g per kg of seed of one or more compounds according to claims 1-Ho is used. 10 U6. Process for preparing a fungicidal composition, characterized in that one or more compounds according to claim 1-Ho, in free form and / or in the form of an acceptable salt and / or complex form in the field of agriculture, if desired together with a fungicidal carrier and / or diluent, in a dosage form suitable for such application. U7. Process according to claim H6, characterized in that 0.0005 - 90 wt.% Of one or a number of compounds according to claims 1-Ho, in free form and / or in an agricultural form acceptable salt form and / or in the form of a metal complex. H8, Process according to claim Ut, characterized in that 0.0005 - 10% by weight of one or more compounds according to claims 1-Ho, in free form and / or in an agricultural area acceptable salt and / or metal complex form. H9. Process according to claim UT, characterized in that a concentrated preparation containing 2-80 wt.% Of one or more compounds according to claim 1-H0, in free form and / or in an agriculture-acceptable salt-30 and / or metal complex form. 50. Process for preparing an aromatic compound, characterized in that a compound of formula 1 defined in claim 1 is prepared by a) a compound of formula 2, wherein R °, R, R '35 and R, M are the have the meanings indicated above, in an inert, 8 0 06 1 7 0 - «4? organic solvent to react with a compound of formula 3, wherein X represents an alkali metal, b) prepare a compound of formula 1a, wherein R 2 and R have the meanings indicated above, by the methyl group of a compound of formula 1b, wherein R ° and R have the meanings indicated above to be oxidized, or c) prepare a compound of the formula 1e, wherein R and R ° have the meanings indicated above and alk represents an alkyl group with at most b carbon atoms, by a compound of the formula 1a esterify with an alkanol of the formula H, wherein alk has the meaning indicated above} or a reactive functional derivative thereof. 51. Methods as described in the description and / or examples. 52. Molded preparations obtained using a method according to any one of the preceding claims. 06 80 06 17 0 p / = h "y— \? M / ** Μ! · '". · ", I ζ_> ί;“ .- “Ι R. n = J HOOC' - 'R · N = 1 R "1 la - <j Ptp -— / r · N ^ J alkOOC cht, 1b 1c RR ΓΜλ KC, —N VS <, l" J | \> χ.Ν J alk-OH jf ^ -R "' CH} - S® CH® R '\ f R * V - R * -C-0 6 R 5 2. <3 '; -ο:. · - »: i 7 8 9» 8 0 0 6 17 0