CS235510B2 - Fungicide agent and method of efficient substances production - 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

A fungicidal composition comprising, as an active ingredient, a compound of formula (I)

OH ^R / = \ I / ^ = _R .íbr ^{c '!} 'M

R 0 (I) wherein the general symbols have the meanings given below.

Further, a process for the production of the aforementioned active ingredients is described.

23ЪЮ

The invention relates to a process for the preparation of .alpha.-aryl-1H-1H-triEZol-1-ethanol, in particular. aliaalkyl-alpha-phenyl-11,11,2,4-triazole-1-ethanols, their use as fungicides and agrochemical agents facilitating this use.

The present invention describes a process for the preparation of compounds of formula I

OH

in which

R ° represents Al ^ nominal with ^k u ^pt nu s 1 ^{and 12} carbon uhlíto c ^yk loal ^alkyl nominal s ^to u ^pt Nu 3 and ^also carbon atoms or cycloalkylalkyl skuptnu with 4 to 11 carbon atoms, wherein cykloelkylovl pure contains 3 and C 8-C a alkyl and C čist-C a alkyl, the above-mentioned cycloalkyl and cycloalkylalkyl groups are optionally substituted with one or two C až-C el alkyl groups.

R represents a hydrogen atom, a halogen atom of from 9 to 35, a C1-C4 alkyl group, a triflomethyl group, a C1-C4 alkoxy group, a C1-C4 alkyl group or a nitroscape group, and

R * represents a halogen atom having an atomic number of from 9 to 53, a C1-4 alkyl group, a triflooroethyl group, a C1-4 alkoxy group, a C1-4 alkyl group, a C1-4 alkyl group, a nitroscape group , cyano, phenyl, phenoxy, or COCO, wherein

R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, characterized in that the compound of formula II

in which

R ^0, Greek ^'s mount defined, NEC ^hl in an inert organic ^p ou extended ^by adding an organic solvent with a compound of formula III

(III) wherein

X is an alkali metal.

The reaction can be provádětpři temperature potybuuící the obvila from 0 to ¹ 80 ° С preferably from 4 ⁰ to 12 ⁰ C, in the ^u E ⁱ NEM ₄ ineotním, the combined organic rozpoitétědle n ^] ^ i ^ C ^k l ^ and ^ ^d the organic amide kθrbuoylfvélkkl; lazy as dtmetylfomamidl. As is customary, the compound of formula (III) is preferably reacted via a reaction of the formula (III). with a strong base such as an alkali metal hydride, for example with sodium hydroxide, in an inert organic solvent, which is conveniently the same as that used in the reaction according to the invention.

The reaction product resulting from the process according to the invention can be isolated from the reaction mixture in which it is formed by treating the mixture by conventional means.

239 91 О

Compounds of formula I in which H * is not a carboxyl group can be prepared and used in the form of acid addition salts. The compounds of formula (I) are ethanol derivatives and can therefore exist in free form and in alternative forms, such as a fused etoxide such as sodium ethoxide, or in the form of a complex with a metal such as a metal selected from Ib, Ha, lib, 71b, VIIb and VII of the periodic system of elements such as copper and zinc, and with anions such as enion. chloride, sulfate, nitrate, carbonate, acetate, citrate, dimethylditookarbamate and the like.

Salts of the compounds of formula (I) are preferably agronomically acceptable salts.

The aforementioned acid addition salts, dried etoxides and metal complexes can be prepared from the corresponding free form in a conventional manner, and vice versa.

Compounds of formula (II) may be prepared by reacting a compound of formula (V)

R R '

rO — C = O (V) in which

K ⁰ , as defined above, with the reaction product of a strong base and an ammonium iodide which is an agent of the formula VI

C ^H 3

CH ₃ - · CH (VT)

The reaction described above is carried out in an inert organic solvent. E is a known type of reaction used to prepare thpoxy derivatives from ketones.

Many of the compounds of formula (V) are known and those not known per se can be prepared from known compounds by procedures analogous to those known for the preparation of known compounds. Numerous compounds of formula II are also known.

The compounds of formula (I) are useful as fungicides in combating fungi ^, lopatogenic fungi, including in particular powdery mildew and rust fungi, as shown in the standard in vivo and in vitro tests described below. For this purpose, the compounds of formula (I) may be applied to plants, seeds or soil in the manner customary in the use of fungicidal agents. It will be appreciated that the amount of compound of formula (I) administered will depend upon known factors, such as the compound used, whether it is prophylactic or therapeutic, whether the compound is applied by spraying or foliaring, it treats the soil or is used here as a seed dressing agent, on the type of fungus to be treated and at the time of application.

In general, however, the results of application of the active ingredient to the place where the crop is grown, whether on the crop or in the soil, at a dose ranging from about 0.005 to 2, are achieved. Preferably from about 0.01 to 1 kg of active ingredient per hectare. The treatment may be repeated as necessary, for example at 8-day to 10-minute intervals.

In the case of the active substances as seed mooids, satisfactory results are obtained with the active compound in a dose of from about 0.05 to 0.5, preferably from about 0.1 to 0.3 g / kg of seed.

The term 'soil' includes all the usual growth environments, whether natural or artificial.

The invention also relates to fungicidal compositions comprising as active ingredient a compound of formula I in free form or in the form of an agronomically acceptable salt, and an inert carrier or diluent.

These compositions generally contain from about 0.000% to about 90%, preferably from about 0.1% to about 60%, of the mono -ootic active ingredient. Said compositions may be in a concentrated form which is diluted prior to administration or in a diluted form which can be administered directly. Examples of specific forms are wettable powders, emulsion concentrates, dusts, spray formulations, granules and sustained release formulations, which may contain conventional carriers and other diluents and / or auxiliaries customary in the field of agrochemistry.

The dosage forms of these compositions generally contain from about 0.000 to about 10% by weight of the active ingredient of the formula I as active ingredient. Typical spray suspensions may contain, for example, from 0.0005 to 0.05%, preferably from 0.001 to 0.02%, of the active ingredient. Concentrated forms of fungicidal compositions generally comprise from about 2% to about 90%, preferably from about 5% to about 70%, by weight of the compound of formula (I) as the active romronone. Emulsion concentrates generally comprise from about 10 to 70%, preferably from about 20 to 60% by weight of the active ingredient. Solid forms of particulate formulations are preferred.

Compositions especially formulated for spray application preferably contain a surfactant, such as liquid polygly, a series or ligoiosulfoate.

In addition to conventional carriers and surfactants, the compositions of the present invention may contain other special purpose additives such as stabilizers, deactivators (in the case of solid formulations on active surface carriers), plant adhesion promoters. , corrosion inhibitors, antifoams and colorants.

Other fungicides, bactericides or other beneficial agents, such as insecticides, may also be included in the compositions of the invention, and such combinations also fall within the scope of the invention.

The following are examples of the preparation of the fungicidal compositions of the present invention.

(a) a powder of parts of a compound of formula I, for example alpha-tert-butyl-alaa - (- ethylphenyl) -1H-1,2,4-triazul-1-etaoull, is milled with 2 dfly lalrylsilate; 3 parts of sodium ligoiosulfonate and 45 parts of finely divided kaolinite until the median particle size is less than 5 µm. The resulting spray formulation can be applied by foliar spraying as well as root dressing.

b) Grandma!

0.55 wt.% Of the quartz sand is sprayed onto the 94.5 parts of quartz sand. 5 parts by weight of a compound of the formula I, for example alpha-tert-butyl-ala- (p-oetylpheoyl) -1H-1 powder, 2,4-triazul-1-ethanol, and the resulting mixture is further intimately mixed to give a granular composition with a mean particle size of from 0.3 to 0.7 mm. Grandat can be applied by frying into the soil around the treated plants. ,

e) Emulsion concentrate

25. masses, parts by weight of a compound of the formula I, for example alpha-t-bityl'-alpha- (p-phenylphenD-1H-1,2,4-triazole-1-ethoxy), containing 30% by weight, parts by isooctyl-ethyl-octaglycoletri and 45 parts by weight of a petroleum fraction having a boiling point of 210 DEG-280 DEG C. (d = 0.92), and the concentrate is then diluted with water to the desired concentration.

d) A seed dressing of parts of a compound of the sacrificed formula I, for example alpha-tert- _β- bllll-aaa (β-methyllecyl) -1H-1,2,4-triastl-H-etacllll with 1.5 parts of the adduct disililine glycol ether and ethylene oxide, 2 parts of spindle oil, 5H parts of finely ground grit and 0.5 parts of rhodamit B dye. The obtained dry powdered monidine seed has good adhesion and can be applied to the seed, for example by stirring for 2 to 5 minutes in a slowly rotating vessel.

Among the fungi against which the compounds of formula I are particularly active are, for example:

A. Class of Baaidiomycctes, including

Al. uredinales fungi such as Uromyces fungi on such plants as the bean and beans such as Uroes csppiciculatls, and ornamental plants such as Uromyces dianthi, fungi of the genus Herníiaia on such plants as the coffee plant, e.g. HHmíieia vaststrix, fungi of the genus Puccinia and such bean-like species such as cereals (for example, gnat, oat, barley) such as Puccitia gramitis (grass rust), Puccinia reelcdits (wheat rust) and Puccinia striioorais (wheat rust), cnbo on ornamental plants, pelargontis grains and Puccinia antirrhLnL, fungi of the genus Phakopsora and other plants such as soybeans, for example Phakopsora paclhy ^ hzi, fungi of the genus Melampsora and such plants, such as lcu, for example Melamppora liti (rnz flax) and fungi of the genus Trsnz for example Trenzschheia pruci (plum rust) on plums;

A2. fungi of the order Uusicagicales such as fungi of the genus Ussilago and such plants such as barley, pines, maize and sugar cane, for example Ustilago mmydis (corn cob) and maize and dust. barley barley, a

A3. fungi of the order rheumatoid arthritis and stone fruit, for example Sternum purpurum leaves, apple and plum; -

B. Class Ascomcetes, including

Bl. fungi of the order Erysipheles, such as fungi of the genus Erysiphn, on such plants as cucumbers, cucumbers, wheat, and sugar beet, for example Erysiphn graminis f. sp. tritiei (grass powdery mildew) and wheat, and Erysiphe cichoгscealUi ta cucumbers, SpohaaroЪНесa fungi, on cucumbers and roses, for example Spohaerothtea pannosa (powdery mildew), Podosplhanre fungi on apple trees, pear plums (eg Podosphaera lerne) those of apple trees, fungi of the genus лс ^ пи!) those of plants such as on vines, for example Uncinula cncrtoe (powdery mildew) nn viccé vine, fungi of the genus Oidium and a large number of different plants ε fungi of the genus Levemu!) on such plants. on cotton and some mallow (Malvacnn), for example Eewallula ts-c on cotton;

23 »10

C. class Oycetes, comprising

C. fungi of the genus Phytophthore sp. Phytophthora cactorum _t for example, Phytophthora Phytophthora cinam.om.i pairnstics and various disease susceptible plants and

C2. Aphanomyces fungi on plants such as peas and sugar beet, for example, Aphanomyces euteěches on sugar beet, e

D. class Deuttrornycetes, including

D1. Heeminthosporum fungi on plants such as barley and maize, for example Helminthosporium seed,

D2. Septoria fungi on plants such as hayloft, tomato and celery, for example, Septoria tritici on wheat;

D3. Rhizoctonia fungi on plants such as cotton and potatoes, for example nhizoctonia solani.

D4. fungi of the genus Fusarium sp., for example Fusarium oxysporum f. sp. lycopersici (wilting of tomatoes) on tomatoes, Fusarium oxysporum, f. sp. vasinfecuum on cotton, Fusarium oxysporum f. sp. cubense on bananas, Fusarium solani (root pea) on vegetables, Fusarium cuimorum on cereals and Fusarium graminearum on cereals;

05. Thilaviopsis fungi not on plants such as cotton, tobacco, etc., such as Thilaviopsis basicola (black root rot) not on cotton,

D6. Fhome fungi on plants such as sugar beet, rape, etc. · such as Phome betae (heart disease and dry rot) on sugar beet,

D7. fungi of the genus Piriculeria spp., for example, Piricularia oryzae on rice; and

D8. fungi of the genus Cooietotichuum spp., for example, ColletotrCiumum indemuthianum (bean anthracnose) on fezoles.

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

Test A

In vivo test against Stubborn appenduculatus (bean cut)

The beans of the bean (Phaseolus vulgaris) were grown for 9 days in 6 cm diameter plastic dishes filled with peat and sand. The test plants are sprayed with a spray formulation containing 0.000 8 to 0.05% (for example 0.000 8%, 0.003%, 0.012% and 0.05%) of the active substance. The treatment can be carried out by spraying on the leaf until almost run off or by watering the soil (28 ml of preparation per dish). After drying the plants. Inoculate by spraying a spore suspension (500,000 to 700,000 spores / ml) and incubate for 7 days. in the incubation chamber at 100% relative. humidity and 21 ° C. The efficacy of the treatment with the active ingredient is determined by comparing the number of rust / l-ist piles on the treated plants with that of untreated, similarly inoculated control plants.

Compounds of formula (I), in particular those of below. the examples, for example the compounds of Examples 1, 1A, 1B, 1C, 2A, 2B, 2D, 2F, 2G, 2H, 2L, 2N, 2P, 2Z-1, 2Z-3, 2Z-4, 22-7, 21-8, 21-9, 21-11, 21-13, 2Z-14, 2Z-15, 2Z-24, 2Z-27, 2Z-28, 2Z-32, 2Z-33, 2Z-41 to 2Z -44 and 3, used in the form of the above-described wettable powder, show a significant degree of fungicidal activity in the above test, both in contact and systemic action (the active substance takes root).

With similar results, analogous tests were performed using the following crops and fungi:

coffee wheat pseni.ce wheat wheat flax geranium snapdragon

Hemňleia vaasaárix (Rust of the Ears)

Puucinia graminis (Black Rust Grass)

Puucinia recondita (Wheatgrass)

Pucccnia striiormnis

Melampsora linea

Puucinia pelargosni 'zsnθait

Puucinia annirrhini (rust)

Test B

In vivo test against Erysiphe cichoracearum (paadí)

The cucumber (Cucumis sotivus) is sown in a 6 cm plastic bowl filled with a mixture of peat and sand for 7 days. The roostins are then coated with a postostasis preparation containing 0.000 8 to 0.05% (for example 0.000 8%, 0.003%, 0.012% and 0.05%) of the active ingredient. The treatment can be carried out by spraying on the leaf until almost run off or by watering the soil (28 ml of preparation for each raisin). After drying, the plants are inoculated by dusting with freshly collected conidia of the fungus and incubated for 7 days. in an incubation chamber at 60 to 80% relative humidity and 25 to 30 ° C. The efficacy of the active compound is determined by comparing the degree of infestation of treated fungi with that of untreated, similarly inoculated control plants.

Compounds of formula (I), in particular compounds of the Examples below, for example compounds of Examples 1, 2A, 2B, 2C, 2D, 2F, 2G, 2H, 2L, 2N, 2P, 2Q, 2R, 2S, 2T, 2U , 2 / 2Z-1, 22-3, 2Z-4, 2Z-6 to 2Z-9, 2Z-1 1, 2Z-13 to 2Z-1>, 2Z-24, 22-26, 2Z-27, 2Z-28, 22-35, 2Z-40 to 22-47, 1Α, 1B, 1C and 3, used in the form of the above-described wettable powder, exhibit a significant degree of fungicidal efficacy ₉ in both the above contact test. systemic action (active substance takes root).

Similar results are obtained in tests analogous to Test B carried out with the following crops and fungi:

wheat: Erysiphe graminis i sp. tritici · Barley: Erysiphe graminis i. sp. hordei (fallen grass on barley) apple tree: P-odosphaera luecotrcchr (fallen apple tree) grapevine: uncinula necator (grape vine)

The test B described above to determine the efficacy of Erysiphe iichoraiearui is repeated with the preferred compound of Example 1, which is applied both by foliar spray and soil dressing, but at lower concentrations, 0.000 2% and 0.000 05%, respectively. yet 100% of the fungus is still treated, further demonstrating the remarkable effectiveness of the compounds of the invention.

In the wall test, when applied to the compound at 0.000012% and 0.000003% concentrations respectively, a spray application of 70% and 100%, respectively, was achieved. 50% and 90% resp. 70% efficacy.

By repeating Test B above against Erysiphe gram. hordei at 0.000 2% resp. 0.000 05% achieves 70% resp. 55% efficacy and 80% resp. 70% ^ плоШ.

Repeating test B against Erysiphe graminis f. Sp. tritici when applied to the above compound in concentrations of 0.0002% resp. 0.000 05% doodi for spray application 80% resp. 60% efficiency, 90% resp. 70% efficiency.

The results of tests against various species of mildew and rust inducing fungi carried out with representative compounds of the invention as described above in Examples A and B are summarized in Table I. Comparative results obtained using two standard comparatives known from DOS 26 54 890 under analogous conditions, are given in Table II.

2355Ю

Efficacy test against mildew and rust inducing fungi

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<n X o X o Φ- 't • φ

Tr — CH — CHOH— <Λ | <2 approx. 500 120 to 500 approx. 30 approx. 30> 500

1

Legend:

Tr -

N --- N-

comparative active substances are known from Examples 1 and 12 of DOS No. 26 54 890

In these tables, the results are given in EC 50 values, which are the concentrations of the respective active substances which achieve 90% control of the respective fungal disease.

Compared to the structurally closely related comparators known from DOS No. 26 54 890, the active compounds after the invention show a very favorable action against powdery mildew on cereals and / or an excellent anti-rust effect.

Test C

In vitro test against Uutilago maydis

Different quantities of active ingredient are applied to malt agar plates to achieve active ingredient concentrations of 0.8 to 200 ppm (e.g. 0.8, 3.2, 12.5, 50 and 200 ppm). The plates are then inoculated by either spraying a sputum suspension with Uutilago maydis or placing a piece of agar containing sponge in the center of the plate. The plates were incubated at room temperature for 2 to 5 days. The efficacy of drug treatment is determined by comparing fungal growth on treated plates with fungal growth on untreated, similar inoculated plates.

In Test C, the compounds of formula I exhibit moderate to good activity. For example, the compounds of Examples 1, 2A and 2Z-1 below exhibit in the assay. C in low and high good efficiency.

In an analogous test for Fusarium oxysporum f. Sp. show compounds of Formula I, for example those of Examples 2A, 2B, 2D, 2P, 2R, 2S, 2Z, 2Z-32, 22-34, and 2Z-46 of moderate to good activity. .

The fungi of the aforementioned genera cause considerable damage to the zenithing and it is difficult to prevent or treat the onemooning caused by them. In addition to being able to control these fungi, the compounds of formula I are non-phytotoxic at the effective doses required to treat the plants against these fungi and are of particular interest because they are also able to eat fungi systemically, as found, for example, Uromyces appencliculatus on bean.

In further tests carried out analogously to Test C using the compound of Example 1 at concentrations of 13, 50 and 200 ppm, it was found that at least one of these concenations, the above compound showed 100% activity (except where indicated). otherwise) against the following fungi:

Phytophthora ced ^ o ^ j ^ i ^ m (maximum efficiency 45%)

Phytophthora cinamomi (maximum efficacy 65%) Aphenomyces euteiches

Ste’reum purpureum

Thielaviopsis besicole

Piricularie oryzae

Cotletotreihum lindemuthinnum (maximum efficiency 90%).

In further tests carried out analogously to Tests A and B, the compound of Example 1 below showed a spray rate of 32%, 125% and 500 ppm 75%, 95% rsp. 100% activity against Helminthosporium on barley, with 20% phytotoxicity when applied at a higher dose.

Test D

In vivo test against Rhhzoctonia solani (Potato Root)

The fungus is cultured in sterile Zonnoit and corn flour (10: 1 imoOnnot / imoOnosS) to which water is added at a ratio of about 1: 1 (irnootoot / irnootnot). Cultivation was carried out at 25 ° C for 14 days. The sponge is admixed with a porous peat brew sand mixture which is then treated with a suspension containing the active ingredient to a concentration of from 10 to 160 ppm (e.g., 10, 40 and 160 ppm) based on the substrate volume. The substrate is transferred to 5 cm diameter pots, which are then planted with cotton seedlings (cotyledons stage). Planted pots are inkubuuí 14 days in an incubation chamber at 4 ° ^{C 2} to ⁶⁰ and ^70% гпЫ vlhkot ^ !, načj ^F is determined fungus attack roots and hypocotyls comparison to untreated, similarly inoculated plants konnmlních.

Compounds of formula (I) show good efficacy in Test D. The compound of the following example 1, used in the form of the wettable powder described above, exhibits, for example, 100% disease control activity, with no phyto-effect at a lower dose. toxic.

In a test carried out analogously to Test D against Phoma betae (heart disease and dry rot) on sugarbeet, the compounds of formula I, for example the compounds of Examples 1, 1A, 1B, 1C, 2A, 2B, 2D, 2N, 2P, 2R, 2T, 2Y, 2Z, 2Z-1, 2Z-4, 2Z-7, 2Z-8, 2Z-11,22-15, 22-32, 22-33, 2Z-34 and 2Z-41 good efficiency.

From the foregoing, it will be apparent to those skilled in the art that the compounds of the invention, in addition to their considerable interest and value for combating powdery mildew and rust, are of particular interest in combating important soil fungal fungi transmissible by seed.

strange . the value and the advantage of the invention are evidenced and / or confirmed by more detailed investigations of the compound of Example 1 below, which exhibits remarkable properties in some cases with remarkable properties:

1. Stability of action which still allows 100% destruction of Uromyces spp. on creeping bean when sprayed with 0.012% spray 8 days prior to inoculation;

2. good stability and aqueous spray suspensions, as evidenced by 100% activity against Ummyces spp. on creeping bean, when applied at a concentration of 0.012% active ingredient, which is used up to 3 days after preparation;

3. rapid and permanent penetration of the active substance into the leaves of treated plants, as evidenced by 100% efficacy of the preparation with a final concentration of 0.012% after

(a) daily washing of the leaves of the creeping bean from as little as 10 minutes after application of the active substance and subsequent soaking of Ummyces spp.

(b) a 15-minute washing of the vine leaves 2 hours after application of the active substance and subsequent infestation with a fungus of the genus Unncnula,

c) simulated rainwater washing of the leaves of the coffee tree (50 mmmhh rainfall, the simulated rain being applied for 15 minutes at 2 hours after application of the active substance, followed by drying, second fifteen minutes of rain, new oschnuuf, third fifteen minutes of rain) and finally infesting the coffee tree with Hemmieia vastatrix, a

d) a simulated rain bean leaf wash (rainfall 50 mrn / h), the simulated rain being applied first for 10 hours at 2 hours after application, followed by drying, a second 10 minute application of rain, new o ^ h ^ nu: ^, the third 10 minutes. the application of rain and finally infesting the rossiin of the climbing bean with the fungus Uromyces sp., and

4. the excellent systemic character of the action of taansport of the active substance after its absorption by the leaves of the lower or upper part of the grapevine into the untreated parts of the plant, with 70% and 70% respectively being obtained; 75% proo! Unninula sponge on untreated upper and lower lesions, suggesting that this transport to untreated leaves takes place both acropetally and basipetally.

A further evaluation of the efficacy of the compound of Example 1 below revealed 100% fungicidal activity (compared to untreated standard plants) when the drug was applied at a concentration of 0.012% at 3 days (before sporulation) after infection of the creeping bean with Uromyces spp.

When applied at a concen- tration of 0.05% to creeping bean plants with already copulated rust clusters of Uromyces spp. se. from 10 days after application, 60% of the control of visible symptoms of the disease (compared to the treated accounts, the crop plants) will reach 60%. just 3 days. after 50%, 50% of the coating is applied.

The above further evaluations of the efficacy of the compound of Example 1 indicate the desired curative efficacy and at least a partial efficacy.

In the tests described above, other compounds of formula (I), in particular Examples 2A, 2B, 2D, 2F, 2G, 2H, 2L, 2N, 2P, 2Z-1, 2Z-3, 2Z-4, 2Z-7, 2Z-9, 2Z-11, 2Z-13 to 2Z-15, 2Z-24, 2Z-32, 2Z-33, 2Z-43 to 2Z-45 and 3 are also very good up to 1Z. 1: it has fungicidal activity. The fungicidal activity of the compound of Example 2A is at least the same as that of the compound of Example 1, and the compound of Case 2Z-33 also exhibits the same order of magnitude as the compound of Example 1.

Preferred compounds of formula I satisfy one or more, preferably all, of the following requirements:

a) R c represents an alkyl group having 2 to 10 carbon atoms, in particular an alkyl group having 3 to 10 carbon atoms, and in particular an alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or a cycloalkylemyl group, contains 3 to 6 carbon atoms;

b) R represents a hydrogen, fluorine, chlorine or bromine atom, a trifluoromethyl group or an alkyl group having 1 to 4 carbon atoms;

(c) ϋ ”represents a fluorine, chlorine or bromine atom, a (C1-C4) alkyl group, a (C1-C4) alkoxy group, a (C1-C4) cycloalkyl group, a cyano group, a phenyl group or a phenoxy group.

Even more preferred compounds of the aforementioned preferred group of compounds of formula (I) satisfy one or more, preferably all of the following requirements:

e.) № znlmnn ^and stylish Sapin having ³ to ⁶ carbon atoms, ^{Y b} not on the amount of lift the stencil to 6 carbon atoms, such as cyclopropyl and cyklopnntylovst,

b) R represents a hydrogen, fluorine, chlorine or bromine atom, a tri: Ulsomethyl group or a (C 1 -C 2) -tyl group; and

c) R * represents a fluorine or chlorine atom, a cyano group, an alkyl group having 1 or 2 carbon atoms or an alkoxy group having 1 or 2 carbon atoms, or

d) k represents a hydrogen atom and R * represents a phenyl group or a phenoxy group attached to the pera-position of ring A.

Particularly preferred compounds of the formula I are those in which R 0 is a propyl or butyl group, for example n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl, in particular n-propyl and isopropyl, as well as a branched butyl group, in particular a tert-butyl group. Other branched C 5 -C 6 alkyl groups, for example isopentyl and neopentyl, also appear to be of particular interest. Of particular interest are also those compounds in which R 0 represents a cyclopropyl, cyclopentyl or cyclohexyl group.

The invention is illustrated by the following non-limiting examples. In these examples, all temperatures are given in degrees Celsius.

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

0.62 g of 61.4% sodium hydride was washed three times with petroleum ether and then 10 ml of dimethylformamide was added with stirring. 1.1 g of triazole in 10 ml of dimethylformamide are slowly added to the resulting suspension while stirring, and the mixture is stirred at 20 DEG C. until gas evolution ceases. 3.0 g of 2- (tert-butyl) -2- (4-methylphenyl) oxirane was then added to the resulting mixture, and the mixture was heated to 90 ° C with stirring for 6 hours. The reaction mixture was poured into water, extracted with ethyl acetate and, after drying, chromatographed on silica gel using hexane / chloroform (50:50) as eluent.

A yellow oily material is obtained which crystallizes on standing to give a solid which, after recrystallization from ethanol, yields n-tert-butyl - (p-methylphenyl) -1H-1,2,4-triazole-1-ethanol, m.p. to 71 ° C. The corresponding hydrogen oxalate (Example IA) had a melting point of 147-150 ° C, the p-methylbenzenesulfonate (Example 1B) had a melting point of 215-220 ° C, the hydrochloride (Example 1G) had a melting point of 247-250 ° C, and sodium ethoxide derived from the compound in the title (example ID) melts above 250 ° G.

Example2

The following additional compounds of the invention were prepared in an analogous manner to Example 1:

A. 3'-tert-butyl-alpha- (p-chlorophenyl) -1H-1,2,4-triazole-1-ethanol, m.p.

114-115 ° G,

B. alpha-tert-butyl-alpha- (o, p-dichlorophenyl) -1H-1,2,4-triazole-1-ethanol, melting point up to 64 ° C,

G. alpha-tert-Butyl-alpha- (m, p-dichlorophenyl) -1H, 1,2,4-triazole-1-ethanol melting point

56-157 ° C,

D. alpha-tert-Butyl-alpha-phenyl-1H-1,2,4-triezol-1-ethanol, m.p. 84-86 ° C,

E. alpha-n-decyl-alpha- (p-methylphenyl) -1H-1,2,4-triazole-1-ethynol,

F. alpha-tert-butyl-alpha- (p-fluorophenyl) -1H-1,2,4-triazole-1-ethanol, m.p.

104-106 ° C,

G. alpha-tert-butyl-alpha- (p-methoxyphenyl) -1H-1,2,4-triazole-1-ethanol of melting point up to 79 ° C,

H. alpha-n-butyl-alpha- (o, p-dichlorophenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 109-110 ° C;

I. alpha-n-propyl-alpha- (p-chlorophenyl) -1H-1,2,4-triazole-1-ethanol,

J. alpha-isobutyl-alpha- (p-chlorophenyl) -1H-1,2,4-triazole-1-ethanol,

K. alpha-methyl-alpha- (p-chlorophenyl) -1H-1,2,4-triazole-1-ethanol,

L. alpha-tert-butyl-alpha- (p-biphenylyl) -1H-1,2,4-triazole-1-ethanol, m.p.

117-118 ° C,

M. alpha-tert-butyl-alpha- (m, p-ethylenedioxyphenyl) -1H-1,2,4-triazole-1-ethanol,

N. alpha-tert-butyl-alpha- (m-cyanophenyl) -1H-1,2,4-triazole-1-ethanol, m.p.

123-124 ° C,

C. alpha-tert-butyl-alpha- (m-nitrophenyl) -1H-1,2,4-triazole-1-ethanol,

P. alpha-tert-butyl-alpha (p-phenoxyphenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 112-113 ° C,

Q. alpha-Methyl-alpha- (m, p-dichlorophenyl) -1H-1,2,4-triazole-1-ethanol of melting point up to 99 ° C,

R. alpha-n-propyl-alpha-phenyl-1H-1,2,4-triazole-1-ethanol, m.p. 81-83 ° C,

S. alpha-ethyl-alpha- (p-chlorophenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 108-109 ° C

T. alpha-n-butyl-alpha-phenyl-1H-1,2,4-triazole-1-ethanol, m.p. 67-68 ° C,

U. alpha-isopentyl-alpha-phenyl-1H-1,2,4-triazole-1-ethanol, m.p. 78-80 ° C;

V. alpha-n-propyl-alpha- (p-methylphenyl) -1H-1,2,4-triazole-1-ethanol of melting point up to 88 ° C,

W. alpha-methyl-alpha- (p-methylphenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 78 and 80 ° C,

X. alpha-n-pemtyl-alpha-phenyl-1H-1,2,4-triazole-1-ethanol, m.p. 89-90 ° C;

Y. alpha-8-isopropyl-alpha-phenyl-1H-1,2,4-triazole-1-ethanol, m.p. 71-73 ° C;

Z. alpha-n-butyl-alpha- (p-chlorophenyl) -1H-1,2,4-triazole-1-ethanol, m.p.

109 ° C

Z-1. alpha-n-butyl-alpha- (p-methylphenyl) -1H-1,2,4-triazole-1-ethanol of melting point up to 80 ° C,

Z-2. alpha-methyl-alpha- (m-trifluoromethylphenyl) -1H-1,2,4-triazole-1-ethanol as an oil,

Z-3. alpha-B-tert-butyl-alpha- (m-trifluoromethylphenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 120-122 ° C;

Z-4. alpha-tert-butyl-alpha- (methylphenyl) -1H-1,2,4-triazole-1-ethanol, m.p.

Z-5. alpha-tert-butyl-alpha- (o-methylphenyl) -1H-1,2,4-triezol-1-ethanol,

Z-6. alpha-tert-butyl-alpha- (p-tert-butylphenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 108-110 ° C,

Z-7. alpha-tert-butyl-alpha- (p-ethylphenyl) -1H-1,2,4-triazole-1-ethanol, m.p.

Z-8. alpha-tert-butyl-alpha- (m-phenoxyphenyl) -1H-1,2,4-triazole-1-ethanol, m.p.

133-135 ° C,

Z-9. alpha-tert-butyl-alpha- (m-methoxyphenyl) -1H-1,2,4-triazole-1-ethanol of melting point up to 61 ° C,

Z-10. alpha-tert-butyl-alpha- (p-trifluoromethoxyphenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 80-83 ° C;

Z-11. alpha-cyclohexyl-alpha- (p-methylphenyl) -1H-1,2,4-triazole-1-ethanol, m.p.

102-103 ° C,

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

Z-13. alpha-octyl-alpha-β-p-methylphenyl-1H-1,2,4-triezol-1-ethanol, m.p. 79 ° C,

Z-14. elle-dodecyl-11H- (p-methyllenyl) -1H-1H-triazole-1-ethanol with a melting point of up to 79 ° C,

From — 15. δlff-errc.butll-lffep (p-bmoffenyl) -1H-1,2,4-triazole-1-eyanol, melting point

124 to 125 ° C, ‘

Z-16. (.alpha.-neopentyl-.alpha.-.beta.-p-methyllenyl) -1H-1H-triazole-1-ethanol,

Z-17. ' ellf-sec-butyl-alpha- ( ^p- methylphenyl) -1H-1,2,4-triazole-1-ethanol,

Z-18. slfa-O, 1-dimethyl-propyl-1-fl- (p-methylphenyl) -1H-1,2,4-triazole-1-ethanoo,

Z-19. fllf-tert-butyl-1 H- (m-chlorophenyl) -1H-1,2,4-triazole-1-ethanol,

Z-20. fl-cyclopropyl-fl-8- (p-methyleyl) -1H-1,2,4-triazol-1-one,

Z-21. [alpha] 1-J (2-methylcyclopropyl) -α [alpha] - (p-methylphenyl) -1H-1,2,4-triazole-1-ethanone,

Z-22. Fl-cyclohexylmethyl-β-methyl- (p-methyllenyl) -1H-1,2,4-triazole-1-eyanol, m.p. 79-81 ° C;

Z-23. [beta] -cyclopentylmethyl-alla- (p-methyllenyl) -1H-1,2,4-triphenyl-1-ethanol with a melting point of 74 to 76 [deg.] C,

Z-24. ? -? - (1-ethylpropyl)-? -? - (p-methyllenyl) -1H-1,2,4-triazol-1-ethan, melting at 87-89 ° C,

Z-25. alla- (1-methylbenzyl) -f1fa- ( ^p- methylphenyl) -1H-12,44-riazoo-1-ethanol,

Ž-26. alpha-tert-ethyl-4- (m-bromo-p-methylphenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 155-158 ° C;

Z-27. Mp-tert-butyl-4-methyl- (1-methyl-phenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 102-104 ° C;

Z-28. alpha-tert-butyl-1 H- (1 H -pyr-p-methylphenyl) -1 H -1,2,4-trlazol-1-enephenol, m.p. 144-147 ° C,

Z-29. 11f-eerc.lyУ1-. 11f- (m-chloro-m-methoxyphenyl) -1H-1,2,4-trifluoro-1-e efOll2

Z-30. (1-tert-Butylphal- (p-trifluoromethyl-3-ylphenyl) -1H-1,2,4-tetraazolylethanol),

Z — 31. flff-tert-butyl-1 H- (m-chloro-mleenoxyphenyl) -1H-1H-yriazole-1-ethanoo,

Z-32. alpha-cyclopentyl-ala-leeyl-1H-1H-triazole-4-ethanol; in the form of oil,

Z-33. flp-cyclopropyl-alpha- (p-chlorophenyl) -1H-1,2,4-triazol-1-ethanol in the form of an oil,

Z-34. elff-cyklobuУyl-flf6- ^(p illorieeyyl) -1H-1, 2,4-1-УrifZol eУfOol mp '83 to 84 ° C,

Z-35. mp-eerc.llyУy-11α- (m, ^β- dimethyleyl) -1H-1,2,4-triazole-1-ethanol, m.p. 120-122 ° C,

Z-36. flff-errc.lylII-1f: -ao-m-methyl-m-methylphenyl-1H-1,2,4-traezol-1-ethanol,

Z-37. alpha-tert. balyl-alla- (o-methyl-m-non-ylthiophenyl) -1H-, 2,4-) trans-1-ol,

Z-38. flff-er bu f У У--f - - (- (m-methyl-p-pheno: rel rel rel) l l) 1) H-1-thiazoo-1-yand,

Z-39 · alf-er c. У У У - - (((-(((((((((o (o (o o o

Z-40. [alpha] 1-cyclobulyl-alpha-phenyl-1H-12,4-triazol-1-one in the form of an oil,

Z-41. flfa-sec.bltyl-flfa- (p-chloroeryl) -1H-1,2,4-) tri- zole-1-ethanol as an oil,

2-42. alpha-tert. butyl-aFiaamrnm'ldichОartlnyl.) - L Н-1, 2,4-triazco-1-ethanol, m.p. 145 and ¹⁴⁷ ° Η

Z-43. alf8-terc.biityl-alpha- (m-chlorophenyl) -1 H-i, ₅ 2 4-triazol-l-ethanol, m.p.

126-127 ° C,

Z-44. 11-tert-Butylphenyl- (p-phenylphenyl) -1H-1,2,4-trifluorol-1-phtholene, m.p.

105 to 107 ° C,

2-45. [beta] -cyclopentyl-[beta] - (p-methylenyl) -1H-1,2,4-triazole-1-ethanol,

2-46. 11f-isobityl-phthalenyl-1H-1,2,4-triazole-1-ethino,

Z-47. alla- (1-meeyl.cyУlooP OyУ ⁰⁾ -ff ^and -P-mθeyУfθ nУ ⁿ ') 1H-2.44-1-rifzol etfnol m.p. 126 FZ-128 DEG C.

Z-48. alla-methyl-alla-β-bieenylyl) -1H-1,2,4-triazole-1-ethanol, m.p. 115-120 ° C,

2-49. alla-tert-butyl-aaa-p-joieenyl) -1H-1,2,4-triazole-1-ethanol of melting point up to 80 ° C,

Z-50. alpha- (J-heptyH-αiaa-β-methylphenyl) -1H-1,2,4-triazole-1-ethanol in the form of ole-e,

2-51. [alpha] - ([beta] - (2-peneyl) palfa-p-methylphenyl) -1H-1,2,4-triazole-1-ethanol of melting point up to 91 [deg.] C,

2-52. alla- (tert-butyl) -flf - (m, m) odlethylphenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 128-130 ° C,

Z-53. Alla-tert-butylfaffp - (- eno-4-methylphenyl) -1H-1,2,4-triazole-1-ethanol, m.p. 160-161 ° C;

Z-54. Alla-butyl-olla - 3,5 <0initro-4pmetyllenyl) P1H-1,2,4-triazol-te ^pl of ethanol ot ^{th of} n ^{s 194} and ^{from 196} ° C.

Example 3 alpha-tert-butyl-.alpha .- [beta] -carbonylphenyl) -1H-1,2,4-triazolepleteethole and its potassium salt

A mixture of 1.3 g of alla-tert-butyl-alpha - (- methylphenyl) -1H-1,2,4-triazole-1-ethanol, 1.89 g of potassium mannanosate and 19 ml of water was heated to stirring for 1 hour. reflux. The reaction mixture is filtered while hot, the residue is washed with 10 ml of hot water, clarified with charcoal and concentrated to a small volume (4 ml) in vacuo. Drying of the residue under high vacuum to give the potassium salt Alla-terc.butylf8la - (p-frb0oxylenyl) p ^{1 H} -l, ^{2,4-triazol-1} _-etaeolu) M.P. ^p s ¹⁹ 4 ° C.

The above reaction was repeated using three times the amount of the above compounds, washing the filtrate with ether, washing the ether from the wash with water, and stirring the combined aqueous layers with stirring ^; The precipitate is filtered off with suction, washed several times with ether and dried under high vacuum. Alpha-tert-butyl-.beta .- (p-aphenylphenyl) -1,2,2,4-triazole-1-eaanol, m.p. 248-250 ° C.

Example 4

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

2.2 g of 61.4% sodium hydride are washed three times with petroleum ether, then 70 ml of dimethylsulfoxide are added, the mixture is heated to 70 ° C with stirring, the temperature exits to 85 ° C as a result of the exothermic reaction, followed by heating for 40 minutes. at 75 ° C. The reaction mixture was cooled to 0 ° C in an ice / sodium chloride cooling bath and, while maintaining the temperature below 18 ° C, a solution of 7.0 g of trimethylsulfonium iodide in 50 ml of dimethylsulfoxide and 20 ml of tetrahydrofuran was added dropwise. A solution of 3.0 g of tert-butyl-p-methyl-phenylketone in 30 ml of tetrahydrofuran was added to the resulting mixture while maintaining the temperature below 10 ° C under stirring under nitrogen, then the mixture was first stirred at 0 ° C for 30 minutes and then 2 hours at room temperature. The reaction mixture is poured into 400 ml of water, extracted with diethylene chloride, the organic phase is washed with water and brine, dried and evaporated to give 2- (tert-butyl) -2- (4-methylphenyl) oxirane as a yellow solid. oils.

Example 5 alpha- (tert-butyl) -alpha- (p-methoxycarbonylphenyl) -1H-1,2,4-triazole-1-ethanol

To a flask cooled to 0 ° C containing an ethereal solution of diezomethane prepared in the usual manner from 3.39 g of N-methyl-N-nitroso-p-toluenesulfonamide, a solution of 1.5 g of alpha- (tert-butyl) is added dropwise while stirring in ice. - alpha - (p-carboxyphenyl) -1H-1,2,4-triazole-1-ethanol in 85 ml dry tetrahydrofuran. The resulting mixture was allowed to stand under ice-cooling until virtually no starting triazole was found by thin layer chromatography. To decompose excess diazomethane, a few drops of acetic acid were added, tetrahydrofuran was evaporated, the residue was extracted with ether and washed with 2N sodium hydroxide solution. After drying, white crystals formed on standing, which were filtered off and recrystallized from a mixture of dichloromethane and ether. The title compound is obtained, melting at 152-154 ° C.

Claims (8)

P R E 2 M Ё M VINALES A fungicidal composition, characterized in that it contains, as active ingredient, a compound of the general formula I (I) in which: R c is C 1 -C 12 alkyl, C 3 -C 3 cycloalkyl C 8 -C 11 cycloalkylalkyl, wherein the cycloalkyl moiety contains 3 to 8 carbon atoms and the alkyl moiety is 1 to 3 carbon atoms, wherein the aforementioned cycloalkyl and cycloalkylalkyl groups are optionally substituted by one or two alkyl groups having 1 to 8 carbon atoms; 3 carbon atoms, R represents a hydrogen atom, a halogen atom of from 9 to 35, a C1-C4 alkyl group, a trifluoromethyl group, a C1-C4 alkoxy group, a C1-C4 alkylthio group or a nitro group er 'represents a halogen atom C 9 -C 3 alkyl, C 1 -C 4 alkyl, trifluoromethyl, C 1 -C 4 alkoxy, trifluoromethoxy, C 1 -C 4 alkylthio, nitro, cyano, phenyl, phenoxy, or phenoxy; -COOR ** group where R ** is a hydrogen atom or a C 1 -C 4 alkyl group together with a β carrier or diluent. 2. A composition according to claim 1, wherein the active ingredient is a compound of the above formula (I) in which: R represents a hydrogen atom, a halogen atom having an atomic number from 9 to 35, a trifluoromethyl group or an alkyl group having 1 to 4 carbon atoms, R * represents a halogen atom and an atomic number of from 9 to 35, an alkyl group having from 1 to 3 C 4 -C 4 alkoxy, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, cyano, phenyl or phenoxy; and H ° is as in point 1 · 3. A composition according to claim 1 or 2, wherein the active ingredient is a compound of the above formula (I) in which: R represents a hydrogen, fluorine, chlorine or bromine atom, a trifluoromethyl group or an alkyl group having from 1 to 4 carbon atoms, R * represents a fluorine or chlorine atom, a cyano group, an alkyl group having 1 to 2 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, and R ° is as defined above · 4. A composition according to claim 3, wherein the active ingredient is a compound of the above formula (I), wherein: R 0 represents a tert-butyl or cyclopropyl group and the remaining general symbols have the meanings given above. 5. A composition according to claim 3, wherein the active ingredient is a compound of formula (I) wherein R0 is cycloalkylalkyl having from 3 to 8 carbon atoms in the cycloalkyl moiety and from 1 to 3 carbon atoms in the alkyl moiety, and the remaining general symbols are as defined above. 6. A process according to claim 1, wherein the compound of formula (I): R °, R and R * are as defined above, reacted in an inert organic solvent with a compound of formula III (III) wherein: X is an alkali metal 7. A process as claimed in claim 6, wherein the corresponding compounds of formulas II and III are used as starting materials to form compounds of formula I in which R @ 0 is a branched alkyl group having 3 to 6 carbon atoms or a cycloalkyl group. C 3 -C 6 carbon atoms. ‘ 8. The process of claim 6, wherein the corresponding compounds of formulas II and III are used as starting materials to give compounds of formula I wherein R0 is C3-C8 cycloalkylalkyl. cycloalkyl moiety and 1 to 3 carbon atoms in the alkyl moiety.