DE3042303A1 - ORGANIC COMPOUNDS, THEIR PRODUCTION AND USE - Google Patents

Description

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Organic compounds, their manufacture and use

The invention relates to α-aryl-1H-imidazole-1-ethanols, in particular a-alkyl or cycloalkyl-a-phenyl-1H-imidazole-1-ethanols, their use as fungicides and in compositions with which they simplify use in agriculture.

The invention very particularly includes compounds of the formula

I.

wherein R ^{0 is} an alkyl radical with 2 to 6 carbon atoms, a cycloalkyl radical with 3 to 6 carbon atoms, a cycloalkylalkyl radical in which the cycloalkyl radical contains 3 to 6 carbon atoms and the alkyl part contains 1 to 3 carbon atoms, the cycloalkyl radical and / or the cycloalkylalkyl radical can optionally be substituted by one or two alkyl radicals with 1 to 3 carbon atoms *,

R is hydrogen, halogen with an atomic number from 9 to 35, an alkyl radical with 1 to 4 carbon atoms, an alkoxy radical with 1 to 4 carbon atoms, an alkylthio radical with 1 to 4 C atoms or nitro and

R ^{1 is} hydrogen, halogen with an atomic number. from 9 to 35, an alkyl radical with 1 to 4 carbon atoms, an alkoxy radical with 1 to 4 carbon atoms, an alkylthio radical with 1 to 4 carbon atoms, -CF in the 3-position of the ring A, nitro, -CN, -COOR ", an optionally substituted phenyl radical

of the formula ~ \ Q2 ° ° of the one optionally substituted Phenoxy radical in position 4 of ring A of Eomel -0-R " Hydrogen or an alkyl radical with 1 to 4 carbon atoms

mean,

R and R 'together contain one or two C atoms, alkylenedioxy radical which is attached to two adjacent C atoms of the phenyl ring A is substituted and

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Y ₀ and Y independently of one another denote hydrogen, halogen with an atom number from 9 to 35, an alkyl radical with 1 to C atoms or an alkoxy radical with 1 to 4 C atoms, with the following, if R _{0 stands} for jv-butyl:

a) at least one of the radicals R and R 'different from hydrogen is and

b) R or R 'do not represent halogen.

Halogen atoms with an atomic number of 9 to 35 are fluorine, chlorine or Bromine.

The process for making compounds of Formula I is thereby

marked that one

a) a compound of the formula

R ⁰ °

wherein R °, R and R 'have the meanings given above, with a compound of the formula

X - NJ III,

wherein X is an alkali metal atom, converts in an organic solvent, b) to compounds of the formula

OH R ,

X C - CH "- K i Ia ι
R °

■ <J

to obtain,

wherein R ° and R have the meanings given above, the CH group in a compound of the formula

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Ib,
R ⁰

wherein R ⁰ and R have the meanings given above, oxidizes or

c) a compound of the formula
OH

^ Sv-C-CH. - N ^ I Ic
AIk-OOC X ^ t ι 2 X = J

R ⁰

to obtain,

wherein R and R ^{0 have} the meanings given above, a compound of the formula Ia with an alcohol of the formula Alk - OH IV,

or a functional derivative of this compound, in which Alk has the meanings given,
esterified.

The process of the reaction a) may be carried out at temperatures from 0 ° to 18O ⁰ C, preferably between 40 ° to 120 ⁰ C, in an inert organic solvent according to conventional methods are performed, for example in an amide of an organic carboxylic acid such as dimethylformamide.

The compound of the formula III can be obtained by known methods, advantageously by reacting imidazole with a strong base such as an alkali metal hydride, e.g., sodium hydride, in an organic Solvent, which is advantageously the same solvent which is used according to process a).

The oxidation according to method b) can be carried out with the aid of an oxidizing agent carried out, which is the oxidation of a CH_ group to a COOH group enables.

Suitable oxidizing agents are potassium permanganate, manganese dioxide and the like Oxidizing agent, advantageously potassium permanganate. The reaction will advantageously carried out in aqueous solution. A suitable reaction

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temperature for the process b) is from 20 ° to 150 ⁰ C, advantageously between "60 ° to 12O ⁰ C.

The compounds of formula Ia are depending on the reaction conditions in In the form of the free acid or in salt form (replace the H atom of -COOH by a cation).

The cure form of the formula Ia can be broken down into the corresponding saline forms be transferred by known methods and vice versa. The cation of the salt form of a compound of the formula Ia is advantageously a Acceptable cation commonly used and tolerated in agriculture, like a Na, K or KH cation.

The esterification process c) can be carried out according to methods known per se, with compounds which contain a functional reactive hydroxyl group. The esterification with an alcohol a compound of formula TV can be carried out most conveniently at temperatures of 30 ° to 8O ⁰ C, preferably under anhydrous conditions and in the presence of an acid, for example hydrochloric acid. Suitable solvents for this reaction are organic solvents or an excess of the alcohol according to formula IV.

Suitable functional compounds of the alcohols of formula IV are the corresponding diazoalkanes, for example diazoalkanes with 1 to 3 carbon atoms or an alkyl halide, in particular a chloride, bromide or iodide. The reaction with a diazoalkane can be carried out by methods known per se under anhydrous conditions and in an inert organic solvent. A suitable reaction temperature is from -20 ° to 40 ⁰ C, more usually -5 ° to 20 ° C. If the reaction is carried out with an alkyl halide, the compounds of the formula Ia are advantageously used in salt form, for example as an alkali metal or silver salt. Such a reaction is advantageously carried out in an inert organic solvent and at temperatures from 0 ° to 100 ⁰ C, in particular at 40 ° to 90 ⁰ C.

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The reaction products according to processes a), b) and c) can according to known methods obtained from the reaction mixture. and according to known Methods are worked up and cleaned.

Of the compounds of the formula I ₁ in which R 'is different from -COOH, the salt forms can be prepared and used.

The compounds of formula I are ethanol derivatives and can therefore be used in free form or in compounds derived therefrom, such as ethanolate salt form, e.g. in the sodium ethanolate form and in a metal complex form, e.g. of metals from group Ib, Ha, Hb, VIb, VIIb and VIII of the periodic table, such as. Copper and zinc, and with anions such as chloride, sulfate, kitrate, carbonate, acetate, Citrate, dimethyldithiocarbonate, etc.

All salts of the compounds of formula I come advantageously in one for the agriculture-compatible salt form in question.

The acid addition salt forms, the ethanolate salt form and the metal complex form can be carried out from the corresponding free form by known methods and vice versa.

The compounds of formula II can be obtained by reacting a Compound of formula

ν,

Ro - C -

wherein R ₀ , R, R ¹ and R " ^{1 have} the meanings given above, with the reaction product VI, prepared from a strong base and trimethylsulfonium iodide, which reaction product is produced by a compound of

formula

? ^H 3
H ₃ C - S®-CH ₂ ° VI

can be represented,

these reactions in an inert organic solvent be performed.

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This process is known for the production of * epoxy compounds from ketones.

Some compounds of the formula V are known and those are known as such are not known, can be prepared from known compounds analogously to the processes which enable the preparation of known compounds.

Many compounds of formula II are also known.

The compounds of the formula I are suitable as fungicides for combating phytopathogenic fungi, especially in the case of dusty or powdery meltau, mold or fire fungi and in the case of rust or fire fungi, as in the following by standardized in vivo and in vitro - Tests illustrated. The compounds of formula 1 can be used on plants, seeds or in the soil by a known method, as is customary for fungicidal compounds.

It should be noted or noted that the amount of a compound of formula 1, 'ttelcne is used'; ¹ depends on '^ k ^ i ren; 'like * k ^r .B;' From the 'vert'end the ⁴ treatment prophylactic'otter therapeutically ¹ durckgeiu'hrl ^e wi r ^, ^r ol the compound as a spray in a foliage, as a treatment in the soil or as a seed or seed treatment or' -Cover, the treatment

: .. ■ · ■ · <'. , ■ . ·· (. ■ ■. '■:.. ·>".;:,.:;.;!;; r -i -.- fJÜh β i %. ·) ■■ i' ii k. insane

or type of treatment of the genus or species, the "fungi and the application

In general, satisfactory results are obtained when the compound at Bepflanzungsort, kg either at the plant or in the soil in an amount of about 0.01 to 5, advantageously jvonjun ^ efähr Q.01 _r Biis 2 eingefetzt / hectare of active substance or active ingredient we ^. ^ ie.treatment can be repeated if desired, e.g. _t . in one. 67 to 30 day interval. If the compound is used in a Asian treatment ^^ wi one obtains satisfactory results, if the connection ^ in, .euiejr ^ Meng ^ _ί from about 0.05 to .0.5, advantageously from about _{ 0 ^ 1 until ^, ^^ g / men is used. _; . . _r _. f -. ^ Aai Vjnr der; »'.» - On

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The term "soil" in the meaning of soil, hollow, etc., encompasses any Growth medium, i.e. type of soil, be it natural or artificial.

The invention includes as an additional subject fungicidal compositions, containing as a fungicide a compound of the formula I in free Form or in an agriculturally suitable salt form and a inert fungicidal carriers or solvents. Generally included the compositions from approximately 0.01 to 90, advantageously from approximately 0.1 to 60 percent by weight, of active substance.

The compositions can be in concentrated form, which one can use before the application diluted or in a diluted form, which can be used directly.

Examples of preferred forms are wettable powders, emulsion concentrations, Dust forms, spray forms, granulates and forms in which the active substance is released with delay, forms in which the usual Carriers and other thinners and / or other auxiliaries are incorporated which are common or suitable in agriculture are.

Application forms of such compositions generally contain between 0.01 and 10 percent by weight of a compound of formula I as active ingredient. Concentrated forms of compositions for the fungicidal use generally contain between 2 and 80, advantageously approximately between 5 and 70 percent by weight of a compound of formula I as active ingredient.

Forms of emulsion concentrations contain between about 10 to 70; advantageously from about 20 to 60 percent by weight of active ingredient. Solid compositions are preferred.

The compositions, which are especially prepared for sprays, advantageously contain a surface-active auxiliary such as a liquid polyglycol ether, a fatty alkyl sulfate or a lignin sulfonate.

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In addition to the usual carriers and surface-active auxiliaries the formulations according to the invention, which are a compound of the Formula I contain other additional aids with special properties for special purposes, e.g. stabilizers, deactivators (for solid formulations bound to carriers with a surface-active compound), active ingredients or auxiliaries to adhere to Improve plants, corrosion inhibitors, and anti-fencing Dyes. In addition, other fungicides, bactericides or other Active ingredients that promote the effect, such as insecticides, in the formulations are attached and further representations of the invention are to be considered.

Examples of the representation of fungicidal formulations are given in described below:

a) Wettable powder continuation

50 parts of a compound of the formula I, e.g. a-tert-butyl-α- (paratnethylphenyl) - IH imidazole ethanol with 2 parts of lauryl sulfate, 3 parts of sodium lignosulfonate and 45 parts of finely divided kaolinite are ground until the average particle size is below 5 Microns is. The wettable powder obtained in this way is before use • dissolved in water or diluted in Kasser up to a concentration from 0.01 - 5% active substance. The spray liquid obtained can be used as a spray for the foliage as well as for soaking the roots or can be used as a root spray.

b) granulate formulation

For 94.5 parts by weight of quartz sand in a drum mixer, 0.5 Parts by weight of a binder (a nonionic surfactant) are sprayed on and the whole thing mixed thoroughly. 5 parts by weight of a compound of formula I, e.g. powdery ct-tert-butyl-α- (para-methylphenyl) -lH-: i ta i d a ζ ο 1-1-ethanol are then added and! powerful mixed to give a granular formulation having a range of particles from 0.3 to 0.7 mm. The granulate can be added to the

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be mixed by treating or raising the plants.

^c ) emulsion concentration

25 parts by weight of a compound of formula 1, for example a-tert-butyla- (para-methylphenyl) -lH ~ i mi d aζ o 1-1-ethanol are nit 30 parts by weight of iso-octylphenyl octaglycol ether and 45 parts by weight of a petroleum fraction with a Mixed boiling point range of 210-280 ⁰ C (D_ _n : 0.92). This concentrate can be diluted with water to the desired concentration.

d) seed coating or seed treatment

45 parts of a compound of the formula I, for example o-tert-butyl-a- (paramethylphenyl) -lH-i mi daζ ο 1 -1-ethanol, are mixed with 1.5 parts of an ethylene oxide addition product of diamylphenol decaglycol ether, 2 parts of spindle oil, 51 parts of finely ground talc and 0.5 parts of rhodamine B are served. The mixture is ground in a contraplex Hühle at 10 ¹ OOO rPrA until the average particle size of 20 microns is reached less than. The dry powder obtained in this way for treating the seed has good adhesion and can be added to seeds or added to the seed, e.g. B. by mixing for 2 to 5 minutes in a slowly rotating kettle.

The compounds of formula 1 can be used against those listed below Fungi are used, i.e. seem to be of particular interest in relation to these:

Λ) Basidiomy c etes containing

A) those of the genus Uredinales , such as those of the species Uromyces in plants, such as in beans, for example Uromyces appendiculatus , and in ornamental plants, for example Uromyces dianthi , those of the species Hemileia in plants, such as in coffee, for example Herileia vastatrix , those of the species Puccinia in plants as in cereals (e.g.

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Wheat, oats, barley), for example Puccinia gratsinis , Puccinia recondite and Puccinia striiforniis , or in the case of ornamental plants, for example Puccinia pelargoniizonalis and Puccinia antirrhir. i, those of the species Phakopsora in plants such as soy, eg Phakopsora pachyrhizi , those of the species Melaropsora in plants such as flax, eg Melampsora lini and those of the species Tranzschelia , eg Tranzschelia pruni in plums;

A “) those of the genus Ustilaginales such as those of the species Ustilago in plants such as barley, wheat, corn and sugar cane, eg Ustilago maydis in corn and Ustilago and a in barley, and

A,) those of the genus Stereun in pome and stone fruit trees, e.g. Stereum purpureum in apples and plums.

B) Ascomycetes containing

B.) those of the genus Erysiphales such as those of the species Erysiphe in plants such as cucumber, barley, wheat and beet sugar, for example Erysiphe graminis f. Sp. tritici with wheat and Erysiph e ci cho r ac ε ar eura with cucumbers; those of the Spo haerotheca species with cucumbers and roses, eg Spo haerot he ca panno sa with roses; those of the species Podosphaera in apples, pears and plums, for example Podosphaera leucotricha in apples; those in the species Uncinula in plants such as grapes, for example Uncinula necator in grapes; those of the species Oidiuni in a large number of plants and those of the species Leveillula in plants such as cotton and other Malvaceae , eg Leveillula taurica in cotton.

C) containing Oomycetes

C.) those of the species Phytophthora spp. , for example Ph. cactorum , Ph. parasitica and Ph. cinaraomi in sensitive plants; and

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C ") those of the species Aphanomyces in plants such as the pea and sugar beet, eg Aphanomyces euteich es in the sugar beet, and

D) containing Deutero m ycetes

D) those of the species Helminthosporium in plants such as barley and grain, e.g. Helm.Sativum ;

D_) those of the species Septori a in plants such as wheat, tomatoes and celery, e.g. Sept. tritici in wheat, tomatoes and celery, e.g. Sept. tritici in wheat;

D) those of the species Rhizoctonia in plants such as cotton and potatoes, for example Rhiz. solani for cotton;

D.) those of the species Fusarium spp. e.g. F. oxysporum f. sp. lycopesici in tomatoes, F. ox ysp orum f. sp. vasinfectun in cotton, F. oxysporun f. sp. cubense in bananas, F. solani in vegetables, F. culreorum in cereals and F. graminearum in cereals;

D_) those of the species Thielaviopsis in plants such as cotton, tobacco, etc., e.g. Thielaviopsis basicola in Baumvol-Ie;

D,) "those of the species Phoma in plants such as sugar beet, rape, etc., e.g. Phoma betae in sugar beet;

D_) those of the species Piricularia spp. , e.g. P. oryzae in rice and

D_) those of the species Colletotrichum spp. E.g. C. lindemuthiamnn in beans.

The following common tests illustrate the possibilities in which the fungicidal activity of the compounds of the formula I can be established or determined.

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Test method A. ·

IS Vivo test using the bean rust fungus (Uromyces appendiculatus) . Phaseolus vulgaris (runner beans) is grown in a mixture of peat and sand or soil in plastic pots 9 cm in diameter "for 9 days. The plants are sprayed with a spray solution containing 0.0008 to 0.05% (ie with a 0.0008%, 0.003%, 0.012% and 0.05% solution) of active substance. The treatment comprises a foliar spraying of emerged, ie sprouted leaves or a soil treatment, ie a soil wetting (28 ml spray liquid per pot) the plants nit a SporerisuS- 'pension inoculated containing 500 ¹ OOO to 700 * 000 spores / ral and for 7 days incubated in a Incubationsraum at 21 ° C and lOOZiger relative humidity. the effectiveness of the treatment Rait the active substance is determined by comparing the Number of pustules or pimples per sheet with such a comparison sheet that was not treated with the active ingredient, but inoculated in the same way. The compounds of formula I, in particular e the compounds as listed herein in the examples, for example the compounds of Examples 1, 2A, 2 Z-2 and 2 Z-II used in the form of a wettable powder formulation as indicated above, give a significant degree of fungicidal activity according to the test listed above, both for treatment by direct contact and for treatment at the root. Similar tests can be carried out on the following useful crops / fungi with similarly good results.

Coffee: Coffee leaf mushroom (Henileia vastatrix )

Wheat: black stem mushroom (Puccinia gransinis)

Wheat: brown leaf rust fungus (Puccinia recondita)

Wheat: yellow or streaky rust fungus (Puccinia striiforais)

Flax: Flax rust mushroom (Helaaspora Lini)

Pelargonium: Pelargonium rust fungus (Puccinia pelargqniizonalis)

Snapdragon rust fungus (Puccinia antirrhini) '

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Test method B

In Vivo test using the powdery cucumber Keltsu. (Erysiphe cic ho racearuni ) Cucuais sativüs (cucumber) is grown in a mixture of peat and sand or soil in plastic pots with a diameter of 6 ca for 7 days. The plants are sprayed with a spray solution which contains 0.0008 to 0.05% (ie with a 0.0008%, 0.003%, 0.012% and 0.05% solution) of active substance. The treatment includes a foliar spraying of emerged, ie sprouted leaves or a soil treatment, ie a soil wetting (28 ml of spray liquid per pot). After the drying, the plants are inoculated with a freshly collected co nidia by dusting and then to 30 ⁰ C une a 60-80% relative humidity for 7 days in a incubiert Incubationsraum at 25 °. The effectiveness of the treatment with the active ingredient is determined by comparing the degree of fungicidal infestation with such a comparative infestation which was not treated with the active ingredient but inoculated in the same way. The compounds of the formula I, in particular the compounds as listed in the examples herein, for example the compounds of Examples 1, 2A, 2C, 2D, 2G, 2J, 2Q, 2T, 2 ZI, 2 Z-2, 2 Z- 5, 2 Z-6, 2 Z-7, 2 Z-9, 2 Z-II and 2 Z-12 used in the form of a wettable powder formulation as indicated above, result in a significant degree (value) of fungicidal activity according to the above Test both for contact treatment and treatment at the root. Similar tests according to test method B can be carried out on the following useful plants / fungi with similarly good results.

Wheat: powdery wheat meltau (Erys. Gram, f. Sp. Tritici)

Barley: powdery barley meltau (Erys. Gram, f. Sp. Hordei )

Apple: powdery apple rye (Podos. Leucotricha)

Grape: powdery grapevine meltau (Uncinula necator )

With regard to the powdery cucumber rope, the above-mentioned Test method B is repeated with the preferred compound of Example 1 (both foliar spraying and soil treatment); whereby

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but the test with lower concentrations of 0.0002% and 0.000053 is carried out, with the result that still a loo or 80% Restriction of fungi is achieved by spraying; a 55% or 10% restriction by soil treatment shows the excellent effectiveness the invention.

Test method C

In vitro using Ustilago maydis (grain brandy). Various concentrations of active ingredient are placed in malt agar plates to achieve concentrations from 0.8 to 200 ppraa.i. (e.g. from 0.8, 3.2, 12.5, 50 and 200 ppm). For this purpose, the plates are inoculated by spraying a U. maydis spore suspension or by inserting an agar plug containing the fungi into the center of the plate. The plates are incubated at room temperature for 2 to 5 days. The effectiveness of the treatment with the active ingredient is determined by comparing the growth of the fungus with those fungi on control plates which were not treated with the active ingredient but were inocubated in a similar manner. The compounds of the formula I result in a moderate to good restriction according to test method C.

The compounds of Example 1, 2C and 2 Z-8, as they are listed later, result, for example, in a good restriction at the higher concentration according to test method C. In an analogous test on Fusarium oxysporu m f. S2j_ results in the compound of Example 1 is a good restriction at lower and higher concentrations.

Fungi of the aforementioned genera result in one in agriculture cause considerable damage and are difficult to control or prevent, or to hold.

In order to combat such fungi, the compounds of the formula I appear to be non-phytotoxic in the plants at the effective amounts and it is therefore indicated that they are of particular interest in order to combat the fungi through targeted action, for example when combating Uromyces appendiculatus in beans.

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Analogous additional tests for test method C at 13, 50 and 200 ppm a.i. show exceptions are specifically labeled, a 100% restriction with the compound of Example 1 in at least one test dosage in the following plants:

Phytophthora cactorura (maximum restriction 85%); Phytophthora cina monii (maximum limit 65%); Aphanomyces euteiches ; Stereurrt purpureum ; Thielaviopsis basicola (". Maximum Eescu reduction 80%); Pirieularia oryzae (maximum limit 70%) and Colletotrichum lindeinuthianum (maximum limit 65%).

Additional tests analogous to test methods A and B with amounts of 32, 125 and 500 ppm ai, carried out with the compound of Example 1 show a 60%, 80% and 90% restriction of Helminthosporium when sprayed without phytotoxicity.

Test method D

In vivo , using Rhizoctonia solani . The fungus is grown in a sterile mixture of Zonolite and Kornraehl (10: 1 w / w), to which water is added in a ratio of approximately 1: 1 (w / w); growth lasts 14 days at 25 ° C. The fungus is then mixed into a practically sterile mixture of peat and sand, which is then treated with a suspension containing the formulated active ingredient, in a concentration of 10 to 160 ppm (e.g. 10, 40 and 160 ppm) calculated on the basis of this Volume of the substrate. The substrate is then placed in pots with a diameter of 5 cm, which have been planted with cotyledonous stage seedlings. The planted pots are incubated at 24 ° C. and at 60-70% relative humidity in an incubation room for 14 days. After this time, a pathological infestation can be determined when comparing the fungicidal infestation on the roots and the hypocotyl with such untreated and similarly inoculated reference plants. The compounds of Example 1, as used in the specified wettable powder formulation, cause, for example, a 100% pathological restriction without phytotoxicity at the lower dosage.

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A test analogous to test method D using Phoma betae on sugar beet results in a 100% restriction with about 20% phytotoxicity at the low dosage.

From the information given above, it emerges that the compounds of the invention are of such importance to the person skilled in the art that they are of particular interest with regard to the monitoring and restriction of soil and seed fungi , for example Helminthosporiun , Photna, RhJ2octonia and Thielaviopsis , and also theirs of significant interest and value in the restriction and control of powdery melt-thaws and rust fungi.

The particular value and advantages of the invention are confirmed and / or set out further in more precise value determinations at the Compound of Example 1 below, which has the following excellent and in some cases noteworthy properties:

1) Continuous treatment of runner beans with spray concentrations of 0.012% 8 days prior to inoculation results in a 70% restriction of Uromyces app . ;

2) a good stability of the aqueous suspensions with the 100% restriction of Uromyces app. In runner beans even 3 days after the preparation of the suspension with a 0.012% concentration;

3) rapid and sustained penetration of the active substance into the leaves, whereby, as stated above, an 80% restriction is ensured at a concentration of 0.012%, after washing the leaves of the grape for 15 minutes two hours after the application of the active substance and followed by infestation by Uncinula ;

4) a 65% restriction on sprinkling the leaves of coffee plants with an amount of rain of 50 MM / hour two hours after the active ingredient has been applied for 15 minutes, followed by a drying phase and a second rain phase for 15 minutes, followed by an infestation of the coffee plant by Hemileia vastatrix and

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5) a 60% i.ge restriction for a simulated rain-washing of the runner bean leaves at an amount of rain of 50 MM / hour two hours after the application of the active ingredient for 10 minutes, followed by the infestation of the runner beans by Uromyces app .

Another advantage of the compound of Example 1 below is a 100% fungicidal activity, which is achieved in the treatment with the active ingredient and a concentration of 0.012% one day after the runner beans were infested with Uromyces app. And a 60% restriction two Days after infestation.

Other compounds of the formula I according to Example 2 show very good to excellent fungicidal activity when following those previously described Procedure used or checked.

Preferred compounds of the formula I have one or more advantageous ones all of the following measures:

a) R ⁰ stands for an alkyl radical with 3 to 6 carbon atoms, for cycloalkyl with 3 to 6 carbon atoms or for cycloalkylmethyl in which the cycloalkyl part has 3 to 6 carbon atoms;

b) R stands for hydrogen, halogen with an atomic number of 9 to 35 or for (1-4C) -alkyl;

c) R ¹ stands for hydrogen, halogen with an atomic number of 9 to 35, for (1-4C) -alkyl, (1-4C) -alkoxy or (1-4C) -alkylthio'oder

d) R '' stands for one of the groups - (("Sb '° or -0- (Qd' ° in para-St-

Y lung bound in ring A.

The particularly preferred compounds of Formula I have one or more and advantageously all of the following measures:

a) R ₀ stands for an alkyl radical with 3 to 5 carbon atoms or for cycloalkyl with 3 to 6 carbon atoms;

b) R represents hydrogen, fluorine or chlorine and

c) R 'stands for hydrogen, halogen with an atomic number of 9 to 35, (1-2C) -alkyl or (1-2C) -alkoxy or

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d) R stands for hydrogen and R 'for a radical

bonded in the para position of ring A, preferably Y ₀ and Y are hydrogen.

In general, R ₀ advantageously represents propyl or branched butyl, ζ.3. n-propyl, isopropyl, seic-butyl, isabutyl or tert-butyl or cyclopropyl or cyclopentyl, but R ₀ is very particularly tert-butyl.

In general, those compounds are preferred in which at least R or R 'are different from hydrogen, in particular stands for an alkyl "radical, e.g. for methyl or ethyl or phenyl in the para-position in the crack A, where the other radical is hydrogen or halogen.

The following examples are intended to illustrate the invention. All temperatures are given in degrees Celsius.

example 1

a-tert-Butyl-a-Cpara-methylpheny ^ -lH-imidazole-1-gthanol

A 0.82g portion of 61.4Zigem sodium hydride is three times with petroleum ether washed and then added to 10 ml of dimethylformamide with stirring. To the suspension obtained in this way, 1.43 g of imidazole, dissolved in 10 ml of dimethylformamide, with bubbles forming when heated. The mixture obtained is heated to 40 ° with stirring for 30 minutes until the formation of bubbles has ended, whereupon 4.0 g of 2-tert-butyl-2- (4-methylphenyl) oxirane be admitted; the entire mixture is heated for 11/2 hours at 70 °. The resulting mixture is then poured into water and the aqueous mixture with ethyl acetate extracted, the organic phase washed with water, dried and evacuated, leaving an oil, which cooled to room temperature will; this gives a solid portion which is recrystallized from a mixture of hexane / tetrachloromethyl (10:90), with the a-tert-Butyl-α- (para-methylphenyl) -lH-itnidazole-l-ethanol with a Melting point of 135-137 ° is obtained.

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Example 2

If the information given in Example 1 is followed, the following are obtained compounds according to the invention:

A) a-n-Butyl-a- (para-methylphenyl) -lH-imidazole-1-ethanol, m.p. 136-138 °.

B) α-tert-butyl-α- (para-chlorophenyl) -lH-imidazole-1-ethanol.

C) a-tert-BuEyl-or- (ortho, para-dichlorophenyl) -lH-imidazole-l-ethanol, M.p. 141-142 °.

D) a-tert-Butyl-a-phenyl-1H-imidazole-1-ethanol, m.p. 124-125 °.

E) «-n-Propy] .- a- (para-methylphenyl) -lH-imidazole-l-ethanol, m.p. 156-157 °,

F) n-tert-butyl-a- (para-fluorophenyl) -lH-imidazole-1-ethanol.

G) a-tert-butyl-α- (para-methoxyphenyl) -lH-iraidäzol-l-ethanol, 153-155 °.

H) a-tert-butyl-a- (meta-nitrophenyl) -III-imidazole-1-ethanol.

I) a-tert-butyl-a- (tneta-trifluoromethylphenyl) -] H-imidazole-1-ethanol.

J) a-tert-butyl-a- (meta-cyanophenyl) -lH-imidazole-l-methanol,

156-157 °.
K) a-tert-butyl-α- (meta, para-methylenedioxyphenyl) -lH-imidazole-l-

ethanol.
L) a-tert-Butyl-a ~ (para-biphenylyl) -lH-imidazole-1-ethanol, m.p. 174-175 °.

M) a-tert-butyl-a- (para-phenoxyphenyl) -lH-imidazole-1-ethanol. N) a-iso-propyl-a- (para-chlorophenyl) -lH-imidazole-l-ethariol. 0) altert-butyl-α- (meta, para-dichlorophenyl) -lH-imidazole-l-ethanol. P) a-iso-butyl-a- (para-methylphenyl) -lH-iroidazole-1-ethanol. Q) a-n-Propyl-a-phenyl-1H-imidazole-1-ethanol, m.p. 119-120 °. R) a-ethyl-a- (para-chlorophenyl) -lH-imidazole-1-ethanol, m.p. 167-168 °.

S) α-neopentyl-α-phenyl-1H-imidazol-1-ethanol, m.p. 169-170 °. T) a-Cyclopropyl-a-ipara-chlorphenyiy-lH-imidazol-l-ethanol, 132-134 °.

U) a-n-pentyl-a-phenyl-1H-imidazole-1-ethanol, m.p. 146-147 °. V) a-Cyclopropyl-a- (para-methy! Phenyl) -lH-imidazole-1-ethanol.

130035/0359

3Q42303

- 24 - Case 136-6377

W) a-Cyclopentyl-a- (para-methylphenyl) -lH-imidazole-1-ethanol. X) α-tert-butyl-α- (para-methylthiophenyl) -lH-imidazole-1-ethiinol. Y) a-SGC.-Butyl-a-Cpara-methylphenyD-1H-imidazole-1-ethanol. Z) a-iso-butyl-a- (para-methylphenyl) -lH-imidazole-1-ethanol. Z-Ii «~ tert-butyl -« - (meta-bromo-para-methylphenyl) -lH-ir.! Idaj'.o 1-1-

Methanol, m.p. 139-142 °.
Z-2) a-tcrt.-Butyl-a- (inetci-fluor-para-inechylphenyl) -llI-iKida2bl -] -

ethanol, m.p. 150-152 °.
Z-3) Q-tert-butyl-a-Cmeta-chloro-para-methylphenylJ-lH-imidazole-l-

ethanol, m.p. 152-156 °.
Z-4) a-tert-butyl-a- (nieta-chloro-nieta-inethoxyphenyl) -lH-imidnzol-ethanol.

Z-5) a-n-Butyl-a-phenyl-1H-inidazol-1-ethanoi, Snip. 138-139 °. Z-6) α-Cyclopentyl-α-phenyl-1H-imidazole-1-ethanol, m.p. 144-145 °. Z-7) o-Isopentyl-a-phenyl-1H-imidazole-1-ethanol, m.p. 169-170 °. Z-8) or-ia-butyl-α- (ortho, para-dichlorophenyl) -lH-imidazole-1-ethanol. Z-9) α-tert-butyl-α- (meta-meta-dichlorophenyl) -lH-imidazo] -l-ethanol,

M.p. 159-161 °.
Z-IO) a-tert-butyl-o! - (meta, para-dimethylphenyl) -lH-itaidazo] -l-ethanol.,

M.p. 145-146 °.
Z-II) a-tert-butyl-α- (para-ethylphenyl) -lH-ir.n.dazol-l-ä't!) Anol,

115-118 °.
Z-12) a-tert-butyl-α- (meta-methylphenyl) -lH-imidazole-l-ethanol,

S; np. 90-92 °.
Z-13) a-tert-butyl-a-ipara-tert-butylphenylJ-lH-imidazole-l-ethanol,

155-157 °.
Z-14) a-tert-butyl-a- (para-methoxyphenyl) -lH-imidazol-l-ethylenol,

153-155 °.
Z-15) a-tert-butyl-a- (ffieta-methoxyphenyl) -lH-imidazole-l-ethanol, m.p. 114-115 °.

Z-Ib) a-tert-butyl-a- (para-cyanopl) enyl) -lH-imidaxol-l-sthanol, 143-145 °.

13 0 0 3 5/0 3 5 9

- 25 - case 136-6S7;

Z-] 7) a-1 sept ntyl-a- (para-ncithylphenyl) -lH-inidazole-l-ethanol,

Snip. 104-105 °.
Z-18) "- (1-methylbutyl) -a - (para-methylphenyl) -lH-imidazole-1-ethanol, Snip. 119-122 °.

B e i s ρ i £ · 1 ■ 3

A 2.2 g portion of 61.4% Natriuir.hydrid is 3 times with Petroliithcr washed, treated with 70 ml of dimethyl sulfoxide and the mixture under Kührcn heated to 70 ° and the reaction with heating up to 85 ° carried out, whereupon the mixture is heated at 75 ° for 40 minutes will. The mixture obtained is cooled to 0 ° in an ice-salt bath and a solution consisting of 7.0 g of Trimethylsulfonicrum iodide, 50 ml of dimethylsulfoxide and 20 ml of tetrahydrofuran, added dropwise while maintaining the temperature below 18 °. The mixture thus obtained is then mixed with stirring a solution consisting of 3.0g tert-butyl-para-methylphenyl-ketone in 30 ml of tetrahydrofuran were added while the temperature was kept below 10 ° will. The resulting reaction mixture is then further stirred at 0 ° for 30 minutes and then at room temperature for 2 hours. The mixture is then poured into 400 ml of water, washed with methylene chloride, the organic phase with water and then with brine, dried and evacuated to a yellowish oil of the compound 2- (tert-buty].) - 2- (4-mc> thylphenyl) oxirane.

130035/0359

Claims (10)

Case 136-6877 SANDOZ-PATENT-GMBH Loerrach Organic compounds, their manufacture and use Claims
1. Compounds of the formula an alkyl radical having 2 to 6 carbon atoms, a Cycloalkyl radical with 3 to 6 carbon atoms, a cycloalkylalkyl radical in which the cycloalkyl radical is 3 up to 6 carbon atoms and the alkyl part contains 1 to 3 carbon atoms, the cycloalkyl radical and / or the cycloalkylalkyl radical optionally by one or two alkyl radicals, with 1 to 3 carbon atoms, can be substituted, R is hydrogen, halogen with an atomic number from 9 to 35, an alkyl radical with 1 to 4 carbon atoms, an alkoxy radical with 1 to 4 carbon atoms, an alkylthio radical with 1 to 4 C atoms or nitro and R ^{1 is} hydrogen, halogen with an atom number of 9 to 35, an alkyl radical with 1 to 4 carbon atoms, an alkoxy radical with 1 to 4 carbon atoms, an alkylthio radical with 1 to 4 carbon atoms, -CF in the 3-position Ring A, nitro, -CN, -COOR ", an optionally substituted phenyl radical of the formula "\ Qy ° or an optionally substituted one Phenoxy radical in the 4-position of the ring Ader formula -C R "hydrogen or an alkyl radical with 1 to 4 carbon atoms" mean, R and R ¹ together contain one or two C atoms, alkylenedioxy radical which is substituted on two adjacent C atoms of the phenyl ring A and 130035/0359 - 2 - Case 136-6877 Y ₀ and Y are independently hydrogen, halogen with an atom number of 9 to 35, an alkyl radical with 1 to C atoms or an alkoxy radical with I to 4 C atoms, with the proviso, if R _{0 stands} for yes-butyl: a) at least one of the radicals R and R ^{1 is} different from hydrogen, and b) R or R 'do not represent halogen. 2. Process for the preparation of compounds of the formula I according to claim 1, characterized in that one a) a compound of the formula R ⁰ wherein R °, R and R * have the meanings given above, with a compound of the formula X - IiJ III, wherein X is an alkali metal atom, reacts in an organic solvent, b) to compounds of the formula OH $ & y C-CH ₂ - ijf ^ j Ia R ° to obtain, in which R ⁰ and R have the meanings given above, the CH group in a compound of the formula OH ^H 3 ^C r ° where R ° and R have the meanings given above, oxidized or 130035/0359 - 3 - Case 136-6877 c) a compound of the formula
OH AIk-OOC ^^ «2 \ —J
R ° to obtain, ■ _t ■ ■ in which R and R ^{0 have} the meanings given above, a compound of the formula Ia with an alcohol of the formula Alk - OH IV, or a functional derivative of this compound, wherein Alk is the Has previously given meanings, esterified. 3. Methods of combating fungi, in particular phytopathogenic fungi in Plants, seeds, seeds or in the soil, characterized in that these.Plant, the seeds, the seeds or the soil with a a non-phytotoxic fungicidal effect exhibiting amounts of a compound of the formula I in free form or in one for agriculture tolerated salt form. 4. Fungicidal composition containing a compound of the formula I according to Claim 1 in free form or in an agriculturally acceptable salt form in conjunction with a fungicidal carrier or a thinner. 5. agents for combating fungi, in particular phytopathogenic fungi, containing a compound of the formula I according to claim 1 as active substance. 6. Compounds according to claim 1, wherein R is hydrogen, halogen with an atomic number of 9 to 35 or (1-4C) -alkyl and R ^{1 is} hydrogen, halogen with an atomic number of 9 to 35, for (1-4C) - Alkyl, (1-4C) -Alkoxy, or for a group of the formula - \ OCi ° or ~ ° "\ Cy °» which is bound in the para position in ring A, is. 7. Compounds of formula I according to claims 1 and 6, wherein R is hydrogen, fluorine or chlorine and R ^{1 is} hydrogen, halogen with an atom number of 9 to 35, for (1-2C) -alkyl or (1-2C) - Alkoxy or para-phenoxy. 130035/0359 - 4 - Case 136-6877 8. Compounds of formula I according to claims 1, 6 and 7, wherein R ° for an alkyl radical with 3 to 6 carbon atoms or, for cycloalkyl, with 3 to 6 Carbon atoms. 9. Compounds of formula I according to claims 1, 6, 7 and 8, wherein R ^{0 represents} a branched butyl radical, cyclopropyl or cyclopentyl. 10. Compound cr-tert-butyl-a- (para-methylphenyl) -lH-iinidazole-l-ethanol gel • Ace Claim 1. 130035/0359