NO822231L - IMIDAZOLYL PROPIONITRILS AND HERBICIDE AGENTS CONTAINING THESE. - Google Patents

Abstract

Imidazolyl propionitriles of general formula. wherein R represents an aromatic hydrocarbon radical which is optionally substituted by one or more, identical or different halogen, (C-C) -alkyl, (C-C) -alkoxy ,. (C 1 -C 4) -alkylthio, trifluoromethyl or nitro substituents, and. (C 1 -C 6) -alkenyl, (C 3 -C 6) -alkenyl, (C 3 -C 6) -alkynyl or phenylalkyl radical which is optionally substituted by one or more, identical or different halogen, (C 1-4) -alkyl, (C 1-4) -alkoxy (C - C growth regulating as well as a bactericidal effect.

Description

The present invention relates to new imidazolyl-propionitrile, methods for the production of these compounds as well as biocidal agents, particularly with fungicidal action, containing these.

Imidazolyl-propionitrile derivatives with fungicidal action are previously known (DE-OS 26 04 047). However, these show a relatively narrow range of activities, which is unsatisfactory.

The task of the present invention is to develop new imidazolyl-propionitriles, which open up widely varied application possibilities, particularly in the field of plant protection and which exhibit a broad spectrum of fungicidal action.

According to the invention, this task is solved by imidazolyl-propionitrile with the general formula:

where

R is an aromatic hydrocarbon group substituted with one or more, the same or different substituents which are halogen,

(C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkylthio, trifluoromethyl or nitro, and

R1 is (C1-C10)-alkyl, (C2-C8)-alkenyl, (C2-C8)alkynyl or phenylalkyl substituted with one or more of the substituents halogen, (C1-C4)-alkyl, (C1-C4)- alkoxy, (C1~C4)-alkylthio, trifluoromethyl or nitro,

and acid addition salts thereof with inorganic or organic acids.

The compounds according to the invention are, in the broadest sense, biocidally active, but are particularly distinguished by a fungicidal effect, whereby they surprisingly surpass known active substances with an analogous constitution and direction of action.

The fungicidal effect extends surprisingly enough against fungi of the most diverse systematic types. By treating above-ground plant parts, they protect against wind-borne pathogens. Against seed-borne disease agents, the compounds can be used for seed treatment. In addition, they work systemically, i.e. they are taken up by the plants' roots, e.g. after introduction with the seed, is transported in the above-ground parts of the plants and protects them against disease-causing agents,

As further effects, a growth-regulating and a bactericidal effect can be mentioned.

Due to the known broad spectrum of action, the compounds are suitable not only for the protection of cultivated plants, but also for material protection and combating human-pathogenic and animal-pathogenic microbes, whereby they provide widely varied application possibilities.

Depending on the special meaning of the substituents, this gives you special areas of application, in which the compounds exhibit an outstanding effect. Thus, they can always be used as fungicides, plant growth regulators or bactericides.

In the compounds denoted by the general formula I, the substituents can e.g. have the following meaning: R can be 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chloro phenyl, 3-chloroferriyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-iodophenyl, 3-iodophenyl,.4-iodophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 3,4 -dichlorophenyl, 2,6-dichlorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2-propylphenyl, 3-propylphenyl, 4-propylphenyl, 2-isopropylphenyl, 3 -isopropylphenyl, 4-isopropylphenyl, 2-butylphenyl, 3-butylphenyl, 4-butylphenyl, 2-sec-butylphenyl, 3-sec-butylphenyl, 4-sec-butylphenyl, 2-t-butylphenyl, 3-t-butylphenyl, 4 -t-butylphenyl, 2-methoxyphenyl, 3- methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 2-methylthiophenyl, 3-methylthiophenyl, 4- methylthiophenyl, 2-ethylthiophenyl, 3-ethylthiophenyl, 4 -ethylthiophenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 3-fluoro-4-methoxyphenyl, 2-chloro-5-nitrophenyl, 4-chloro-2-fluorophenyl, 3,4,5-trimethoxyphenyl or 5-chloro-2-nitrophenyl

and

R 1 can be (C 1 -C 2 O)-alkyl, e.g. methyl, ethyl, propyl,

butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, 2,2-dimethylpropyl-1,3,3-dimethyl-butyl-2, (C 1 -C 8 )-alkenyl, e.g. 2-buten-1-yl, 3-methyl-2-buten-1-yl, hexenyl, heptenyl, octenyl, (C -C0 )-alkynyl. e.g. propargyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, phenylalkyl, e.g. benzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3-bromobenzyl, 4-bromobenzyl, 2,4-dichlorobenzyl, 2,6-dichlorobenzyl, 3,4-dichlorobenzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2-nitrobenzyl, 3-nitrobenzyl, 4-nitrobenzyl, 2-trifluoromethylbenzyl, 3-trifluoromethylbenzyl, 4-trifluoromethylbenzyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-ethoxybenzyl, 3-ethoxybenzyl, 4-ethoxybenzyl, 2-propoxybenzyl, 3-propoxybenzyl, 4-propoxybenzyl, 2-butoxybenzyl, 3-butoxybenzyl, 4-butoxybenzyl, 2-methylthiobenzyl, 3-methylthiobenzyl, 4- niethylthiobenzyl, 2-ethylthiobenzyl, 3-ethylthiobenzyl, 4-ethylthiobenzyl, 2-butylthiobenzyl, 3-butylthiobenzyl, 4-butylthiobenzyl.

Examples of inorganic and organic acids for forming the acid addition salts include the hydrohalic acids, such as hydrochloric acid and hydrobromic acid, further phosphoric acid, sulfuric acid, especially nitric acid, mono- and bi-functional carboxylic acids and hydroxycarboxylic acids, such as e.g. acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid, as well as the sulphonic acids, e.g. p-toluenesulfonic acid and 1,5-naphthalene disulfonic acid.

These acid addition salts can be obtained by the usual salt formation methods, e.g. by dissolving a compound of formula I in a suitable solvent and adding the acid.

Of the compounds according to the invention, they are distinguished by a fungicidal effect which in the general formula I has the substituents where: R has a phenyl group which has one or more, identical or different substituents which are halogen, (C^-C^^)-alkyl, (C 1 -C 4 )-Alkoxy, (C 1 -C 4 )-Alkylthio, Trifluoromethyl or Nitro, and

R^ is (C^-C^)-alkyl, allyl, propargyl or a benzyl group which is optionally substituted with one or more, identical or different groups which are halogen, (C^-C^)-alkyl, (C^- (C 1 -C 4 )-Alkoxy, (C 1 -C 4 )-Alkylthio, trifluoromethyl or nitro.

Preferably, of these, such compounds can be mentioned where

R is phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dichlorophenyl, 2-fluorophenyl, 4-fluorophenyl, 4-bromophenyl, 2-methylphenyl, 4-methylphenyl, 4-methoxyphenyl or 4-nitrophenyl,

and

R.^ is methyl, ethyl, propyl, isopropyl, phenyl, hexyl, allyl,

propargyl, benzyl, 2-chlorobenzyl,.4-chlorobenzyl,. 2,4-dichlorobenzyl, 3,4-dichlorobenzyl.

The following compounds according to the invention have outstanding effects: 2-n-butoxy-2-(2-chlorophenyl)-3-(imidazol-1-yl)-propionitrile hydronitrate

2-n-butoxy-2-(2-chlorophenyl)-3-(imidazol-l-yl)-propionitrile 2-n-butoxy-(-4-chlorophenyl)-3-(imidazol-l-yl)-propionitrile- hydronitrate

2-(4-Chlorophenyl)-3-(imidazol-1-yl)-2-n-propoxypropionitrile hydronitrate

2-(2-Chlorophenyl)-3-(imidazol-1-yl)-2-n-propoxypropionitrile

The compounds according to the invention show particularly fungicidal action, but at the same time excel in a number of cultivated plants by their growth-regulating effects.

As already mentioned, the compounds are transported according to

the invention systemically in the plants.

In this way, they unfold their growth-regulating effect as well

when applied above the ground as a spray treatment.

The growth-inhibiting effect on watercress is particularly pronounced

and cotton.

In addition to the above-mentioned effects, the compounds according to the invention also exhibit a bactericidal effect which allows further application possibilities.

The compounds according to the invention can either be used alone, in admixture with each other or with other active substances. Optionally, other plant protection or pest control agents can be added depending on the desired effect.

Appropriately, the present active substances or their mixtures are used in the form of preparations, such as powders, spreading agents, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers,

respectively diluents, and possibly wetting, binding, emulsifying and/or dispersing aids. Suitable liquid carriers are e.g. water, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethylsulfoxyd, dimethylformamide, and mineral oil fractions and vegetable oils.

Solid carriers are mineral soil, e.g. tonsil, silica gel, talc, kaolin, attapulgite, limestone, silicic acid and plant products, e.g. flour, suitable.

Surface-active substances can be mentioned e.g. calcium lignin sulfonate, polyoxyethylene alkyl phenyl ether, naphthalene sulfonic acids and their salts, phenol sulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates as well as substituted benzene sulfonic acids and their salts.

If the active substances are to be used for seed staining, dyes can also be mixed to give the stained seed a clearly visible colour.

The proportion of the active substance or active substances in the different preparations can vary within wide limits. For example, the agent contains approx. 10 to 90% by weight active ingredient, approx. 90 to 10% by weight of liquid or solid carriers as well as possibly up to 20% by weight of surfactants.

The agent can be applied in the usual way, e.g. with water carrying in spray mixture amounts of approx. 100 to 1000 l/ha. The use of the agent in so-called "Low-Volume" or "Ultra-Low-Volume methods" is also possible, as is their application in the form of so-called microgranules.

For the preparation of the preparations, e.g. the following components:

A. Spray powder

a) 40% by weight active substance

25 wt% clay minerals

20% by weight silicic acid

10 wt% cellulose pitch ("Zellpech")

5% by weight surfactants based on a mixture of the calcium salt of ligninsulfonic acid with alkyl-phenol polyglycol ether

b) 25% by weight active ingredient

60% by weight kaolin

10% by weight silicic acid

5% by weight surfactants on the basis. of the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of ligninsulfonic acid.

c) 10% by weight active substance

60 wt% clay minerals

15% by weight silicic acid

10% by weight cellulose pitch

5% by weight surfactants based on the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of ligninsulphonic acid.

B. Pasta

4 5% by weight active ingredient

5% by weight sodium aluminum silicate

15% by weight of cetyl polyglycol ether with 8 mol of ethylene oxide

2% by weight spindle oil

10 wt% polyethylene glycol

23 parts water

C. Emulsion concentrate

25% by weight active ingredient

15% by weight cyclohexanone

55% xylene by weight

5% by weight mixture of nonylphenylpolyoxyethylene or calcium dodecylbenzene sulphonate.

The new compounds according to the invention can e.g. prepared by propionitrile of the general formula: is reacted with imidazole of the formula: in the presence of a solvent and optionally in the presence of a base, where R and R1 are as indicated above, and Y is halogen, or optionally in the side chain is halogenated alkylsulfonyloxy-or arylsulfonyloxy.

As a halogen, e.g. mention is made of chlorine, bromine or iodine; as alkylsulfonyloxy methyl, ethyl, propyl and trifluoromethylsulfonyloxy are suitable, and as arylsulfonyloxy the benzylsulfonyloxy and p-toluenesulfonyloxy groups can be mentioned.

The reaction can likewise be carried out in the presence of a solvent, and also with the addition of a strong base, e.g. sodium or potassium hydroxide. Furthermore, imidazole alkali metal can also be used instead of imidazole.

As solvents, substances inert to the reactants are suitable, preferably those with a polar, aprotic character such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-pyrrolidone, tetramethylurea, hexamethylphosphoric acid triamide and benzonitrile, but also higher-boiling aromatic and aliphatic hydrocarbons such as toluene, chlorobenzene or xylene are usable.

The reaction temperature can be varied within wide limits. Temperatures between 100°C and 200°C are preferred. Turnovers take place under normal or positive pressure.

The imidazolyl-propionitrile according to the invention are generally solid, colorless and airless oils. The resulting acid addition salts are colorless and odorless, crystalline compounds. The oils dissolve poorly in water and more or less well in organic solvents such as e.g. alcohols, ethers or chlorinated hydrocarbons. The acid addition salts are partially dissolved in 1 water and. good in polar organic solvents such as acetonitrile, N,N-dimethylformamide, lower alcohols, chloroform and methylene chloride.

The following examples illustrate the preparation of the compounds according to the invention.

Example 1

3-(imidazol-1-yl)-2-phenyl-2-propoxy-propionitrile- hydronitrate

(Connection No. 1)

15 g (0.053 mol) of 3-methylsulfonyloxy-2-phenyl-2-propoxy-propionitrile and 17.89 g (0.263 mol) of imidazole were kept at 140°C for 16 hours with the addition of 1 ml of dimethylformamide

under the exclusion of moisture.

The reaction mixture was poured onto ice water, extracted twice with 75 ml of methylene chloride, the methylene chloride phases were washed twice with water, dried with magnesium sulfate and, after filtering off the drying agent, evaporated in vacuo. The remaining dark oil was dissolved in isopropanol and slightly more than the theoretical amount of 100% nitric acid was added. To complete the fining, some diethyl ether was added. The precipitated product was filtered off with suction and dried.

Yield: 12 g = 71% of the theoretical

Melting point: 168-171°C (decomposition)

Example 2

3-(imidazol-1-yl)-2-phenyl-2-propoxy-propionitrile

(Connection No. 2)

6.2 g (0.0195 mol) of the hydronitrate was dissolved in methanol and made basic with dilute ammonia solution under ice bath cooling. After dilution with water, extract with acetic acid ethyl ester, the organic phase is washed with water and then dried with magnesium sulphate. After filtration, the reaction mixture was evaporated in vacuo. An oil remained which was dried under vacuum.

Yield: 4.85 g = 97% of the theoretical nD<31>= 1.5260.

In an analogous manner, the following compounds according to the invention were prepared.

The compounds to be used as starting materials, 3-aryl or 3-alkyl-sulfonyloxy-propionitrile with the general formula II where Y means aryl or alkylsulfonyloxy, has not yet been described in the literature. You get these aryl or alkylsulfonyloxy compounds of the general formula II by reacting the partially known or by methods known per se (see e.g. Rubin et al., JACS 61_, 192 f

(1945); Hess et al., Ber. dt, chem. Ges. 50, 394 (1917)) available phenylacetonitrile of the general formula III: where Z and R are as indicated for formula I, which are hydroxymethylated by methods known per se and the thus obtained 3-hydroxy-propionitrile of the general formula : where Z and R are as indicated for formula. I, with suitable sulfonic acid derivatives, such as e.g. sulfonic acid chloride, optionally with the addition of an acid binder. The hydroxymethylfor compounds of the general formula IV are not known from the literature to date.

The 3-halopropionitrile with the general formula II where Y is halogen known from the literature are obtained by reacting the above-mentioned phenylacetonitrile with the general formula III with dihalomethanes in a manner known per se.

In the following, the production of a starting material is described.

3- methylsulfonyl- 2- phenyl- 2- propoxy- propionitrile

27 g (0.154 mol) . 2-phenyl-2-propoxy-acetonitrile dissolves

in 120 ml of pyridine and 18.5 g (0.614 mol) of paraformaldehyde is added. To this suspension, 7.7 ml of tetrabutylammonium hydroxide (TBAOH) are added under ice cooling, and the mixture is stirred vigorously for 17 hours. The reaction mixture is poured onto ice water and extracted twice with ether. The ether phase is then washed twice with aqueous sodium chloride solution and dried with magnesium sulphate. After defiltration of the drying agent and re-rotation in vacuum, a colorless oil is obtained which shows uniformity by thin-layer chromatography and can be further processed without further purification.

Yield: 28.4 g = 90% of the theoretical

3- hydroxy- 2- phenyl- 2- propoxy- propionitrile

28 g (0.136 mol) of 3-hydroxy-2-phenyl-2-propoxy-propionitrile are dissolved in 200 ml of toluene and 19.5 g (0.171 mol) of methanesulfonic acid chloride are added. At 10°C, 18.6 g (0.184 mol) of triethylamine are added dropwise. The mixture is stirred for 30 minutes at room temperature, the precipitated triethylamine hydrochloride is filtered off and evaporated. The residue is taken up in ether, washed with dilute HCl solution, water and sodium bicarbonate solution, and again twice with water. You dry with magnesium sulphate, extract the drying agent and evaporate. The oily residue is dried in a vacuum. It turns out to be thin-layer chromatographically pure. Yield: 32.27 g = 86% of the theoretical

nD= 1.5000

3- methylsulfonyl- 2- phenyl- 2- propoxy- propionitrile

The following design examples serve to illustrate the application possibilities of the compound according to the invention, which occurs in the form of the preparations listed above.

Example 3

The effect of the seed treatment against Helminthosporium spee. on construction.

Barley seed with a natural occurrence of Helminthosporium gramineum was untreated, respectively. processed as indicated in

the table, sown in plant pots with soil and kept at temperatures below +16°C for germination. After germination, the sprouts were illuminated daily for 12 hours with artificial light. After approx. After 5 weeks, all emerged as well as the plants attacked by the fungus were counted for each stage of the experiment.

The fungicidal effect was calculated as follows;

The compounds were used as 20% spray powder.

Joint forging dde1

Methoxyethyl-Hg-siiicate 2.63 87

Example 4

The effect of prophylactic foliar treatment against Erysiphe cichoracearum on pumpkin plants in greenhouses.

After drying the spray coating, young pumpkin plants sprayed wet with the stated active substance concentrations were inoculated by dusting with powdery mildew spores of Erysiphe cichoracearum and incubated together with inoculated untreated control plants in a greenhouse at 24°C. After 1 week, the occurring powdery mildew area was estimated as a % of the total leaf area. The herbicidal effect was calculated as follows:

The compounds were formulated as 20% spray powders.

Example 5

The effect of the foliar treatment against Piricularia oryzae on rice seedlings in the greenhouse.

Young rice plants were sprayed while dripping wet with the concentration of active ingredient indicated in the table. After drying the spray coating, the treated plants as well as untreated control plants were inoculated by spraying a suspension of spores (about 200,000 per ml) of the leaf spot producer Piricularia oryzae and inoculated moist at +25 to +27°C in a greenhouse.

After 5 days, it was determined how many percent had been attacked by leaf beetles. From these attack numbers, the fungicidal effect was calculated as follows: ,„„-10 0 . attack in processed 0 ... n 100 - r 2—, r , . 5-^—t= % effect

Attack in untreated

The compounds were formulated as 20% spray powders.

Example 6

Effect of prophylactic foliar treatment against Botrytis cinerea on tomato plants in greenhouses.

Young tomato plants were sprayed dripping wet with it

the active substance concentration indicated in the table. After drying the spray coating, the treated plants as well as untreated ones were inoculated by spraying a suspension of spores (approx. 1 million per ml of fruit juice solution) of the fungus Botrytis cinerea and incubation moist at approx. 20°C in greenhouse. After collapse of the untreated plants (= 100% attack), the degree of attack of the treated plants was determined. The fungicidal effect is calculated as follows:

100 . attack in treated „ . ,

100-—r —.—r. —=%effect

Attack in untreated

The compounds according to the invention were available as 20% formulations.

S ammen1i gnirig's attempt

1-(4-chlorophenoxy)-

3,3-dimethyl-1-(1,2,4-

triazol-1-yl)-2-butanone 0.025 60

Example 7

Effect of prophylactic foliar treatment against Plasmopara viticola on grape plants in greenhouses.

Young grape plants with approx. 5 to 8 leaves were sprayed dripping wet with the specified concentration, after drying the spray coating, the underside of the leaves was sprayed with an aqueous slurry of sporangia of the fungus (approx. 20,000 per ml) and immediately incubated in a greenhouse at 22 to 24°C and most possible water vapor saturated atmosphere.

From the second day, the humidity for 3 to 4 days was taken back to normal height (30 to 70% saturation) and then for one day held at water vapor saturation. Then, for each leaf, the percentage of the surface affected by the fungus was noted, and the average for each treatment was calculated to determine the fungicidal effect, as follows:

The compounds were formulated as 20% spray powders.

Example 8

In the laboratory, cress seeds treated with an aqueous emulsion of the agent according to the invention.

The concentration of the active ingredient in the emulsion was 100 ppm. For this purpose, a slide was arranged in a 200 ml cylindrical glass tube with 10 ml active substance emulsion.

There was stretched filter paper on the slide. When the filter paper was permeated with the solution, 10 cress seeds were evenly distributed over this. A Petri dish was then coated over the glass cylinder. Two glass cylinders were used for each substance.

After 7 days, the length of the shoots and roots of the germinated seeds was measured.

The table shows the values in relation to the control Expressed as a percentage.

It turned out that the new compounds exerted a strong influence on root and shoot growth in watercress. This is expressed by the fact that they promote (>100%) or inhibit (<100%) the individual parts.

Example 9

Cotton was grown under greenhouse conditions to the cotyledon stage.

The new compounds were sprayed on the plants in amounts of 1 and 2 kg active substance/ha. 3 weeks after application, the plants' total length and the length of the first internode were measured. In the table, the results are stated in the form of percentages in total

equation with control.

The results show a reduction in growth that was stronger than the comparison preparation. Means of comparison

Example 10

Effect of seed treatment against cereal powdery mildew Erysiphe graminis on barley.

Seeds of summer barley were untreated or stained with 100 g active substance/100 kg sown in soil in planters and allowed to stand at temperatures around 20°C in greenhouses until germination. After formation of the first leaf, the plants were inoculated by brushing over plants infested with powdery mildew. A week later, it was noted what percentage of the leaf surface was covered with powdery mildew. A fungicidal effect was calculated as follows:

Any incompatibility of the treatment was judged after germination of the plants. The assessment was made according to the following form:

0 = total destruction

1 = 90% destruction

2 = 80% destruction

3 = 70% destruction

4 = 60% destruction

5 = 50% destruction

6 = 40% destruction

7 = 30% destruction

8 = 20% destruction

9 = 10% destruction

10 = undamaged

The new compounds were available as spray powder with 20% active substance content.

In contrast to the comparator, the new compounds showed not only a complete effect against Erysiphe graminis, but also a complete compatibility with the barley plants,

Connection number

Means of comparison

1-(4-chlorophenoxy)-3,3-

dimethyl-1-(1,2,4-

triazol-1-yl)-2-butanone 100 4

Example 11

Effect of prophylactic foliar treatment against leaf spot disease (Cercospora beticola) on sugar beet (Beta vulgaris).

Sugar beet plants with 4 well-developed leaves were sprayed dripping wet with the indicated concentration. After drying the spray coating, the treated plants as well as untreated control plants were sprayed with a suspension of

15,000 Cercospora spores per milliliters. At 26°C and water vapour-saturated air, the plants were incubated for 4 days in a greenhouse and were then kept at 22°C for a further 10 days in a greenhouse. Then the proportion of the attacked leaf surface was noted. The efficacy of the fungicide was calculated as follows:

,-100. attack in treated „ . ,

100 - r 2—. r .. —-— = % effect

Attack in untreated Comparator

Example 12

Inhibition of fungal growth on nutrient solution.

20 ml of a nutrient solution of grape juice and water (1:1) was filled into 100 ml glass flasks and added to the powdered active substance preparation. Then spores of Penicillium digitatum were inoculated. After an incubation period of 5 days at 22 - 24°C, the fungal development on the surface of the nutrient solution was determined.

Grading: 0 = no fungal growth

1 = individual fungal colonies on the surface

2 = 5 - 10% of the surface covered by fungus

3 = 10 - 30% of the surface covered by fungus

4 = 30 - 60% of the surface covered by fungus

5 = 60 - 100% of the surface covered by fungi Active ingredient, active ingredient concentrations in the nutrient solution and results are listed in the following table. Means of comparison

Untreated nutrient solution

Control - 5

Example 13

Effect of prophylactic foliar treatment against true vine mealybug Uncinula necator.

Young vines of the Sylvan variety with 8 to 10 leaves were sprayed dripping wet with the concentrations indicated in the table. After drying the spray coating, the plants were dry-pollinated with conidium spores of the fungus Uncinula necator and were incubated in a greenhouse at 22°C for 12 days. Then, the degree of powdery mildew attack on the leaf surface was assessed as a percentage, and the fungicidal effect was calculated as follows:

The attack reached 88.3% on untreated plants. The agent was available as a 20% spray powder. The effect is indicated in

the table.

Example 14

Effect of prophylactic foliar treatment against apple scab Venturia inaequalis in open fields.

Shoots of apple plants of the variety MM 106 in growth were sprayed dripping wet with a 0.1% active ingredient concentration. After drying the spray coating, a suspension of conidium spores was formed

(330,000 per milliliter) sprayed on the leaves, and then the shoots were exposed to infection by the fungus for 3 days under partial shade after covering with polyethylene bags. The bag was then removed. After a total of 2 1/2 weeks of trial duration,

the degree of scouring surface calculated as a percentage. The untreated control plant showed 99% attack. The result of the treatment was calculated as follows:

The compounds were available as 20% spray powder.

Connection number

Example 15

Effect of foliar treatment against apple scab Venturia inaequalis in the open field.

Shoots of apple plants of variety MM 106 which were in growth were sprayed with a suspension of conidium spores (330,000 per milliliter) and then kept moist by covering with polyethylene bags. The plants were in partial shade. After 3 days the bag was removed. 7 days after inoculation, the plants were treated dripping wet with 0.1% active ingredient concentration. After a further 1 1/2 weeks, the degree of apple scab-infested leaf surface was calculated as a percentage, which on an untreated plant amounted to 99%. The new compounds were available as 20% spray powders. The effect of the treatment was calculated as follows;

Connection number

Means of comparison

2-Butyl-3-(imidazol-1-yl)-2-phenyl-propionitrile hydronitrate 90

Example 16

Prophylactic foliar treatment against Erysiphe graminis

on construction,

Barley plants in the first leaf stage were sprayed dripping wet with the specified concentration of active ingredient with the addition of an alkaryl polyglycol ether as wetting agent (0.05%). After drying the spray coating, these plants as well as untreated control plants were evenly coated with powdery mildew-infected cereal plants, and were then incubated in a greenhouse at 20 - 22°C for 1 week. Then the average powdery mildew infestation in each pot (18 to 20 plants) was noted. The fungicidal effect was calculated according to the formula:

The new compounds were available as 20% formulations.

Example 17

Effect of prophylactic foliar treatment against Uromyces appendiculatus (bean rust) in greenhouses.

Bush bean plants in the stage with semi-developed primary leaves were sprayed dripping wet with 100 ppm active ingredient concentration. After drying the spray coating, the treated plants as well as untreated control plants were sprayed with a suspension of uredospores of Uromyces appendiculatus. The plants were incubated for 2 days in a humidity cabinet at 22°C and then kept under greenhouse conditions at about 22°C. 11 days after spraying the spores, the rust blisters were counted (on average 253 per leaf in the untreated control plant). The fungicidal effect was calculated as follows:

The new compounds were available as 20% formulations and showed over 90% efficacy.

Example 18

Effect of prophylactic foliar treatment against Helminthosporium teres (= Pyrenophora teres), net spot disease on barley.

Young barley plants in the first leaf stage were sprayed dripping wet with the specified concentrations. After drying the spray coating, the treated plants and untreated control plants were sprayed with a suspension of conidial spores of Helminthosporium teres and grown in a humidity chamber for 2 days at 20-22°C. One week after inoculation, the percentage attack on the leaf surface was noted. The fungicidal effect was calculated as follows:

The compounds were available as 20% formulations.

Example 19

Effect of prophylactic foliar treatment against dwarf rust Puccinia hordei on barley in an air-conditioned plant growth chamber.

Young barley plants in the first leaf stage were sprayed dripping wet with the specified concentration. After drying the spray coating, the treated plants as well as untreated control plants were inoculated by brushing with dwarf rust-infected plants and brought into a plant growth chamber. The plants were cultivated at 15 C for 10 days, the first two days under almost moisture-saturated air. Then the percentage of the leaf surface affected by rust was noted. The fungicidal effect was calculated as follows:

The compounds were available as 20% formulations.

The table shows the good effect for a majority of the new connections.

Example 20

Effect of prophylactic foliar treatment against yellow rust Puccinis striiformis on barley in an air-conditioned plant growth chamber.

Young barley plants in the first leaf stage were sprayed dripping wet with the specified concentrations. After drying the spray coating, the treated plants as well as untreated control plants were sprayed with a suspension of uredospores of Puccinia striiformis in 1,1,2-trifluoro-1,2,2-trichloroethane and incubated in a plant growth chamber at 15°C. During the first two days, moisture-saturated air was provided. After 15 days, the percentage of leaf surface affected by rust was noted.

The fungicidal effect was calculated as follows:

Means of comparison

Example 22

Effect against Pseudomonas phaseolicola, the cause of fatty spot disease on beans, in vitro.

After heat sterilization at 45°C, biomalt agar was cooled and then mixed with the test substances in an aqueous preparation and poured into plastic Petri dishes. After solidification of the nutrient medium, the dishes with treated agar as well as with untreated agar as a control, were inoculated with a suspension of the fat spot-causing Pseudomonas phaseolicola in the center using an inoculum. The dishes were then incubated at 22°C. After 2 1/2 weeks, the radial extent of the grown bacterial colonies was measured. From the average of two repetitions per test section, the bacteria-inhibiting effect was calculated as follows: ,„»Radial growth in treated . 100 _ , .. , 100 - —T- ,.—t i—r—; r—r —r= % inhibitory effect

Radial growth in untreated

The compounds were available as 20% formulations.

% inhibitory effect of 250 ppm active substance in agar against Pseudomonas phaseolicola.

Example 21

Effect of seed treatment against Helminthosporium sativum on barley in a climate-controlled plant growth chamber. Barley seed with artificial infestation of Helminthosporium sativum was dusted with 50 g of agent containing the active ingredient per 100 kg. For each experimental stage, 2 g of was treated, respectively. untreated seed, sown in plastic pots of 6.5 x 6.5 cm. Sand was used as substrate. Each experimental stage was repeated 2 times. The pots were placed in a plant growth chamber at 15°C. After 4 weeks, the germinated plants were examined with regard to percentage attack on the stem. From the average of the repeated treatments, the fungicidal effect was calculated as follows:

The agent according to the invention was available as a 20% formulation. Means of comparison

Example 22

Effect against Pseudomonas phaseolicola, the cause of fatty spot disease on beans, in vitro.

After heat sterilization at 45°C, biomalt agar was cooled and then mixed with the test substances in an aqueous preparation and poured into plastic Petri dishes. After solidification of the nutrient medium, the dishes with treated agar as well as with untreated agar as a control were inoculated with a suspension of fat spot- the developer Pseudomonas phaseolicola in the center using a dipper. The dishes were then incubated at 22°C. After 2 1/2 weeks, the radial extent of the grown bacterial colonies was measured. From the average of two repetitions per test phase, the bactericidal effect was calculated as follows:

The compounds were available as 20% formulations.

% inhibitory effect of 250 ppm active substance in agar against Pseudomonas phaseolicola.

Means of comparison

2-butyl-3-(imidazol-1-yl)-2-

phenyl propionitrile hydronitrate 4 2

Example 23

Effect of prophylactic foliar treatment against downy mildew Erysiphe graminis on barley in greenhouses.

Young barley plants in the first leaf stage were sprayed dripping wet with the specified concentrations. After drying the spray coating, the treated plants as well as untreated control plants were inoculated with dry powdery mildew spores, by coating the experimental plants with infected plants. The experimental plants were then grown in greenhouses at 20 to 22°C, and after one week the percentage attack of the leaf surface was determined. The fungicidal effect was calculated as follows:

The compounds were available as 20% formulations.

By proceeding as described in the preceding examples, the following compounds can be prepared: 3-(imidazol-1-yl)-2-phenyl-2-propoxy-propionitrile hydronitrate 3-(imidazol-1-yl)-2-phenyl -2-propoxy-propionitrile 2-butoxy-3-(imidazol-1-yl)-2-phenyl-propionitrile hydronitrate 2-butoxy-3-(imidazol-1-yl)-2-phenyl-propionitrile 2-allyloxy- 3-(imidazol-l-yl)-2-phenyl-propionitrile hydronitrate 2-allyloxy-3-(imidazol-l-yl)-2-phenyl-propionitrile 2-ethoxy-3-(imidazol-l-yl)- 2-Phenyl-propionitrile hydronitrate 2-ethoxy-3-(imidazol-l-yl)-2-phenyl-propionitrile 3-(imidazol-l-yl)-2-methoxy-2-phenyl-propionitrile hydronitrate 3-( imidazol-1-yl)-2-methoxy-2-phenyl-propionitrile 2-(2-chlorophenyl)-3-(imidazol-1-yl)-2-propoxy-propionitrile hydronitrate

2-butoxy-2-(4-chlorophenyl)-3-(imidazol-1-yl)-propionitrile hydronitrate

2-butoxy-2-(2-chlorophenyl)-3-(imidazol-1-yl)-propionitrile hydronitrate

2-allyloxy-2-(2-chlorophenyl)-3-(imidazol-1-yl)-propionitrile hydronitrate

2-(4-Chlorophenyl)-3-(imidazol-1-yl)-2-propoxypropionitrile hydronitrate

2-allyloxy-2-(4-chlorophenyl)-3-(imidazol-1-yl)-propionitrile hydronitrate

2-(2-Chlorophenyl)-3-(imidazol-1-yl)-2-propoxy-propionitrile

2-butoxy-2-(4-chlorophenyl)-3-(imidazol-1-yl)-propionitrile 2-butoxy-2-(2-chlorophenyl)-3-(imidazol-1-yl)-propionitrile 2-allyloxy- 2-(2-chlorophenyl)-3-(imidazol-1-yl)-propionitrile 2-(4-chlorophenyl)-3-(imidazol-1-yl)-2-propoxy-propionitrile 2-allyloxy-2-(4 -chlorophenyl) -.3-(imidazol-l-yl)-propionitrile 2-benzyloxy-3-(imidazol-l-yl)-2-phenyl-propionitrile-hydro-

nitrate

2- benzyloxy-3-(imidazol-1-yl)-2-phenyl-propionitrile 3-(imidazol-1-yl)-2-isopropyloxy-2-phenyl-propionitrile hydronitrate

3-(imidazol-1-yl)-2-isopropyloxy-2-phenyl-propionitrile 2-(4-chlorophenyl)-2-hexyloxy-3-(imidazol-1-yl)-propionitrile hydronitrate

2-(4-Chlorophenyl)-2-hexyloxy-3-(imidazol-1-yl)-propionitrile 2-allyloxy-3-(imidazol-1-yl)-2-(2-methylphenyl)-propionitrile hydronitrate

2-(3,4-Dichlorophenyl)-3-(imidazol-1-yl)-2-propoxy-propionitrile hydronitrate

2-butoxy-2-(2,4-dichlorophenyl)-3-(imidazol-1-yl)-propionitrile hydronitrate

2-allyloxy-2-(2,4-dichlorophenyl)-3-(imidazol-1-yl)-propionitrile hydronitrate

2-ethoxy-2-(3,4-dichlorophenyl)-3-(imidazol-1-yl)-propionitrile hydronitrate

2-allyloxy-3-(imidazol-1-yl)-2-(2-methylphenyl)-propionitrile 2-(3,4-dichlorophenyl)-3-(imidazol-1-yl)-2-propoxy-propionitrile 2- allyloxy-2-(374-dichlorophenyl)-3-(imidazol-1-yl)-propionitrile 2-butoxy-2-(2,4-dichlorophenyl)-3-(imidazol-1-yl)-propionitrile 2-allyloxy- 2-(2,4-dichlorophenyl)-3-(imidazol-l-yl)-propionitrile 2-ethoxy-2-(3,4-dichlorophenyl)-3-(imidazol-l-yl)-propionitrile 3-(imidazol -1-yl)-2-phenyl-2-(1,2,2-trimethyl-propoxy)-propionitrile hydronitrate

3-(imidazol-1-yl)-2-(2-methoxy-ethoxy)-2-phenyl-propionitrile hydronitrate

2-(.2,2-dimethylpropoxy)-3-(imidazol-1-yl)-2-phenyl-propionitrile hydronitrate

2-(2,2-dimethyl-propoxy)-3-(imidazol-1-yl)-2-phenyl-propionitrile

2-(2-Fluorophenyl)-3-(imidazol-1-yl)-2-propoxy-propionitrile hydronitrate

2-butoxy-2-(2-fluorophenyl)-3-(imidazol-1-yl)-propionitrile hydronitrate

2-(4-Fluorophenyl)-3-(imidazol-1-yl)-2-propoxy-propionitrile hydronitrate

2-butoxy-2-(4-fluorophenyl)-3-(imidazol-1-yl)-propionitrile hydronitrate

2-allyloxy-2-(2-fluorophenyl)-3-(imidazol-1-yl)-propionitrile hydronitrate

2-ethoxy-2-(2-fluorophenyl)-3-(imidazol-1-yl)-propionitrile hydronitrate

2-(2-Fluorophenyl)-3-(imidazol-1-yl)-2-methoxy-propionitrile hydronitrate

3-(imidazol-1-yl)-2-phenyl-2-(1,2,2-trimethyl-propoxy)-propionitrile

3-(imidazol-1-yl)-2-(2-methoxy-ethoxy)-2-phenyl-propionitrile 2-(2-fluorophenyl)-3-(imidazol-1-yl)-2-propoxy-propionitrile 2- butoxy-2-(2-fluorophenyl)-3-(imidazol-1-yl)-propionitrile 2-(4-fluorophenyl)-3-(imidazol-1-yl)-2-propoxy-propionitrile 2-butoxy-2- (4-fluorophenyl)-3-(imidazol-1-yl)-propionitrile 2-(2-fluorophenyl)-3-(imidazol-1-yl)-2-methoxy-propionitrile 2-ethoxy-2-(2-fluorophenyl) )-3-(imidazol-1-yl)-propionitrile 2-allyloxy-2-(2-fluorophenyl)-3-(imidazol-1-yl)-propionitrile 2-allyloxy-2-(4-fluorophenyl)-3- (imidazol-1-yl)-propionitrile hydronitrate

2-ethoxy-2-(4-fluorophenyl)-3-(imidazol-1-yl)-propionitrile hydronitrate

2-(4-Fluorophenyl)-3-(imidazol-1-yl)-2-methoxy-propionitrile hydronitrate

2-ethoxy-2-(4-fluorophenyl)-3-(imidazol-1-yl)-propionitrile 2-(4-fluorophenyl)-3-(imidazol-1-yl)-2-methoxy-propionitrile 2-allyloxy- 2-(4-fluorophenyl)-3-(imidazol-1-yl)-propionitrile 2-decyloxy-3-(imidazol-1-yl)-2-phenyl-propionitrile hydronitrate 2-(3,3-dimethylbutoxy)- 3-(imidazol-1-yl)-2-phenyl-propionitrile hydronitrate

3-(imidazol-1-yl)-2-octyloxy-2-phenyl-propionitrile

2-(3,3-dimethoxybutoxy)-3-(imidazol-1-yl)-2-phenyl-propionitrile

2-(4-Bromophenyl)-2-butoxy-3-(imidazol-1-yl)-propionitrile hydronitrate

2-(4-Bromophenyl)-3-(imidazol-1-yl)-2-propoxy-propionitrile hydronitrate

2-(4-bromophenyl)-2-hexyloxy-3-(imidazol-1-yl)-propionitrile hydronitrate

3-(imidazol-1-yl)-2-(2-methylphenyl)-2-propoxy-propionitrile hydronitrate

2-hexyloxy-3-(imidazol-1-yl)-2-(2-methylphenyl)-propionitrile hydronitrate

2-(4-Bromophenyl)-2-butoxy-3-(imidazol-1-yl)-propionitrile 2-(4-Bromophenyl)-3-(imidazol-1-yl)-2-propoxy-propionitrile 2-(4 -bromophenyl)-2-hexyloxy-3-(imidazol-1-yl)-propionitrile 2-butoxy-3-(imidazol-1-yl)-2-(2-methylphenyl)-propionitrile 2-butoxy-3-(imidazole -1-yl)-2-(2-methylphenyl)-propionitrile hydronitrate

2-hexyloxy-3-(imidazol-l-yl)-2-(2-methylphenyl)-propionitrile 2-decyloxy-3-(imidazol-l-yl)-2-phenyl-propionitrile 3-(imidazol-l-yl )-2-(2-methylphenyl)-2-propoxy-propionitrile 2-butoxy-2-(3-chlorophenyl)-3-(imidazol-1-yl)-propionitrile 2-(3-chlorophenyl)-2-hexyloxy- 3-(Imidazbl-1-yl)-propionitrile hydronitrate

2-decyloxy-3-(imidazol-1-yl)-2-(2-methylphenyl)-propionitrile hydronitrate

3-(imidazol-1-yl)-2-(2-methylphenyl)-2-octyloxy-propionitrile 2-decyloxy-3-(imidazol-1-yl)-2-(2-methylphenyl)-propionitrile 2-butoxy- 3-(imidazol-1-yl)-2-(4-methoxyphenyl)-propionitrile hydronitrate

2-butoxy-3-(imidazol-1-yl)-2-(4-methoxyphenyl)-propionitrile 2-(4-chlorophenyl)-2-hexyloxy-3-(imidazol-1-yl)-propionitrile hydrogen oxalate

2-(4-Chlorophenyl)-2-hexyloxy-3-(imidazol-1-yl)-propionitrile hydrogen sulfate

Claims (12)

1. Imidazolyl propionitriles, characterized in that they have a general formula in which R denotes an aromatic hydrocarbon residue which is optionally substituted with one or more, the same or different halogen, (C^-C^)-alkyl, (C^-C^)-alkoxy, (C1-C4)-alkylthio, trifluoromethyl or nitro substituents , R^^ denotes (C-^ -C^ )-alkyl, (C^-Cg)-alkenyl, (C3-Cg) alkynyl or a phenylalkyl radical which is optionally substituted with one or more, the same or different halogen, (C^ - C^)-alkyl, (C1~ C4 )-alkoxy, (C1~ C4 )-alkylthio, trifluoromethyl or nitro substituents, and their acid addition salts with inorganic and organic acids, 2, Imidazolyl-propionitriles according to claim 1, characterized in that R denotes a phenyl residue which is optionally substituted with one or more, the same or different halogen, (C^-C^)-alkyl, (C^-C^ )- alkoxy, (C1~C4 )-alkylthio, trifluoromethyl or nitro substituents and R 1 is (C 1 -C 1 )-alkyl, allyl, propargyl or a benzyl residue 1 lb which are optionally substituted with one or more, the same or different halogen, (C1-C4 )-alkyl, (Cy-C4)-alkoxy, (C3-C4)-alkylthio, trifluoromethyl or nitro substituents. 3. 2-butoxy-2-(4-chlorophenyl)-3-(imidazol-1-yl)-propionitrile hydronitrate. 4,2-butoxy-2-(2-chlorophenyl)-3-(imidazol-1-yl)r-propionitrile hydronitrate. 5. 2-(4-Chlorophenyl)-3-(imidazol-1-yl)-2-propoxypropionitrile hydronitrate. 6. 2-(2-Chlorophenyl)-3-(imidazol-1-yl)-2-propoxy-propionitrile. 7• 2-butoxy-2-(2-chlorophenyl)-3-(imidazol-1-yl)-propionitrile. 8. Process for the production of imidazolyl-propionitrile according to claims 1-7, characterized in that compounds of general formula is reacted with imidazole of formula in the presence of a solvent and optionally in the presence of a base, in which R and R^ have the above-mentioned meanings, and Y denotes halogen or the optionally halogenated alkylsulfonyloxy or arylsulfonyloxy residue in the side chain. 9, Biocidal agent, characterized in that it contains at least one compound according to claims 1-7; 10/ Biocidal agent according to claim 9 with fungicidal effect. x 11. Biocidal agent according to claim 9 with growth regulating effect, 12. Biocidal agent according to claim 9 with bactericidal effect.