NO831448L - BIOCIDE AGENTS CONTAINING 1,2,4-TRIAZOL-1-YL PROPION NITRILS AND PROCEDURES FOR THE PREPARATION OF THESE - Google Patents

Description

The present invention relates to new 1,2,4-triazol-1-yl-propionitriles, methods for the production of these compounds as well as biocidal agents containing these compounds, in particular with fungicidal action.

Imidazolyl-propionitrile derivatives with fungicidal action are already known (DE-OS 26 04 047). However, these exhibit a relatively narrow spectrum of action, which is unsatisfactory.

The task of the present invention is to develop new propionitrile derivatives 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 of the general formula:

wherein R denotes an aromatic hydrocarbon residue which is optionally substituted with one or more, the same or different substituents selected from halogen, (C-^-C^)-alkyl, (C-^-C^)-alkoxy, (C1~C^ )-alkylthio, trifluoromethyl or nitro, and denotes (C1-C1Q)-alkyl, (C3-C8)-alkenyl, (C3-C8-alkynyl or a phenylalkyl radical which may optionally be substituted with one or more, identical or different substituents selected from halogen, (C-^-C^)-alkyl, (C-^-C^Valkoxy, (C-^-C^)-alkylthio, trifluoromethyl or the nitro group, and their acid addition salts with inorganic and 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 to the opposite of the most diverse systematic types. When treating above-ground plant parts, they protect against wind-borne pathogens. Against seed-borne pathogens, the compounds can be used for seed treatment. Moreover, they act systemically, i.e. they are taken up by the plants' roots, e.g. after introduction with seeds, 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, special areas of application are achieved here in which the compounds exhibit an outstanding effect. Thus, they can always be used as fungicides, plant growth regulators or bactericides.

In the compounds indicated by general formula I, the substituents can for example have the following meaning: R can denote 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 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-butyl-phenyl, 3-butylphenyl, 4-butylphenyl, 2- sec.-butylphenyl, 3-sec.-butylphenyl, 4-sec.-butylphenyl, 2-tert.-butylphenyl, 3-tert.-butyl-phenyl, 4-tert.-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, 3-chloro-5-nitrophenyl, 4-chloro-2-fluorophenyl, 3,4,5-tri-methoxyphenyl or 2-chloro-2-nitrophenyl and

R 1 can denote (C 1 -C 2 )-alkyl, e.g. methyl, ethyl, propyl, pentyl, hexyl, heptyl/octyl, nonyl, decyl, isopropyl, 2,2-dimethylpropyl-1, 3,3-dimethyl-butyl-2, (C3-C8)-alkenyl,

e.g. 2-buten-1-yl, 3-methyl-2-buten-1-yl, hexenyl, heptenyl, octenyl, 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-trlfluoromethylbenzyl, 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- methylthiobenzyl, 2-ethylthiobenzyl, 3-ethylthiobenzyl, 4-ethylthiobenzyl, 2-butylthiobenzyl, 3-butylthiobenzyl, 4-butylthiobenzyl.

Examples of inorganic and organic acids for the formation of the acid addition salts include the hydrohalic acids, such as e.g. hydrochloric acid and hydrobromic acid, furthermore phosphoric acid, sulfuric acid, especially nitric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids such as e.g. acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbitan acid, malic acid, as well as sulphonic acids such as e.g. p-toluenesulfonic acid and 1,5-naphthalenedisulfonic 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.

Among the compounds according to the invention, they are distinguished by a fungicidal action which in general formula I has substituents where: R denotes phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 4- bromophenyl, 2-fluorophenyl, 4-fluorophenyl or 2-methylphenyl and

R^ denotes ethyl, allyl, propyl, isopropyl, butyl or hexyl.

Preferably, mention should be made of such compounds in which

R denotes phenyl, 4-chlorophenyl or 2-methylphenyl, and

R^ denotes propyl, isopropyl or butyl.

The following compounds according to the invention have outstanding effects: 2-isopropoxy-2-phenyl-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate,

2-butoxy-2-(2-methylphenyl)-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate,

2-phenyl-2-propoxy-3-(1,2,4-triazol-1-yl)-pro<p>ionitrile, hydronitrate,

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

2-(4-chlorophenyl)-2-propoxy-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate,

2-isopropoxy-2-phenyl-3-(1,2,4-triazol-l-yl)-propionitrile, 2-butoxy-2-(2-methylphenyl)-3-(1,2,4-triazol-l -yl)-propionitrile, 2-hexyloxy-2-phenyl-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate,

2-butoxy-2-(4-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propionitrile, 2-(4-chlorophenyl)-2-propyloxy-3-(1,2,4 -triazol-1-yl)-propionitrile, 2-hexyloxy-2-(2-methylphenyl)-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate,

2-butoxy-2-phenyl-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate,

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

2-ethoxy-2-phenyl-3-(1,2,4-triazbl-l-yl)-propionitrile, hydronitrate,

2-allyloxy-2-phenyl-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate,

2-(2-chlorophenyl)-2-propoxy-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate,

2-(4-Chlorophenyl)-2-hexyloxy-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate

2-hexyloxy-2-(2-methylphenyl)-3-(1,2,4-triazol-1-yl)-propionitrile,

2-butoxy-2-phenyl-3-(1,2,4-triazol-1-yl)-propionitrile, 2-(2-chlorophenyl)-2-butoxy-3-(1,2,4-triazol-1 -yl)-propionitrile, 2-ethoxy-2-phenyl-3-(1,2,4-triazol-1-yl)-propionitrile,

2-allyloxy-2-phenyl-3-(1,2,4-triazol-l-yl)-propionitrile, 2-(2-chlorophenyl)-2-propoxy-3-(1,2,4-triazol-l -yl)-propionitrile.

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

Depending on the plant species and amount of application, they also exhibit herbicidal action.

As the new compounds cause qualitative as well as quantitative changes on the plants and also changes in the plants' metabolism, they belong to the class of plant growth regulators which are characterized by the following application possibilities: Inhibition of the vegetative growth of woody and herbaceous plants, for example at roadsides, rail installations o.l., to avoid too strong growth, growth inhibition in cereals to avoid dead spots, and in cotton to achieve an increase in yield.

Impact of the branching of vegetative and generative organs in ornamental and useful plants to increase flowering or in tobacco and tomatoes to inhibit side shoots.

Improvement of fruit quality, for example an increase in the sugar content of sugar cane, sugar beet or fruit, and at the same time ripening of the fruit, which leads to a higher yield.

Increase in resistance to climatic effects such as cold and drought.

Impact of latex flow in rubber plants.

Formation of parthenocarpic fruit, pollen sterility and hereditary influence are also application possibilities.

Control of seed germination or bud development.

Leaf fall or impact of fruit fall to facilitate harvesting.

The new compounds were particularly suitable for impact

of the growth of beta-beet, but also exhibits the desired growth-regulating effect on grain, soya and cotton.

Depending on the application target, the amount of application is generally 0.05 to 5 kg of active substance/ha, but possibly higher application amounts can also be used.

The period of use depends on the purpose of use and

the climatic conditions.

Quite surprisingly, the new compounds are more widely active or more effective than the known products with the same direction of action.

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, elixirs, 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.

As solid carrier substances 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, 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 100 to 1000 l/ha. Application of the agent in so-called "Low-Volume" or "Ultra-Low-Volume" methods is also possible as well as 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% by weight cellulose pitch (Zellpech)

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

b) 25% by weight active ingredient

60% by weight kaolin

10% by weight silicic acid

5% by weight surfactants based on the sodium salt of N-methyl-N-oleyltaurine and the calcium salt of ligninsulfonic acid

c) 10% by weight active ingredient

60 wt% clay minerals

15% by weight silicic acid

10% by weight cellulose pitch (Zellpech)

5% by weight surfactants based on the sodium salt of N-methyl-N-oleyltaurine and the calcium salt of ligninsulfonic acid

B. Pasta

45% 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, for example, be prepared by reacting propionitrile of the general formula: with 1,2,4-triazole of the formula: or its alkali compounds in the presence of a solvent and optionally in the presence of a base, in which R and R meanings given above and Y denotes halogen, or possibly the halogenated alkylsulfonyloxy or arylsulfonyloxy residue in the side chain.

Examples of halogens include chlorine, bromine or iodine; suitable as an alkylsulfonyloxy radical are, for example, the methyl, ethyl, propyl and trifluoromethylsulfonyloxy group, and as an arylsulfonyloxy radical, suitable examples are the benzylsulfonyloxy and p-toluenesulfonyloxy group.

The reaction can be carried out both with an excess of 1,2,4-triazole, possibly in the presence of a solvent, and also with the addition of a strong base, e.g. sodium or potassium hydroxide. Furthermore, instead of 1,2,4-triazole, 1/2,4-triazole alkali metals can also be used.

As a solvent, substances that are inert to the reactants can be used, preferably polar, aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetramethylurea, hexamethylphosphoric acid triamide and benzonitrile, but also higher-boiling aromatic and aliphatic hydrocarbons such as toluene, chlorobenzene or xylene can be used.

The reaction temperature can be varied within wide limits. A temperature between 100 and 200°C is preferably used. The conversion takes place under normal or positive pressure.

The new 1,2,4-triazol-1-yl-propionitrile are generally solid, colorless and odorless substances. The resulting acid addition salts are colorless and odorless, crystalline compounds. The free bases 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 dissolve partially in water and well in polar organic solvents such as acetonitrile, N,N-dimethylformamide, lower alcohols, chloroform and methylene chloride.

The following examples illustrate the preparation

of the new connections.

Example 1

2-isopropoxy-2-phenyl-3-(1,2,4-triazol-1-yl)-propionitrile hydronitrate .. : :

Connection No. 2

To 0.55 mol of sodium hydride suspended in 50 ml of dry DMF was added with stirring and while cooling 0.55 mol of 1,2,4-triazole. Then 0.11 mol of 2-isopropoxy-3-methyl-sulfonyloxy-2-phenylpropionitrile in 50 ml of DMF was added, and the mixture was kept for 1.5 hours at 150°C. After cooling, the mixture was extracted three times with 100 ml of ether, the combined ether phases were washed. 2 times with water and dried with magnesium sulfate. The ether was evaporated in vacuo, 50 ml of isopropanol was added to the residue and 6.8 ml of concentrated nitric acid was added dropwise while cooling while stirring. After adding 80 ml of ether, the mixture was stirred for 1/4 hour, and the product

were divorced. The product was recrystallized from isopropanol.

Melting point: 185-189°C (decomposition)

Yield: 15 g = 43% of theoretical

DMF = dimethylformamide

Example 2

2-isopropoxy-2-phenyl-3-(1,2,4-triazol-1-yl)- propionitrile Compound No. 3 10 g 2-isopropoxy-2-phenyl-3-(1,2,4-triazol- 1-yl)-propionitrile hydronitrate was dissolved in methanol and 8 ml of 32% ammonia water was added. The mixture was poured into water, extracted with acetic acid ethyl ester, dried over MgSO4, after which the acetic ester was evaporated in vacuo, the residue was added with a little acetate and active carbon, boiled, separated and evaporated under vacuum. The solid thus obtained was analytically pure.

M.p.: 176-177°C

Yield: 6.65 g = 83% of theoretical

In an analogous manner, the following compounds were prepared.

Physical

They used 3-aryl or 3-alkylsulfonyloxy-propionitrile of general formula II where Y denotes aryl or alkylsulfonyloxy, has not previously been described in the literature.

These are obtained by partially known or per se known methods (e.g. Rubin et al., JACS §1_, 192 f

(1945); Hess et al., Ber. date chem. Ges. 50, 394 (1917)) available phenylacetonitrile of general formula III: in which R and R1 have the previously indicated meanings, are hydroxy-methylated in a manner known per se, and that the thus obtained 3-hydroxypropionitrile of general formula IV: with suitable sulfonic acid derivatives, such as e.g. sulfonic acid chlorides, optionally with the addition of an acid binder. The hydroxymethyl compounds of general formula IV were previously not known from the literature.

In what follows, the production of an output connection is described.

3- roethy1sulfohy1- 2- pheny1- 2- propdxy- pr opi oni tr i1

27 g (0.154 mol) of 2-phenyl-2-propoxy-acetonitrile was dissolved

in 120 ml of pyridine and added 18.5 g (0.614 mol) of paraformaldehyde. 7.7 ml was added to this suspension under ice-cooling

tetrabutylammonium hydroxide (TBAOH) as a 40% solution, and the mixture was vigorously stirred. After a few hours (DC control), the mixture was poured into ice water and extracted with ether. The ether phase was washed with dilute hydrochloric acid and then with sodium chloride solution and dried with magnesium sulfate. After filtering off the desiccant and evaporation in a vacuum, a colorless oil was obtained which, by thin-layer chromatography, proved to be uniform and which could be processed further without further purification.

Yield: 28.4 g = 90% of theory of 3-hydroxy-2-phenyl-2-propoxy-propionitrile.

20

n^ : 1.5027 28 g (0.136 mol) of 3-hydroxy-2-phenyl-2-propoxy-propionitrile were dissolved in 200 ml of toluene and 19.5 g (0.171 mol) of methanesulfonic acid chloride were added. At 10°C, 18.6 g (0.184 mol) of triethylamine was added dropwise. The mixture was stirred for 30 minutes at room temperature, the precipitated triethylamine hydrochloride was filtered off, and the solution was evaporated. The residue was taken up in ether, washed with water, dried over magnesium sulfate and evaporated. The oily residue showed up by thin-layer chromatography! to be clean.

Yield: 32.27 g = 86% of theory of 3-methylsulfonyl-2-phenyl-2-propoxy-propionitrile.

20

n^ : 1.5000

The subsequent examples serve to illustrate the application possibilities of the compounds according to the invention, which occur in the form of the preparations listed above.

Example 3

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

Young barley plants 1 stage with the first leaves were sprayed dripping wet with the indicated concentrations. After drying the spray coating, the treated plants as well as untreated control plants were inoculated with dry powdery mildew spores, the test plants being coated with infected plants. The test plants were then grown in greenhouses with wood

20 to 22°C, and after one week the percentage attack on the leaf surface was assessed. The fungicidal effect was calculated as follows:

The compounds were available as 20% formulations.

Example 4

Effect of prophylactic foliar treatment against Erysiphe cichoracearum on pumpkin plants in greenhouses

Young pumpkin plants were sprayed dripping wet with the indicated active substance concentrations, after drying the spray coating, 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 one week, the affected powdery mildew area was estimated as a percentage of the total leaf area.' The fungicidal effect was calculated as follows:

The note "s" in the following table means that the fungicidal effect was also determined on the growth of the plants (after the treatment) and was found to be positive. That is that the active ingredient is transported systemically to the growth and here too showed a hundred percent effect against powdery mildew.

The new compounds were available as 20% formulations.

Example 5

Percentage 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 conidium spores of Helminthosporium teres and grown in a humidity chamber for 2 days at 20 to 22°C. The plants were then grown in greenhouses at 20 to 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 6

Effect of prophylactic foliar treatment against dwarf rust Puccihia 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 concentrations. 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 grown at 15°C for 10 days, the first two days under nearly 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.

Example 1 7

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 grease stain-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 phase, the bactericidal effect was calculated as follows:

The compounds were available as 20% formulations.

Example 8

Steam activity against Helminthosporium is tested on barley in greenhouses

To determine the steam activity, a pot with approx.

20 barley sprouts in the beginning second leaf stage placed between two barley pots with dried spray coating after a drip-wet treatment. The dripping wet treatment was carried out with an active ingredient concentration of 0.1%. A conidia suspension of the net spot-causing Helminthosporium teres was sprayed over all three pots in each experimental stage, which had been prepared in an aqueous solution of 0.05% sodium oleate and 0.02% gelatin and which

contained 100,000 spores per milliliters. After spraying the spores, the three pots in each experimental phase were placed in polyethylene bags for 3 days and kept at greenhouse conditions of approx. 20°C. The bags were then opened by cutting at leaf tip height. After 8 days, the number of web spots in each pot was counted. The fungicidal steam effect was calculated as follows:

The new compounds were available as 20% formulations. All vapor exposures were plant compatible.

Connection according to

S ammene1in gn ingsmidde1

1-(4-chlorophenoxy)-3,3-dimethyl-1-86

(1,2,4-triazol-1-yl)-butanone

Example 9

Systemic effect of soil treatment before germination against sugar beet mealybug Erysiphe polygoni in greenhouses

Plant pots were sprayed with sugar beet after sowing

0.3 kg of active ingredient per hectares and placed next to untreated plant pots in greenhouses at 20°C. After germination of the beet plants

(12 to 14 per pot) one waited until the plants had developed both first leaves and then inoculated by dusting with dry spores of true beet mealybug Erysiphe polygoni. 3 weeks later (6 weeks after soil treatment) the attack on the leaves was determined. The fungicidal effect could only take place through absorption of the substance from the plant roots and was calculated as follows:

The compounds were available as 20% formulations. All treatments proved to be compatible with the plants and led to vigorous, dense growth compared to the untreated control.

Connection according to

Example 10

Soya and wheat were sprayed with emulsions of the test substance in pre-emergence. The application rate was 2 kg of active substance/ha. The plants were then grown in greenhouses and measured after 3 weeks.

The table shows the recorded percentage growth inhibition.

Same tendency connection part e

2-ChloroethyltriiæthylaniTDniuirichloride 0 17

It turned out that the new compounds were generally stronger than the comparison compound.

Example 11

In pre-emergence, rice was treated in amounts of 2 kg of active substance/ha with the new compounds. After 3 weeks of cultivation in a greenhouse, the percentage growth inhibition was determined.

This is indicated in the following table.

Comparison connection

2-chloroethyltrimethyl-

ammonium chloride 0

The growth inhibition obtained with the new compounds was not obtained using the comparison compound.

Example 12

In pre-emergence, sugar beet was sprayed in an amount of

2 kg of active ingredient/ha. The percentage growth inhibition and the color of the plants were determined after cultivation for 3 weeks in a greenhouse.

The results are shown in the following table.

Means of comparison

2-chloroethyltrimethyl-

ammonium chloride 0 0

^Table for color: 0 = as control

1 = intensive green

2 = dark green

The new compounds affect the growth of the beets, which could not be achieved using the comparison compound.

Example 13

Effect of prophylactic foliar treatment against the leaf spot pathogen Fusarium culmorum on cob millet (Pennisetum glaucum) in a greenhouse

Young millet plants (about 30 in each pot) in the beginning second leaf stage were sprayed dripping wet with the indicated concentrations. After drying the spray coating, the treated as well as untreated control plants were sprayed with a conidial suspension of Fusarium culmorum and placed in a moist greenhouse at 2°C. After 4 days, the percentage of the leaf surface attacked was determined. The fungicidal effect was calculated as follows:

The new compounds were available as 20% formulations.

Example 14

Effect of prophylactic foliar treatment against the leaf spot pathogen Cercospora beticola on sugar beet in greenhouses

Sugar beet plants with at least 2 well-developed leaves were sprayed dripping wet with the indicated concentrations. After drying the spray coating, the treated plants as well as untreated control plants were sprayed with a conidia suspension of Cercospora beticola and incubated moist in a greenhouse at 26°C for 2 days. The plants were then grown under normal greenhouse conditions. 2 weeks after treatment, the percentage attack was determined.

The fungicidal effect was calculated as follows:

The compounds were available as 20% formulations.

Example 15

Effect of seed treatment against seed-borne Helminthosporium sativum (caused by. footyke) on barley

Barley seed infected with Helminthosporium sativum was treated with 50 mg of active substance per 100 g. From each treatment as well as from the untreated group, 2 g of seeds were sown in two repetitions in pots and incubated at 15°C in a climate chamber. After germination, the plants were artificially illuminated in a 12-hour rhythm. After 4 weeks, the percentage of leg-thick plants was determined. In the untreated control group, all the plants were diseased.

The compounds were available as 20% formulations.

Example 16

Effect of seed treatment against the seed borer Phoma betae on sugar beet

Sugar beet grain infected with Phoma betae was treated with 250 mg of active substance per 100 g. From the treated as well as untreated seed grain, 25 grains were sown in pots, repeated four times, and these were placed in a climate chamber at 15°C. After germination of the plants, these were artificially illuminated in a

12 hour rhythm. Until the end of the experiment after 7 weeks, the diseased plants were counted and removed weekly. A total of diseased plants in the untreated control group was 76.1% of the germinated plants. The protective effect of the treatment was calculated as follows:

The new compounds were available as 20% formulations.

Means of comparison

β-(1,1'-biphenyl-4-yloxy)-α-(1,1-dimethylethyl)-1H-1,2,4-triazol-1-

ethanol 51

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-2-butanone 57

Claims (9)

1. 1,2,4-triazol-1-yl-propionitriles of general formula: in which R denotes an aromatic hydrocarbon residue which may optionally be substituted with one or more, the same or different substituents which are halogen, (C-^ -C^ )-alkyl, (C^-C^ )-alkoxy, (C-^-C )-alkylthio, trifluoromethyl or nitro, and R 1 denotes (C 1 -C 4 )-alkyl, (C 1 -C 8 )-alkenyl, (C 3 -C 8 )-alkynyl or a phenyl radical which may optionally be substituted with one or more , the same or different substituents which are halogen, (C-^-C^)^-alkyl, (C1-C4 )-Alkoxy, (C1-C4 )-alkylthio, trifluoromethyl or nitro, and their acid addition salts with inorganic and organic acids. 2. 1,2,4-triazol-1-yl-propionitriles according to claim 1, characterized in that R denotes a phenyl radical which is optionally substituted with one or more, identical or different substituents which are halogen, (C^ -C^ )- alkyl, (C₁ -C₁ )-alkoxy, (C₁ -C₁ )-alkylthio, trifluoromethyl or nitro, and R1 denotes (Ci-CiQ)-alkyl, (C-Ci-Ci)-alkenyl or a benzyl residue which may optionally be substituted with one or more, identical or different substituents which are halogen, (C-Ci-Ci)-alkyl , (C1~C4 ^Alkoxy, (Ci~C£ -alkylthio, trifluoromethyl or nitro. 3. 1,2,4-triazol-1-yl-propionitrile according to claim 1, characterized in that these are isopropoxy-2-phenyl-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-isopropoxy-2-phenyl-3-(1,2,4-triazol-1-yl)-propionitrile/ or 2-hexyloxy-2-(2-methylphenyl)-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-butoxy-2-(2-methylphenyl)-3-(1, 2,4-triazol-1-yl)-propionitrile, or 2-butoxy-2-(2-methylphenyl)-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-hexyloxy -2-(2-methylphenyl)-3-(1,2,4-triazol-1-yl)-propionitrile, or 2-butoxy-2-phenyl-3-(1,2,4-triazol-1-yl) )-propionitrile, hydronitrate, or 2-butoxy-2-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-ethoxy-2-phenyl-3- (1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-phenyl-2-propoxy-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrite, or 2- (3-Chlorophenyl)-2-hexyloxy-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-butoxy-2-phenyl-3-(1,2,4-triazol- 1-yl)-propionitrile, or 2-phenyl-2-propoxy-3-(1,2,4-triazol-1-yl)-propionitrile, or 2-ethoxy-2-phenyl-3-(1,2, 4-triazol-1-yl)-propionitrile, or 2-hexyloxy-2-phenyl-3-(1,2,4-triazbl-1-yl)-propionitrile, hydronitrate, or 2-allyloxy-2-phenyl-3 -(1,2,4-triazol-1-yl)-propion yttril, hydronitrate, or 2-butoxy-2-(4-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-allyloxy-2-phenyl-3-(1 ,2,4-triazol-1-yl)-propionitrile, or 2-Methoxy-2-phenyl<-3-(1,2,4-triazol-1-yl)-propionitrile, or 2-hexyloxy-2-phenyl-3-(1,2,4-triazbl-1- yl)-propionitrile, or 2-(2-chlorophenyl)-2-hexyloxy-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-(2-chlorophenyl)-2-propoxy -3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-(4-chlorophenyl)-2-propoxy-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-(4-chlorophenyl)-2-hexyloxy-3-(1, 2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-(4-chlorophenyl)-2-propyloxy-3-(1,2,4-triazol-1-yl)-propionitrile, or 2-butoxy-2-(4-chlorophenyl)-3-(1,2, 4-triazol-1-yl)-propionitrile, or 2-(2-methylphenyl)-2-octyloxy-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-decyloxy-2 -(2-methylphenyl)-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-(2-methylphenyl)-2-octyloxy-3-(1,2,4-triazole -1-yl)-propionitrile, or 2-(2-chlorophenyl)-2-butoxy-3-(1,2,4-triazol-1-yl)-propionitrile, or 2-(2-chlorophenyl)-2- propoxy-3-(1,2,4-triazol-1-yl)-propionitrile, or 2-butoxy-2-(2,4-dichlorophenyl)-3-(1,2,4-triazol-1-yl) -propionitrile, hydronitrate, or 2-butoxy-2-(2,4-dichlorophenyl)-3-(1,2,4-triazol-1-yl)-propionitrile, or 2-allyloxy-2-(2,4- dichlorophenyl)-3-(1,2,4-triazol-1-yl)-propionitrile, or 2-(3,4-dichlorophenyl)-2-propoxy-3-(1,2,4-triazol-1-yl )-propionitrile, hydronitrate, or 2-(3,4-dichlorophenyl)-2-propoxy-3-(1,2,4-triazol-1-yl)-propionitrile, or 2-(3,4-dichlorophenyl)- 2-hexyloxy-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-(3 ,4-dichlorophenyl)-2-hexyloxy-3-(1,2,4-triazol-1-yl)-propionitrile, or 2-(4-fluorophenyl)-2-propoxy-:3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-(4-fluorophenyl)-2-propoxy-3- (1,2,4-triazol-1-yl)-propionitrile, or 2-butoxy-2-(4-fluorophenyl)-3-(1,2,4-triazbl-1-yl)-propionitrile, hydronitrate, or 2-butoxy-2-(4-fluorophenyl)-3-(1, 2,4-triazol-1-yl)-propionitrile, or 2-(2-fluorophenyl)-2-propoxy-3-(1,2,4-triazol-1-yl)-propionitrile, or 2-(2- fluorophenyl)-2-propoxy-3-(1,2,4-triazol-1-yl)-propionitrile, or 2-butoxy-2-(2-fluorophenyl)-3-(1,2,4-triazol-1 -yl)-propionitrile, hydronitrate, or 2-butoxy-2-(2-fluorophenyl)-3-(1,2,4-triazol-1-yl)-propionitrile, or 2-(2-fluorophenyl)-2- hexyloxy-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-(2-fluorophenyl)-2-hexyloxy-3-(1,2,4-triazol-1-yl) -propionitrile, or 2-(4-bromophenyl)-2-propoxy-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-(4-bromophenyl)-2-propoxy<-3-(1,2,4-triazol-1-yl)-propionitrile, or 2-(4-bromophenyl)-2-hexyloxy-3-(1,2 ,4-triazbl-l-yl)-propionitrile, hydronitrate, or 2-(4-bromophenyl)-2-hexyloxy-3-(1,2,4-triazbl-l-yl)-propionitrile, or 2-(2 ,4-dichlorophenyl)-2-propoxy-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-(2,4-dichlorophenyl)-2-propoxy-3-(1, 2,4-triazol-l-yl)-propionitrile, or 2-(2-methylphenyl)-2-pentyl-3-(1,2,4-triazol-l-yl)-propionitrile, hydronitrate, or 2-( 2-methylphenyl)-2-pentyl-3-(1,2,4-triazol-1-yl)-propionitrile, or 2-(4-methylphenyl)-2-propoxy-3-(1,2,4-triazole -1-yl)-propionitrile, hydronitrate, or 2-hexyloxy-2-(4-methylphenyl)-3-(1,2,4-triazol-1-yl)-propionitrile, hydronitrate, or 2-(4-methylphenyl)-2-propoxy-3-(1,2,4-triazol-1-yl)-propionitrile, or 2-hexyloxy-2-(4-methylphenyl)-3-(1,2, 4-triazol-1-yl)-propionitrile, or 2-butoxy-2-(4-methylphenyl)-3-(1,2,4-triazol-1-yl)-propionitrile. 4. Process for the production of 1,2,4-triazol-1-yl-propionitrile according to claims 1-3, characterized in that compounds of the general formula: is reacted with 1,2,4-triazole of formula: or its alkali compounds in the presence of a solvent and optionally in the presence of a base, in which and R£ have the meanings given above and Y denotes halogen or the optionally halogenated alkylsulfonyloxy or arylsulfonyloxy residue in the side chain. 5. Biocidal agent, characterized in that it contains at least one compound according to claims 1 to 3. 6. Biocidal agent according to claim 5, with fungicidal action. 7. Biocidal agent according to claim 5, with growth regulating effect. 8. Biocidal agent according to claim 5, with bactericidal effect. 9. Biocidal agent according to claim 5, in mixture with carrier and/or auxiliary substances.