DE3422244A1 - 1-Azolyl-2-phenylcyclopropane derivatives - Google Patents

Abstract

Novel 1-azolyl-2-phenylcyclopropane derivatives of the formula <IMAGE> in which A represents a nitrogen atom or a CH group and R represents optionally substituted phenyl, and their acid addition salts and metal salt complexes, a process for the preparation of the novel substances, and their use as plant growth regulators and fungicides. Novel compounds of the formulae <IMAGE> and <IMAGE> in which A and R have the abovementioned meanings and X and R<1> have the meanings given in the description, and their use as intermediates for the preparation of substances of the formula (I).

Description

1-Azolyl-2-phenyl-cyclopropane derivatives

The present invention relates to new I-azolyl-2-phenyl-cyclopropane derivatives, a process for their production and their use as plant growth regulators and fungicides.

It has already become known that certain 2,2-dimethyl-5-phenyl-4- (1,2,4-triazol-1-yl) -4-penten-3-ones or W- (1, 2,4-triazol-1-yl) -acetophenone have good fungicidal properties (Compare JP-OS 1978-130 661 and DE-OS 2 431 407). 1- (2-chlorophenyl) -4,4-dimethyl-2- (1 , 2,4-triazol-1-yl) pent-1-en-3-one, 1- (2,4-dichlorophenyl) -4,4-dimethyl-2- (1,2,4-triazol-1 -yl) -pent-1-en-3-one and (1,2,4-triazol-1-yl) methyl (4-methylphenyl) ketone for combating fungi insert.

The effect of these substances is, however, especially at low application rates, not always fully satisfactory.

In addition, the plant growth-regulating effect of these azole derivatives not always sufficient.

There were now new 1-azolyl-2-phenyl-cyclopropane derivatives of the formula in which A stands for a nitrogen atom or the CH group and R stands for optionally substituted phenyl, as well as their acid addition salts and metal salt complexes found.

The substances of the formula (I) according to the invention can, depending on their arrangement the substituents on the rotating ring occur in the form of different geometric isomers. The invention concerns both the individual isomers and their mixtures.

It has also been found that the 1-azolyl-2-phenylcyclopropane derivatives of the formula (I) and their acid addition salts and metal salt complexes are obtained if substituted 1-vinylazolyl-keto derivatives of the formula are obtained in a first stage in which A and R have the meaning given above and R1 is alkyl, alkoxy, alkylthio, alkoxyalkyl, alkylthioalkyl, alkenyl, alkynyl and optionally substituted phenyl, phenoxy, phenylthio, phenoxyalkyl, phenylthioalkyl, phenylalkoxy, phenylalkylthio, phenylalkoxyalkyl or phenylalkylthioalkyl, with Dimethyloxosulfonium methylide of the formula + 6 (III) (CH3) 2SOCH2 in the presence of a diluent and the resulting azolylcyclopropane oxiranes of the formula in which A, R and R1 have the meaning given above, in a second stage with azoles of the formula in which X stands for a nitrogen atom or a CH group, is reacted in the presence of an alkali alcoholate and in the presence of a diluent; and the resulting azolylcyclopropane carbinols of the formula in which A, X, R and R1 have the meaning given above, optionally heated in the presence of a diluent after prior isolation, and optionally then adding an acid or a metal salt to the compounds of the formula (I) thus obtained.

Finally, it was found that the new 1-azolyl-2-phenyl-cyclopropane derivatives of the formula (I) and their acid addition salts and metal salt complexes are strong plant growth regulators and have fungicidal properties.

Surprisingly, the substances according to the invention show better results plant growth regulating and fungicidal effectiveness than the constitutionally similar, Compounds 1- (2-chlorophenyl) -4,4-dimethyl-2- (1 , 2,4-triazol-1-yl) pent-1-en-3-one, 1- (2,4-dichlorophenyl) -4,4-dimethyl-2- (1,2,4-triazol-1 -yl) -pent-1-en-3-one and (1, 2,4-triazol-1-yl) methyl (4-methyl-phenyl) ketone.

The 1-azolyl-2-phenyl-cyclopropane derivatives according to the invention are generally defined by the formula (I). A is preferably used in this formula for a nitrogen atom or the CH group and R for optionally simple or multiply, identically or differently substituted phenyl, where as substituents The following may be mentioned: halogen, alkyl, alkoxy and alkylthio each having 1 to 4 carbon atoms; Haloalkyl, haloalkoxy and haloalkylthio each having 1 to 2 carbon atoms and 1 up to 5 identical or different halogen atoms, such as fluorine and chlorine atoms; Alkyl and dialkylamino each with 1 to 4 carbon atoms in each alkyl part; optionally by alkyl having 1 or 2 carbon atoms and / or Halogen-substituted phenyl and optionally by alkyl having 1 or 2 carbon atoms and / or halogen substituted phenoxy.

Particularly preferred are those compounds of the formula (I) in where A stands for a nitrogen atom or the CH group and R for optionally single to triple, in particular single or double, the same or different substituted phenyl, where the following may be mentioned as substituents: fluorine, chlorine, Methyl, isopropyl, tert-butyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, Trifluoromethylthio, methylamino, dimethylamino, and in each case optionally through Fluorine, chlorine and / or methyl substituted phenyl or phenoxy.

Particularly preferred are those compounds of the formula (I), in which A stands for a nitrogen atom and R for optionally one to three times, in particular once or twice, identical or different substituted Phenyl, where mentioned as substituents gels: fluorine, chlorine, methyl, isopropyl, tert. -Butyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, Methylamino, dimethylamino, and in each case optionally by fluorine, chlorine and / or Methyl substituted phenyl or phenoxy.

Preferred compounds according to the invention are also addition products from acids and those 1-azolyl-2-phenyl-cyclopropane derivatives of the formula (I), in which A and R have the meanings that are already preferred for these radicals were called.

The acids that can be added preferably include hydrohalic acids, such as hydrochloric acid and hydrobromic acid, especially the Hydrochloric acid, also phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as acetic acid, maleic acid, Succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, as well as sulfonic acids such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid.

Compounds according to the invention which are also preferred are addition products from salts of metals of the II. to IV. main and the I. and II. as well as IV. to VIII. Subgroup of the periodic table and those 1-azolyl-2-phenyl-cyclopropane derivatives of formula (I), in which A and R have the meanings which are already preferred for these remnants were named.

Here are salts of copper, zinc, manganese, magnesium, tin, Iron and nickel are particularly preferred.

The anions of these salts are those which are different from those Derive acids that lead to physiologically acceptable addition products. Particularly preferred acids of this type in this context are the hydrohalic acids, such as hydrochloric acid and hydrobromic acid, also phosphoric acid, Nitric acid and sulfuric acid.

If, for example, 1- (2,4-dichlorophenyl) -4,4-dimethyl-2- (1,2,4-triazol-1-yl) -1-penten-3-one is used as the starting material in the first stage and sets in the second stage the 2-tert-butyl- / 2- (2,4-dichlorophenyl) -1- (1,2,4-triazol-1-yl) -cyclopropan-1-yl / -oxirane with 1 , 2,4-triazole, the course of the process according to the invention can be represented by the following equation: The 1-vinyl-azolyl-keto derivatives to be used as starting materials for the process according to the invention are generally defined by the formula (II). In this formula, A and R preferably represent those meanings which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as preferred for these substituents and R1 represents straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkoxy with 1 to 4 carbon atoms, straight-chain or branched alkylthio with 1 to 4 carbon atoms, alkoxyalkyl with 1 to 4 carbon atoms in the alkoxy part and 1 to 4 carbon atoms in the alkyl part, alkylthioalkyl with 1 to 4 carbon atoms in the alkylthio part and 1 to 4 Carbon atoms in the alkyl part, for alkenyl and alkynyl with 2 to 4 carbon atoms each, and for phenyl, phenoxy, phenylthio, phenoxyalkyl with 1 to 4 carbon atoms in the alkyl part, phenylthioalkyl with 1 to 4 carbon atoms, which are optionally mono- to triple, identically or differently substituted in the phenyl part in the alkyl part, phenylalkoxy with 1 to 4 carbon atoms in the alkoxy part, phenylalkylthio with 1 to 4 carbon atoms in the alkylthio part, phenylalkoxyalkyl with 1 to 4 carbon atoms each in the alkoxy and alkyl part and phenylalkylthioalkyl with 1 to 4 carbon atoms each in the alkylthio and alkyl part, with phenyl substituents being those that are already in connection with the description of the substances of the formula (I) according to the invention are preferably mentioned for the radical R.

The 1-vinyl-azolyl-keto derivatives of the formula (II) are known (cf. EP-OS 0 032 239, EP-OS 0 044 993, DE-OS 3 229 274, JP-OS 1978-130 661 and DE-OS 2 838 847).

This also applies to the first stage of the process according to the invention The required dimethyloxosulfonium methylide of the formula (III) is also known (cf. J. Am.

Chem. Soc. 87: 1363-1364 (1965)). It will do the above implementation Processed in a freshly prepared state by putting it in situ through implementation of trimethyloxosulfonium iodide with sodium hydride or sodium amide, in particular with potassium tert-butoxide or sodium methylate, in the presence of a diluent generated.

Also for the second stage of the process according to the invention Azoles of the formula (V) required as starting materials are generally known compounds of organic chemistry.

Those occurring as intermediates in the process according to the invention Azolylcyclopropane oxiranes of the formula (IV) and azolylcyclopropane carbinols of the formula (VI) are not yet known.

They represent interesting intermediate products and show in corresponding Application rate or concentrations also fungicidal and plant growth regulating Properties.

Suitable diluents for the first stage of the invention Process inert organic solvents in question. These preferably include Ethers, such as tetrahydrofuran or dioxane, as well as aliphatic and aromatic hydrocarbons, such as in particular benzene, toluene or xylene.

The reaction temperatures can be used when carrying out the first stage of the method according to the invention can be varied over a wide range. In general work between 0 and 1000C, preferably between 10 and 600C.

When carrying out the first stage of the method according to the invention it is preferable to use 1 mole of substituted 1-vinylazolyl-keto derivative of the formula (II) 1 to 3 moles of dimethyloxosulfonium methylide of the formula (III), generated in-situ from trimethyloxosulfonium iodide in dimethyl sulfoxide and potassium tert. butoxide. The isolation of the resulting azolylcyclopropane oxiranes of the formula (IV) takes place in the generally accepted manner.

Suitable diluents for the second stage of the invention Process inert organic solvents in question. Are preferably used Nitriles, such as, in particular, acetonitrile; aromatic hydrocarbons, such as benzene, Toluene and dichlorobenzene; Formamides, such as, in particular, dimethylformamide; and hexamethylphosphoric triamide.

The second stage of the process according to the invention is carried out in the presence an alkali alcoholate carried out. These preferably include the methylates and ethylates of sodium and potassium and, in particular, potassium tert-butylate.

The reaction temperatures can be used when carrying out the second Stage of the process according to the invention can be varied over a wide range. In general, the compounds of the formula are not isolated in between (VI) between 120 and 2000C, preferably between 120 and 1800C. With intermediate insulation the compounds of the formula (VI) are generally worked between 50 and 1200C, preferably between 80 and 1100C.

The subsequent cleavage of the isolated intermediates takes place generally between 100 and 1900C, preferably between 120 and 1800C.

When carrying out the second stage of the process according to the invention 1 to 4 is preferably used for 1 mole of azolylcyclopropanoxirane of the formula (IV) Moles of azole of the formula (V) and 1 to 4 moles of alkali metal alcoholate. Isolation of the End products of the formula (I) or the intermediates of the formula (VI) takes place in generally accepted manner.

The acid addition salts of the compounds of the formula (I) can be used in simply by using common salt formation methods, e.g. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, e.g. hydrochloric acid, and in a known manner, e.g. by filtering off, isolated and optionally by washing with an inert organic solvent getting cleaned.

The metal salt complexes of the compounds of formula (I) can in can easily be obtained by conventional methods, for example by dissolving the Metal salt in alcohol, e.g. ethanol and adding to compounds of the formula (I). Metal salt complexes can be isolated in a known manner, e.g. by filtering off and, if necessary, purify by recrystallization.

The active ingredients according to the invention intervene in the metabolism of plants and can therefore be used as growth regulators.

The following applies to the mode of action of plant growth regulators previous experience that an active ingredient also several different ones Can have effects on plants. The effects of the substances depend essentially on them from the time of application based on the stage of development of the plant as well as the amounts of active ingredient applied to the plants or their environment and the type of application. In any case, the crop plants should be growth regulators influence in a certain desired way.

Plant growth regulating substances can be used, for example, to inhibit of the vegetative growth of the plants. Such an inhibition of growth is of economic interest for grasses, among other things, because it can the frequency of grass cuttings in ornamental gardens, parks and sports facilities, at roadsides, at airports or in orchards. The inhibition is also important the growth of herbaceous and woody plants on and near roadsides of pipelines or overhead lines or, more generally, in areas where a strong growth of the plants is undesirable.

The use of growth regulators for inhibition is also important the growth in length of grain. This reduces the risk of twisting ("storage") of plants reduced or completely eliminated before harvest. Besides, you can Growth regulators in cereals cause stalk reinforcement, which also counteracts storage. The use of growth regulators to shorten the stalk and stalk reinforcement allows higher amounts of fertilizer to be applied to the yield to rise gladly, without the risk of the grain being stored.

Inhibition of vegetative growth is made possible in many cultivated plants a denser planting, so that higher yields achieved in relation to the soil area can be. An advantage of the smaller plants obtained in this way is also that the Culture can be processed and harvested more easily.

An inhibition of the vegetative growth of the plants can also thereby lead to increased yields that the nutrients and assimilates to a greater extent the flowering and fruiting benefit than the vegetative parts of the plant.

Growth regulators can often also be used to promote the achieve vegetative growth. This is of great use when the vegetative Plant parts are harvested. However, vegetative growth can be promoted also at the same time lead to a promotion of generative growth by the fact that more assimilates are formed, so that more or larger fruits arise.

In some cases, increases in yield can be achieved through an intervention in the plant metabolism can be achieved without any changes in the vegetative Make growth noticeable. Furthermore, a change can be made with growth regulators the composition of the plants can be achieved, which in turn leads to an improvement in quality which can lead to harvested products. So it is for example wisely possible the content of sugar in sugar beet, sugar cane, pineapple and citrus fruits increase or increase the protein content in soy or grain. It is too For example, it is possible to reduce the breakdown of desired ingredients, such as sugar in Sugar beet, or sugar cane, with growth regulators before or after harvest too inhibit. In addition, the production or the outflow of phytochemicals can be reduced influence positively. An example is the stimulation of the latex flow in rubber trees called.

Under the influence of growth regulators it can lead to training parthenocarpic fruits come. The sex of the flowers can also be influenced will. Sterility of the pollen can also be created, which is what happens during breeding and the production of hybrid seeds is of great importance.

The use of growth regulators allows branching control of plants. On the one hand, by breaking the apical dominance, the development be promoted by side shoots, which is particularly in connection with ornamental plants with stunted growth can be very desirable. On the other hand, it is also possible to inhibit the growth of the side shoots. There is great interest in this effect, for example in tobacco growing or when planting tomatoes.

Under the influence of growth regulators, the leaf population of the Plants are controlled so that one Defoliation of the plants is achieved at a desired time. Defoliation of this kind plays a role mechanical harvesting of cotton plays an important role in others, too Cultures such as in viticulture to facilitate the harvest of interest. A defoliation The plants can also be made to prevent transpiration of the plants to reduce the transplanting.

The fruit fall can also be controlled with growth regulators. On the one hand, premature fruit fall can be prevented. On the other hand, can but also the fall of fruit or even the fall of the flowers to a desired one Measures are encouraged ("thinning") in order to break alternation. Understood by alternation one is the peculiarity of some types of fruit, endogenously very different from year to year Bring income. Finally, it is possible to use growth regulators at the time the harvest to reduce the forces required to detach the fruit in order to achieve a to enable mechanical harvesting or to facilitate manual harvesting.

Growth regulators can also be used to accelerate or also delay the ripening of the crop before or after the harvest. This is of particular advantage because it allows an optimal adaptation to the needs of the market. Furthermore, growth regulators can be used in some Cases improve the color of the fruit. It can also use growth regulators also a concentration in time maturity can be achieved. In order to the conditions are created for, for example, tobacco, tomatoes or coffee complete mechanical or manual harvesting can be carried out in one operation can be.

By using growth regulators, the seed or Bud rest of the plants can be influenced, so that the plants, e.g. pineapple or ornamental plants in nurseries, none at a time, sprout or bloom, on which they normally show no willingness to do so. A delay in the Sprouting of buds or germination of seeds with the help of growth regulators can be desirable in frost-prone areas to avoid damage from late frosts to avoid.

Finally, growth regulators can make the plants more resistant against frost, drought or high salinity of the soil. Through this the cultivation of plants is possible in areas that are normally used for this purpose are unsuitable.

The active ingredients according to the invention also have a strong microbicidal effect Effect on and can come in handy for combating unwanted microorganisms can be used.

The active ingredients are suitable for use as crop protection agents.

Fungicidal agents in crop protection are used for control of Plasmodiophoromycetes, Oomycetes, Chytri- diomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

The good plant tolerance of the active ingredients in the control Concentrations necessary for plant diseases allow the treatment of above-ground parts of plants, of vegetation and seeds and of the soil.

The active compounds according to the invention can also be used as crop protection agents particularly good success for combating Podosphaera species, e.g. against the Pathogen causing apple powdery mildew (Podosphaera leucotricha), as well as cereal and rice diseases can be used.

The active ingredients can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, Finest encapsulation in polymeric substances and in coating compounds for seeds, as well as ULV formulations.

These formulations are prepared in a known manner, e.g. Mixing the active ingredients with extenders, i.e. liquid solvents, under Liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents. In the case of using water as an extender For example, organic solvents can also be used as auxiliary solvents. The following liquid solvents are essentially: aromatics, such as xylene, Toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, Alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, Methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water.

With liquefied gaseous extenders or carriers are such liquids are meant which are at normal temperature and under normal pressure are gaseous, e.g. aerosol propellants such as halogenated hydrocarbons and butane, Propane, nitrogen and carbon dioxide. The following can be used as solid carriers: e.g. natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite or diatomaceous earth and synthetic rock powder, such as finely divided Silica, alumina and silicates. Come as solid carriers for granules in question: e.g. broken and fractionated natural rocks such as calcite, marble, Pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic Flours and granulates made from organic material such as sawdust, coconut shells, corn on the cob and tobacco stalks. Possible emulsifiers and / or foam-generating agents are: e.g. non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates. Come as a dispersant in question: e.g. lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latex are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g.

Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as Alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be mixed in the formulations with other known active ingredients, such as fungicides, insecticides, acaricides and herbicides, as well as in mixtures with fertilizers and other growth regulators.

The active ingredients can be used as such, in the form of their formulations or the application forms prepared therefrom, such as ready-to-use solutions, emulsifiable Concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, Dusts and granules. The application happens in the usual Way, e.g.

by pouring, spraying, atomizing, scattering, dusting, foaming, Brushing, etc. It is also possible to apply the active ingredients using the ultra-low-volume method to apply or the active ingredient preparation or the active ingredient itself in the soil to inject. The seeds of the plants can also be treated.

When using the compounds according to the invention as plant growth regulators the application rates can be varied over a wide range. In general 0.01 to 50 kg, preferably 0.05 to 10 kg, are used per hectare of soil area.

When using the substances according to the invention as plant growth regulators applies that the application is carried out in a preferred period of time, its exact Delimitation is based on the climatic and vegetative conditions.

Can also when the substances according to the invention are used as fungicides the application rate varies over a wide range depending on the type of application will. This is how the active ingredient concentrations are in the treatment of parts of plants in the use forms generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight. In the treatment of seeds, amounts of active ingredient are generally used from 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g, is required. With treatment of the soil are active ingredient concentrations of 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02 a, required at the place of action.

The manufacture and use of the substances according to the invention is illustrated by the following examples.

Production Examples Example (1-1) 1st stage 123.7 g (1.1 mol) of potassium tert-butoxide were added in portions over the course of 3 hours to a rapidly stirred suspension of 242 g (1.1 mol) of trimethylsulfoxonium iodide in 250 ml of dimethyl sulfoxide at room temperature.

After 4 hours a solution of 161 g (0.5 mol) of 1- (2,4-dichlorophenyl) -4,4-dimethyl-2- (1, 2,4-triazol-1-yl) -1-penten-3-one in 250 ml of tetrahydrofuran at room temperature added dropwise. After stirring for 15 hours, the mixture was evaporated in vacuo. Of the The residue was stirred into water, and the organic phase was washed with methylene chloride extracted. The methylene chloride solution was dried over sodium sulfate and im Evaporated in vacuo. The remaining oil was made with diisopropyl ether stirred. 153.6 g (87.27% of theory) of 2-tert-butyl-2-Z2- (2,4-dichlorophenyl) -1- (1,2,4-triazol-1-yl) - separated cyclopropan-1-yl7-oxirane in the form of a crystalline solid product.

Melting point: 1,100C.

2nd stage a) without isolation of the intermediate (VI-1) A mixture of 17.6 g (0.05 mol) of 2-tert-butyl-2- / 2- (2,4-dichlorophenyl) -1- (1,2 , 4-triazol-1-yl) -cyclopropan-1-yl7-oxirane (Comp. IV-1), 3.45 g (0.05 mol) 1,2,4-triazole and 2.7 g (0, 05 mol) of sodium methylate in 50 ml of dimethylformamide was heated to 1550 ° C. for 6 hours. The cooled solution was then poured onto water. The organic phase was extracted with methylene chloride. The methylene chloride solution was dried over sodium sulfate and then evaporated in vacuo. The resulting oil was purified by chromatography. (Silica gel Merck "60"; chloroform). 8.9 g (70% of theory) of 1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) cyclopropane with a melting point of 1240 ° C. were obtained.

b) with isolation of the intermediate (VI-1) A solution of 10 g (28.6 mmol) of 2-tert-butyl-2-E2- (2,4-dichlorophenyl) -1- (1,2,4-triazol-1-yl) -cyclopropan-1- yl7-oxirane (Comp. IV-1) in 90 ml of dimethylformamide was added dropwise to a mixture of 6 g (88 mmol) of 1,2,4-triazole and 5 g (88 mmol) of sodium methylate in 100 ml of dimethylformamide at room temperature. After 15 hours of heating at 95 ° C., the mixture was evaporated in vacuo and the residue was dissolved in methylene chloride. The resulting solution was washed with water, dried over sodium sulfate and evaporated in vacuo. The remaining oil was chromatographed (silica gel "Merck 60" / chloroform). 1.4 g (11.6% of theory) of 2- / 2- (2,4-dichlorophenyl) -1- (1,2,4-triazol-1-yl) -cyclopropan-1-yl7-3 were obtained , 3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-ol, melting point 1,600 ° C.

1 g potassium tert. -butylat .wurde in a solution at room temperature of 5 g of 2- / 2- (2,4-dichlorophenyl) -1- (1,2,4-triazol-1-yl) -cyclopropan-1-yl7-3,3-dimethyl-1- (1,2 , 4-triazol-1-yl) butan-2-ol entered in 20 ml of dimethylformamide. The mixture was heated to 1550 ° C. for 20 hours. The cooled mixture was then stirred into 300 ml of water, and the aqueous phase was separated. The oil layer was dissolved in methylene chloride, washed with water, dried over sodium sulfate and evaporated in vacuo. The resulting oil was purified by chromatography (silica gel Merck "60"; chloroform). 2.4 was obtained g (55% of theory) 1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) -cyclopropane vom Melting point 1240C.

The compounds of the formula (I) listed in Table 1 below were obtained in an analogous manner and in accordance with the process according to the invention: Table 1 E.g. RA melting point (OC) No. or refractive index in 7 D-1 I-2 9 N 122 F1 1-3 CN toN 1.5252 F3 1-4 0 N 47 I-5 Cl to N 1.5430 I-6 L to N 1.5432 The intermediates of the formula (IV) listed in Table 2 below were obtained in accordance with Example 1 and the stated process conditions: Table 2 Example No. RA R1 Melting point (OC) IV-2 Cl4) N CH3 142 Cl IV-3 F3CW N CH3 134 The intermediates of the formula (VI) listed in Table 3 below were obtained in accordance with Example 1 and the specified process conditions: Table 3 Example No. RAX R1 Melting point (DC) . VI-2 Cl To NN CH3 214 Use examples In the use examples below, the compounds given below were used as comparison substances: Example A Growth inhibition in soybeans Solvent: 30 parts by weight of dimethylformamide emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier and made up to the desired concentration with water.

Soybean plants are grown in the greenhouse to full development of the first following sheet tightened. At this stage the plants will become dripping wet sprayed with the active ingredient preparations. After 3 weeks, the Increment measured and the inhibition of growth as a percentage of the increment in the control plants calculated. 100% growth inhibition means the stagnation of growth and 0% means a Growth similar to that of the control plants.

In this test, the active ingredient (1-1) according to the invention showed a stronger one Growth inhibition than the compounds (A) and (B) known from the prior art.

Example B Influencing the growth of rice Solvent: 30 parts by weight Dimethylformamide emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate To produce an appropriate preparation of active compound, 1 part by weight is mixed Active ingredient with the specified amounts of solvent and emulsifier and fill with water on the desired concentration.

Rice is grown in climate chambers in small pots filled with vermiculite Tightened up to a size of the 1st leaf of 1-2 cm. Be at this stage the pots up to a height that corresponds to half the height of the pot in the prepared Active ingredient solutions provided.

After the 3rd leaf has developed, the length of all plants becomes determined and expressed as a percentage of the length of the control plants. It mean 100 z a growth as in the control plants; Values below 100% inhibit growth and values over 100% promote growth.

In this test, the active compounds according to the invention show (1-1) and (I-2) a strong growth-inhibiting effect.

Example C Influencing the growth of sugar beets Solvent: 30 parts by weight Dimethylformamide emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate To prepare an appropriate preparation of the active ingredient, mix 1 part by weight Active ingredient with the specified amounts of solvent and emulsifier and fill with water on the desired concentration.

Sugar beets are grown in the greenhouse until the cotyledons are fully developed dressed. At this stage the plants become dripping wet with the active compound preparations sprayed. After 14 days, the growth of the plants is measured and the influence on growth calculated as a percentage of the growth of the control plants. It means 0% influence on growth a growth corresponding to that of the control plants. Identify negative values a growth inhibition, positive values a growth promotion compared to the control plants.

In this test, the active ingredients according to the invention (1-1), (1-2) and (I-3) stronger influence on growth than those known from the prior art Compounds (B) and (C).

Example D Podosphaera test (apple) / protective solvent: 4.7 Part by weight of acetone emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether Zur To prepare an appropriate preparation of the active ingredient, mix 1 part by weight Active ingredient with the specified amounts of solvent and emulsifier and dilutes the Concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the active ingredient preparation to runoff. After the spray coating has dried on the plants are dusted with conidia of the apple powdery mildew pathogen (Podosphaera leucotricha) inoculated.

The plants are then in the greenhouse at 230C and a relative Relative humidity of approx. 70%.

Evaluation is carried out 9 days after the inoculation.

In this test, the compound (1-1) of the present invention showed better fungicidal effect than the known comparative substance (B).

Claims (9)

Claims 1) 1-Azolyl-2-phenyl-cyclopropane derivatives of the formula in which A stands for a nitrogen atom or the CH group and R stands for optionally substituted phenyl, as well as their acid addition salts and metal salt complexes. 2) 1-Azolyl-2-phenyl-cyclopropane derivatives of the formula (I) in which A represents a nitrogen atom or a CH group and R represents phenyl, which can be substituted one or more times, identically or differently by Halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, Alkylthio with 1 to 4 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 5 halogen atoms, haloalkoxy with 1 or 2 carbon atoms and 1 to 5 halogen atoms, haloalkylthio with 1 or 2 carbon atoms and 1 up to 5 halogen atoms, alkylamino with 1 to 4 carbon atoms, dialkylamino with 1 to 4 carbon atoms in each alkyl group, optionally by alkyl with 1 or phenyl and / or optionally substituted with 2 carbon atoms and / or halogen phenoxy substituted by alkyl having 1 or 2 carbon atoms and / or halogen, as well as their acid addition salts and metal salt complexes. 3) Process for the preparation of 1-azolyl-2-phenylcyclopropane derivatives of the formula in which A stands for a nitrogen atom or a CH group and R stands for optionally substituted phenyl, and of acid addition salts and metal salt complexes of compounds of the formula (I), characterized in that substituted 1-vinyl is used in a first stage -azolyl-keto derivatives of the formula in which A and R have the meaning given above and R1 is alkyl, alkoxy, alkylthio, alkoxyalkyl, alkylthioalkyl, alkenyl, alkynyl and optionally substituted phenyl, phenoxy, phenylthio, phenoxyalkyl, phenylthioalkyl, phenylalkoxy, phenylalkylthio, phenylalkoxyalkyl or phenylalkylthioalkyl, with Dimethyloxosulfonium methylide of the formula a + 6 (CH3) 2SOCH, (III) in the presence of a diluent and the resulting azolylcyclopropane oxiranes of the formula in which A, R and R1 have the meaning given above, in a second stage with azoles of the formula in which X stands for a nitrogen atom or a CH group, is reacted in the presence of an alkali alcoholate and in the presence of a diluent; and the resulting azolylcyclopropane carbinols of the formula in which A, X, R and R1 have the meaning given above, optionally heated in the presence of a diluent after prior isolation, and optionally then adding an acid or a metal salt to the compounds of the formula (I) thus obtained. 4) Plant growth regulating and fungicidal agents, labeled by a content of at least one 1-azolyl-2-phenyl-cyclopropane derivative of Formula (I) or an acid addition salt or metal salt complex of a 1-azolyl-2-phenyl-cyclopropane derivative of formula (I). 5) Methods of plant growth regulation and control of mushrooms, characterized in that 1-azolyl-2-phenyl-cyclopropane derivatives of formula (I) or their acid addition salts or metal salt complexes to the plants to be treated or their habitat can act. 6) Use of 1-azolyl-2-phenyl-cyclopropane derivatives of the formula (I) or their acid addition salts or metal salt complexes for regulating the Plant growth and fungus control. 7) Process for the production of plant growth regulators and fungicidal agents, characterized in that 1-azolyl-2-phenyl-cyclopropane derivatives of the formula (I) or their acid addition salts or metal salt complexes with extenders and / or surfactants mixed together. 8) Azolyl-cyclopropane-oxiranes of the formula in which A stands for a nitrogen atom or a CH group, R stands for optionally substituted phenyl and R1 for alkyl, alkoxy, alkylthio, alkoxyalkyl, alkylthioalkyl, alkenyl, alkynyl and in each case optionally substituted phenyl, phenoxy, phenylthio, phenoxyalkyl, phenylthioalkyl, phenylalkoxy , Phenylalkylthio, phenylalkoxyalkyl or phenylalkylthioalkyl. 9) Azolyl-cyclopropane-carbinols of the formula in which A represents a nitrogen atom or a CH group, X represents a nitrogen atom or a CH group, represents optionally substituted phenyl and R1 represents alkyl, alkoxy, alkylthio, alkoxyalkyl, alkylthioalkyl, alkenyl, alkynyl and each optionally substituted phenyl , Phenoxy, phenylthio, phenoxyalkyl, phenylthioalkyl, phenylalky, phenylalkylthio, phenylalkoxyalkyl or phenylalkylthioalkyl.