DE3905317A1 - Cyclopropyl hydroxyalkyl azolyl derivatives - Google Patents

Abstract

Novel cyclopropyl hydroxyalkyl azolyl derivatives of the formula <IMAGE> in which R represents radicals of the formulae <IMAGE> X represents the groups -CH2-CH2-, -CH=CH-, -O-CH2- or -S-CH2-, the hetero atom in each case being bonded to the aromatic or heteroaromatic radical if X represents -O-CH2- or -S-CH2-, or R also represents <IMAGE> if X represents -S-CH2-, and their acid addition salts and metal salt complexes, a process for the preparation of the novel substances and their use as fungicides and plant growth regulators. Novel oxiranes of the formula <IMAGE> in which R and X have the abovementioned meanings, and a process for their preparation.

Description

The present invention relates to new cyclopropyl hydroxyalkyl azolyl derivatives, a process for their Production and their use as fungicides and Plant growth regulators.

It is already known that numerous hydroxyalkyl Azolyl derivatives fungicidal and plant growth regulating Possess properties (cf. EP-OS 00 40 345 and EP-OS 00 52 424). The effectiveness of these substances is very well; at low application rates, the effectiveness however, to be desired in some cases.

New cyclopropyl-hydroxyalkyl-azolyl Derivatives of the formula

in which
R for the remainder of the formulas

and
X represents the groupings -CH₂-CH₂-, -CH = CH-, -O-CH₂- or -S-CH₂-, the heteroatom being connected to the aromatic or heteroaromatic radical when X is -O-CH₂- or -S-CH₂-,
or
R also for

stands when X stands for -S-CH₂-,
as well as their acid addition salts and metal salt complexes.

The substances according to the invention contain an asymmetric substituted carbon atom. You can therefore opt in Isomer forms occur. In addition, you can those substances of the formula (I) in which X for a -CH = CH group, also in the form of cis- or trans- Isomers are present. The invention relates to both individual isomers as well as their mixtures.

It was also found that cyclopropyl-hydroxyalkyl azolyl derivatives of the formula (I) and their acid addition Salts and metal salt complexes are obtained when one Oxiranes of the formula

in which
R and X have the meaning given above,
with 1,2,4-triazole of the formula

in the presence of an acid binder and in the presence a diluent and, if appropriate, in the presence  a catalyst and optionally subsequently to the compounds of the formula thus obtained (I) an acid or a metal salt is added.

Finally, it was found that the new cyclopropyl hydroxyalkyl-azolyl derivatives of the formula (I) and their Acid addition salts and metal salt complexes strong fungicidal and plant growth regulating properties have.

Surprisingly, the inventive Fabrics a better fungicidal and plant growth regulating Effectiveness than the constitutional most similar known connections of the same Direction of action.

The cyclopropyl-hydroxyalkyl-azolyl- Derivatives are clearly defined by formula (I). The substances present in free form are preferred of formula (I).

Also preferred are addition salts of cyclopropyl hydroxyalkyl azolyl derivatives and certain Acids. To the acids that are preferably added can include hydrohalic acids, such as. B. hydrochloric acid and hydrobromic acid, especially hydrochloric acid, also phosphoric acid, Nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as e.g. B. acetic acid, citric acid, salicyclic acid, sorbic acid and lactic acid and sulfonic acids, such as. B.  p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid or Camphorsulfonic acid.

Preferred compounds according to the invention are also Addition products from salts of metals from II to IV. Main and I. and II. As well as IV. To VIII. Subgroup of the periodic table of the elements and cyclopropyl hydroxyalkyl-azolyl derivatives of the formula (I) in which R and X have the meaning given above.

Here are salts of copper, zinc, manganese, magnesium, Tin, iron and nickel are particularly preferred. Anions of these salts are those which which are derived from such acids, which too lead physiologically compatible addition products.

Particularly preferred such acids are in this Connection the hydrohalic acids, such as. B. the Hydrochloric acid and hydrobromic acid, also phosphoric acid, nitric acid and sulfuric acid.

If 2- (1-methyl-cyclopropyl) -2- (2,4-dichlorophenoxy- methyl) -oxirane and 1,2,4-triazole as starting materials, so can the course of the method according to the invention illustrated by the following formula scheme will:  

The starting materials in the process according to the invention required oxiranes are represented by the formula (II) Are defined. In this formula, R and X have the meanings the already related to the description the substances of formula (I) according to the invention for this Substituents were called.

The oxiranes of the formula (II) are hitherto unknown. They can be made by using cyclopropyl ketones of the formula

in which
R and X have the meaning given above, either
α) with dimethyloxosulfonium methylide of the formula

or
β) with dimethylsulfonium methylide of the formula

in the presence of a diluent.

The in the process for the production of oxiranes Formula (II) required as starting materials cyclopropyl ketones of the formula (IV) can be different Create methods.

This gives those cyclopropyl ketones of the formula (IV) in which X is -CH = CH- or -CH₂-CH₂- by aldehydes of the formula

R-CHO (VII)

in which
R has the meaning given above,
with methyl (1-methyl-cyclopropyl) ketone of the formula

in the presence of a catalyst, such as. B. sodium hydroxide or potassium hydroxide, in the presence of a diluent, such as B. methanol or ethanol Temperatures between 10 ° C and 80 ° C implemented and if necessary the resulting ketones of the formula

in which
R has the meaning given above,
in the presence of a hydrogenation catalyst, such as. B. Raney nickel or Raney nickel iron, and in the presence of a diluent, such as. As methanol, ethanol or toluene, hydrogenated at temperatures between 40 ° C and 80 ° C under a pressure between 10 and 120 bar with hydrogen.

Furthermore, those cyclopropyl ketones are obtained Formula (IV) in which X represents -O-CH₂- or -S-CH₂-, by using halogen ketones of the formula

in which
Hal represents chlorine or bromine,
with compounds of the formula

R-Y-H (X)

in which
R has the meaning given above
and
Y represents oxygen or sulfur,
in the presence of an acid binder, such as. As potassium carbonate, and in the presence of a diluent, such as. B. acetone, at temperatures between 20 ° C and 130 ° C.

That in the above process for producing oxiranes of the formula (II) as a reaction component Dimethyl-oxo-sulfonium methylide of the formula (V) is known (see J. Am. Chem. Soc. 87, 1363-1364 (1965)). It is in the above implementation in a freshly prepared state processed by doing it in situ through implementation of trimethyloxosulfonium iodide with sodium hydride or Sodium amide, especially with potassium tert-butoxide or Sodium methylate in the presence of a diluent generated.

That in the above process for producing oxiranes of formula (II) also as a reactant Possible dimethyl sulfonium methylide Formula (VI) is known (cf. Heterocycles 8, 397 (1977)). It is also used in the above implementation freshly made state used by looking at it in situ z. B. from trimethylsulfonium halide or Trimethylsulfonium methyl sulfate, in the presence of a strong base, such as B. sodium hydride, sodium amide, Sodium methylate, potassium tert-butoxide or potassium hydroxide, in the presence of a diluent, such as tert-Butanol or dimethyl sulfoxide generated.  

As a diluent when performing the Process for the preparation of the oxiranes of formula (II) inert organic solvents in question.

Alcohols such as tert-butanol, Ethers such as tetrahydrofuran or dioxane aliphatic and aromatic hydrocarbons, such as Benzene, toluene or xylene, as well as strongly polar solvents, such as dimethyl sulfoxide.

The reaction temperatures can be carried out the above process for the preparation of oxiranes Formula (II) can be varied over a wide range. Generally one works at temperatures between 0 ° C and 100 ° C, preferably between 10 ° C and 60 ° C.

When carrying out the process for producing Oxiranes of the formula (II) are added to 1 mol of cyclopropyl ketone of formula (IV) generally 1 and 3 moles of dimethyloxosulfonium methylide of the formula (V) or Dimethylsulfonium methylide of the formula (VI). The The oxiranes of the formula (II) are isolated after usual methods.

The oxiranes of the formula (II) can be used in the inventive If necessary, process directly without isolation continue to be implemented.

Suitable diluents for the invention Processes inert under the reaction conditions Solvent in question. Preferably used are alcohols, such as. As ethanol, methoxyethanol or  Propanol; Ketones such as B. 2-butanol; Nitriles such as B. Acetonitrile; Esters such as B. ethyl acetate; Ethers such as B. Dioxane; aromatic hydrocarbons such as B. Benzene and toluene; or amides, such as. B. Dimethylformamide. It a small amount of water can also be beneficial to add.

As bases come for the implementation of the invention Process all commonly used inorganic and organic bases. Preferably Alkali metal carbonates such as. B. Sodium and potassium carbonate; Alkali metal hydroxides, such as e.g. B. sodium hydroxide; Alkali metal alcoholates, such as. B. Sodium and potassium methylate and ethylate; Alkali metal hydrides, such as B. sodium hydride; as well as lower tertiary Alkylamines, cycloamines and aralkylamines, such as in particular Triethylamine.

All reaction accelerators customary for such reactions can be used as catalysts when carrying out the process according to the invention. Α, α ′ -azo-isobutyronitrile is preferably usable.

The reaction temperatures can be carried out of the method according to the invention in a larger one Range can be varied. Generally you work at temperatures between 0 and 200 ° C, preferably between 60 and 150 ° C.  

When carrying out the method according to the invention one generally works under normal pressure. It is however also possible, with increased or decreased Pressure to work.

When carrying out the method according to the invention 1 mol of oxirane of the formula (II) is preferably used 1 to 2 mol of 1,2,4-triazole and optionally 1 to 2 moles of acid binder. The processing and the The end products are isolated by customary methods.

Those obtainable by the process according to the invention Compounds of formula (I) can in acid addition Salts or metal salt complexes are transferred.

For the preparation of acid addition salts of the compounds of formula (I) are preferably those Acids that are already associated with the Description of the acid addition salts according to the invention were mentioned as preferred acids.

The acid addition salts of the compounds of formula (I) can be made in a simple manner using conventional salt formation methods, e.g. B. by loosening a connection of the general Formula (I) in a suitable inert solvent and adding the acid e.g. B. hydrochloric acid, be obtained and in a known manner, e.g. B. by filtering, isolated and optionally by washing cleaned with an inert organic solvent will.  

For the production of metal salt complexes of the compounds of the general formula (I) are preferably those Salts of metals in question that are already in the Connection with the description of the invention Metal salt complexes mentioned as preferred metal salts were.

The metal salt complexes of compounds of general Formula (I) can be carried out in a simple manner by customary processes be obtained, e.g. B. by dissolving the metal salt in alcohol, e.g. As ethanol, and adding to compounds of the general formula (I). You can use metal salt Complexes in a known manner, e.g. B. by filtering, Isolate and if necessary by recrystallization clean.

The active compounds according to the invention have a strong microbicidal action Effect on and can be used as fungicides will.

Fungicides are used in crop protection Control of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
Xanthomonas species, such as Xanthomonas oryzae;
Pseudomonas species, such as Pseudomonas lachrymans;
Erwinia species, such as Erwinia amylovora;
Pythium species, such as Pythium ultimum;
Phytophthora species, such as Phatophthora infestans;
Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubense;
Plasmopara species, such as Plasmopara viticola;
Peronospora species, such as Peronospora pisi or P. brassicae;
Erysiphe species, such as Erysiphe graminis;
Sphaerotheca species, such as Sphaerotheca fuliginea;
Podosphaera species, such as Podosphaera leucotricha;
Venturia species, such as Venturia inaequalis;
Pyrenophora species, such as Pyrenophora teres or P. graminea;
(Conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus species, such as Cochliobolus sativus;
(Conidial form: Drechslera, Syn: Helminthosporium);
Uromyces species, such as Uromyces appendiculatus;
Puccinia species, such as Puccinia recondita;
Tilletia species, such as Tilletia caries;
Ustilago species, such as Ustilago nuda or Ustilago avenae;
Pellicularia species, such as Pellicularia sasakii;
Pyricularia species, such as Pyricularia oryzae;
Fusarium species, such as Fusarium culmorum;
Botrytis species, such as Botrytis cinerea;
Septoria species, such as Septoria nodorum;
Leptosphaeria species, such as Leptosphaeria nodorum;
Cercospora species, such as Cercospora canescens;
Alternaria species, such as Alternaria brassicae;
Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.

The good plant tolerance of the active ingredients in the concentrations necessary to combat plant diseases allows treatment from above ground Parts of plants, of seedlings and soil.

The active compounds according to the invention are particularly suitable to combat cereal and rice diseases. This is how powdery mildew and rust diseases, Puccinia recondita, Leptosphaeria nodorum, Pyrenophora teres, Cochliobolus sativus and Pseudocercosporella herpotrichoides on cereals as well as Pyricularia and Pellicularia combat rice particularly well. The fabrics own also a good effect against Sphaerotheca Cucumbers and show high activity in the mycelium growth test.

In addition, the active compounds according to the invention also have plant growth regulating properties.

The active substances according to the invention reach into the metabolism of the plants and can therefore act as growth regulators be used.  

For the mode of action of plant growth regulators Experience has shown that an active ingredient also several different effects on plants can exercise. The effects of the substances depend essentially from the time of application related to the stage of development of the plant as well as from the on the plants or their surroundings applied amounts of active ingredient and the type of application. In any case growth regulators are supposed to regulate the crops in certain influence as desired.

Plant growth regulating substances can be used, for example Inhibition of vegetative growth of the plants used will. Such growth inhibition is under other with grasses of economic interest, because this can reduce the frequency of grass cuts in ornamental gardens, Park and sports facilities on the side of the road Airports or in orchards. From It is also important to inhibit the growth of herbaceous plants and woody plants on and around roadsides of pipelines or overland lines or more generally in areas where there is a strong growth of plants is undesirable.

The use of growth regulators is also important to inhibit the length growth of cereals. Hereby there is a risk of the plants bending reduced or completely eliminated before harvest. In addition, growth regulators in cereals can be a Culm reinforcement that also cause storage counteracts. The application of growth regulators  for shortening the stalk and reinforcing the stalk allows higher Spread fertilizer amounts to increase the yield, without the risk of the grain being stored.

An inhibition of vegetative growth enables many crops a denser planting, so that Additional yields can be achieved based on the floor area can. An advantage of the smaller plants achieved in this way is also that the crop is more easily worked and harvested can be.

An inhibition of the vegetative growth of the plants can also lead to increased yields in that the Nutrients and assimilates to a greater extent and fruiting benefit as the vegetative Plant parts.

With growth regulators, one can often also Achieve vegetative growth. This is of great use if the vegetative parts of the plant be harvested. Promoting vegetative growth can also promote the lead to generative growth in that more assimilates are formed so that more or larger fruits arise.

In some cases, yield increases can be achieved through a Interference in plant metabolism can be achieved without changes in vegetative growth to make noticable. Can also use growth regulators  achieved a change in the composition of the plants be, which in turn leads to a quality improvement who can carry crop products. For example, it is possible the sugar content in sugar beets, To increase sugar cane, pineapple as well as in citrus or the protein content in soy or cereals increase. It is also possible, for example, to break down desired ingredients, such as. B. Sugar in sugar beets or sugar cane, with growth regulators in front of or inhibit after harvest. In addition, the production or the drainage of phytochemicals influence positively. Take the example Stimulation of latex flow in rubber trees.

Under the influence of growth regulators, it can become Formation of parthenocarpic fruits come. Furthermore, the gender of the flowers can be influenced. Can too a sterility of pollen is generated, which at the breeding and production of hybrid seeds is of great importance.

By using growth regulators, the Control branching of plants. On the one hand, by Breaking apical dominance the development of side shoots are promoted, especially in ornamental plant growing very desirable also in connection with growth inhibition can be. On the other hand, it is also possible inhibit the growth of the side shoots. For this Effect exists. B. great interest in tobacco growing or when planting tomatoes.  

Under the influence of growth regulators Leaves of the plants are controlled so that a Defoliate the plants at a desired time is achieved. Such defoliation plays at mechanical harvesting of cotton plays a major role but is also in other cultures such. B. in viticulture to facilitate the harvest of interest. A defoliation the plants can also be made to the Reduce transpiration of plants before transplanting.

The fall of fruit is also possible with growth regulators Taxes. On the one hand, premature fruit fall can be prevented will. On the other hand, the fruit fall can also or even dropping the flowers up to one desired dimensions are promoted ("thinning") to the Breaking alternance. Alternance means that Peculiarity of some types of fruit, endogenous from year to year Year to bring very different yields. In the end it is possible with growth regulators at the time the harvest necessary to remove the fruit Reduce forces to mechanical harvesting to enable or facilitate manual harvesting.

Acceleration can also be achieved with growth regulators or delaying the ripening of the crop Reach before or after harvest. This is special Advantage, because it allows optimal adjustment leads to the needs of the market.  

Furthermore, growth regulators can be used in some cases improve the color of the fruit. In addition, with Growth regulators also focus on time maturity can be achieved. This creates the prerequisites created for z. B. for tobacco, tomatoes or Coffee a full mechanical or manual Harvesting can be done in one operation.

By using growth regulators, the Plant seed or bud rest are affected, so that the plants such. B. pineapple or ornamental plants in nurseries, germinate at a time, sprout or bloom, at which they are usually unwilling to do so demonstrate. A delay in the sprouting of Buds or the germination of seeds with the help of growth regulators may be desirable in areas at risk of frost to avoid damage from late frosts.

Finally, resistance to growth regulators the plants against frost, drought or high salinity of the soil are induced. This will make the Cultivation of plants in areas possible for this are usually unsuitable.

The active ingredients can be in the usual formulations are transferred, such as solutions, emulsions, suspensions, Powders, foams, pastes, granules, aerosols, Very fine encapsulation in polymeric substances and in coating compositions for seeds and ULV formulations.  

These formulations are prepared in a known manner e.g. B. by mixing the active ingredients with extenders, i.e. liquid solvents, under pressure liquefied gases and / or solid carriers, optionally using surfactants Agents, ie emulsifiers and / or dispersants and / or foam-generating agents. In the event of the use of water as an extender can, for. B. also organic solvents as auxiliary solvents be used. As liquid solvents come in essential in question: aromatics, such as xylene, toluene, or Alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. 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, strong polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous Extenders or carriers are such liquids meant, which at normal temperature and are gaseous under normal pressure, e.g. B. aerosol propellants, such as halogenated hydrocarbon as well as butane, propane, Nitrogen and carbon dioxide; as solid carriers come into question: z. B. natural stone powder, such as Kaolins, clays, talc, quartz, attapulgite, Montmorillonite or diatomaceous earth and synthetic Rock powders such as finely divided silica, aluminum oxide and silicates; as solid carriers for granules  come into question: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, Dolomite and synthetic granules from inorganic and organic flours as well as granules from organic Material such as sawdust, coconut shells, corn cobs and Tobacco stem; as an emulsifier and / or foam generator Means are possible: B. non-ionic and anionic Emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ether, e.g. B. alkylaryl polyglycol Ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates as well as protein hydrolyzates; as a dispersant come into question: z. B. lignin sulfite and methyl cellulose.

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used, such as Gum arabic, polyvinyl alcohol, polyvinyl acetate, as well natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Other additives can mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. 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 are used will.  

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

The active compounds according to the invention can be used in the formulations in a mixture with other known active ingredients are present such as fungicides, insecticides, acaricides and herbicides as well as mixtures with fertilizers and others Growth regulators.

The active ingredients as such, in the form of their formulations or the application forms prepared from it such as ready-to-use solutions, emulsifiable concentrates, Emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts and granules will. The application happens in the usual way, e.g. B. by pouring, spraying, spraying, scattering, dusting, Foaming, brushing, etc. It is further possible, the active ingredients according to the ultra-low-volume process apply or the drug preparation or inject the active ingredient into the soil yourself. It can also the seeds of the plants are treated.

When using the substances according to the invention as fungicides the application rate depending on the type of application can be varied over a wide range. That's how they are Active substance concentrations in the treatment of parts of plants in the application forms in general between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%. When treating seeds, in general  Active ingredient amounts from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g. When treating the Soil are active ingredient concentrations of 0.00001 to 0.1 wt .-%, preferably from 0.0001 to 0.02%, at the site of action required.

When using the compounds of the invention as Plant growth regulators can reduce the application rates can be varied over a wide range. In general you use 0.01 to 50 kg per hectare of soil, preferably 0.05 to 10 kg of active ingredient.

When using the substances according to the invention as plant growth regulators applies that the application in one preferred period is made, its exact demarcation according to the climatic and vegetative conditions judges.

The production and use of the invention The following examples show substances.

Manufacturing examples Example 1

A solution of 15.1 g (0.053 mol) of 2- [2- (4-bromophenyl) ethyl] -2- (1-methylcyclopropyl) oxirane, 6.9 g (0.1 mol) of 1,2,4 -Triazole, 0.4 g of sodium hydroxide, 0.4 ml of water and a spatula tip α, α '-azo-isobutyro-nitrile in 100 ml of dimethylformamide is heated to 110 ° C for 15 hours. The mixture is then cooled to room temperature, concentrated by stripping off the solvent under reduced pressure, the remaining residue is dissolved in dichloromethane, washed twice with water, the organic phase is dried over sodium sulfate and the solvent is removed under reduced pressure. The residue is purified by column chromatography (silica gel; dichloromethane: ethyl acetate = 1: 1). In this way, 7.3 g (40% of theory) of 1- (4-bromophenyl) -3- (1-methylcyclopropyl) - 4- (1,2,4-triazol-1-yl) - 3-butanol in the form of a solid with a melting point of 153 ° C.

Manufacture of raw materials

A solution of 12 ml (0.15 mol) of dimethyl sulfide in one Mixture of 50 ml of absolute tetrahydrofuran and 100 ml absolute dimethyl sulfoxide is mixed with 10 ml (0.16 mol) Iodomethane was added and the mixture was stirred at room temperature for 16 hours. The resulting suspension is cooled to below from 5 ° C and first gives a solution of 24.7 g (0.032 mol) of 1- (4-bromophenyl) -3- (1-methylcyclopropyl) - Add 3-propanone in 40 ml of absolute toluene. The reaction mixture is then mixed in at 5 ° C. Stir in portions with 9 g within one hour (0.17 mol) sodium methylate. The reaction mixture is stirred for a further 15 hours at room temperature and then mixed with 500 ml of water. You separate the organic Phase, the aqueous phase extracted twice with Toluene, washes the combined organic phases twice with water, dries over sodium sulfate and removes the solvent under reduced pressure. Man receives 15 g (58% of theory) of 2- [2- (4-bromophenyl) ethyl] -2- (1-methylcyclopropyl) oxirane in the form of a yellow oil.  

A solution of 30 g (0.11 mol) of 1- (4-bromophenyl) -3- (1-methylcyclopropyl) -1-propen-2-one in 300 ml of tetrahydrofuran 5 g of Raney nickel iron are added and stirred for 2 hours at 60 ° C under 90 bar of hydrogen. After filtering and concentrating, 24.7 g (84% theory) 1- (4-bromophenyl) -3- (1-methylcyclopropyl) -3- propanone as a colorless oil.

NMR (CDCl₃, 300 MHz) δ = 2.68 (2H, t, τ = 7.5 Hz) and 2.85 (2H, t, τ = 7.5 Hz)

0.69 (2H, g, τ = 3 Hz) and 1.20 (2H, g, τ = 3 Hz) - cyclopropyl ring.

40.7 g (0.211 mol) of 4-bromobenzaldehyde are dissolved in 150 ml Dissolved ethanol and in quick succession with 75 ml Water, 19.6 g (0.2 mol) of 1-acetyl-1-methylcycloproane and a solution of 0.5 g sodium hydroxide in 5 ml Water at room temperature. After finished The mixture is added for a further hour at room temperature stirred. The resulting precipitate is aspirated with a small amount of a mixture Washed ethanol / water and dried. You get 45 g (85% of theory) of 1- (4-bromophenyl) -3- (1-methylcyclopropyl) - 1-propen-2-one in the form of a yellow solid melting point 94-95 ° C.

Example 2

19.6 g (0.071 mol) of 2- (1-methylcyclopropyl) -2- (2,4- dichlorophenoxy-methyl) -oxirane are mixed with 7 g (0.1 mol) 1,2,4-triazole and 14 g potassium carbonate in 250 ml Dimethylformamide stirred at 100 to 110 ° C for 5 hours. After cooling, the reaction mixture is diluted with 800 ml of water and extracted with methylene chloride. The combined organic phases are washed with water and concentrated under reduced pressure. The solid residue is stirred with cyclohexane, suction filtered  and dried. In this way, 8.7 g (36% of theory) on 1- (2,4-dichlorophenoxy) -2- (1-methylcyclopropyl- 2-hydroxy-3- (1,2,4-triazol-1-yl) propane in Form of a solid with a melting point of 84-86 ° C.

Manufacture of raw materials

31 g (0.25 mol) of dimethyl sulfate are added with stirring 20 ° C to a solution of 15 g (0.25 mol) of dimethyl sulfide added dropwise in 100 ml of acetonitrile. After standing for two days 11.8 g are added to this solution at room temperature (0.22 mol) sodium methylate added. The reaction mixture is stirred at 20 ° C. for 30 minutes and then with 25.9 g (0.1 mol) 1 - [(2,4-dichlorophenoxy) acetyl] -1-methyl-cyclopropane transferred. Then the reaction mixture stirred for 16 hours at room temperature and then in Poured water. It is extracted with methylene chloride, washes the organic phase with water and dries over Magnesium sulfate. After removing the solvent 19.7 g (72% of the Theory) on 2- (1-methyl-cyclopropyl) -2- (2,4-dichlorophenoxymethyl) - oxirane in the form of a colorless oil, the without additional purification for further synthesis is used.  

621 g (3 mol) of 1-bromoacetyl-1-methyl-cyclopropane with stirring at room temperature in a solution of 538 g (3.3 moles) 2,4-dichlorophenol and 455 g (3.3 moles) potassium carbonate added dropwise in 1500 ml of acetone. The reaction mixture is heated under reflux for 4 hours. You filter the solid constituents, the filtrate is concentrated under reduced pressure Pressure and adds a mixture of water and Add methylene chloride. The organic phase is separated off, washed twice with 1N aqueous sodium hydroxide solution, then washed again with water and after the Dry over magnesium sulfate under reduced pressure constricted. The remaining residue is distilled. This gives 433 g (56% of theory) of 1 - [(2,4- Dichlorophenoxy) acetyl] -1-methyl-cyclopropane in the form a liquid that boils at 142-150 ° C / 0.04 mbar. Mp .: 64 to 66 ° C

A solution of 314 g (3.2 mol) of 1-acetyl-1-methyl Cyclopropane in 1.6 liters of methanol is at 0 ° C Stir dropwise with a solution of 511 g (3.2 mol) Bromine added in 800 ml of methylene chloride. After discoloration the reaction mixture is mixed with 3 liters of water. Then extracted with methylene chloride, washed the combined organic phases with water, dry over magnesium sulfate and concentrated under reduced pressure a. The remaining residue is in a water jet vacuum distilled. This gives 523 g (92% of the Theory) on 1-bromoacetyl-1-methyl-cyclopropane in the form a liquid that boils at 87-90 ° C / 16 mbar.

According to the methods described above, the substances listed in Table 1 below formula

produced.  

Table 1

Example 18

According to the method given in Example 1, the Starting substance of the formula

produced.

Examples of use

In the following usage examples, the following are specified compounds as reference substances used:

Example A Soybean growth

Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amounts of solvent and emulsifier and fill with Water to the desired concentration.

Soybean plants are grown to the full in the greenhouse Unfolding of the first following sheet attracted. In this Stage the plants are dripping wet with the active ingredient preparations sprayed. After two weeks, everyone Plants measured the growth and growth in percent of the growth of the control plants. It 100% growth means growth corresponding to that of control plants and 0% growth arrest. Values above 100% characterize growth promotion, while values below 100% indicate growth inhibition.

In this test, the compounds according to the invention show (I-2), (I-9) and (I-13) a very good growth inhibitor Effect.  

Example B Grass growth (Festuca pratensis)

Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amounts of solvent and emulsifier and fill with Water to the desired concentration.

Grass (Festuca pratensis) is grown in the greenhouse up to a height of 5 cm. In this stadium the plants are dripping wet with the active ingredient preparations sprayed. After two weeks, all plants growth measured and growth as a percentage of Growth of the control plants calculated. Mean it 100% growth a growth corresponding to that of the control plants and 0% the stagnation of growth. Values above 100% characterize growth promotion.

In this test, the compound according to the invention shows (I-9), a very good anti-growth effect.  

Example C Rye growth

Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amounts of solvent and emulsifier and fill with Water to the desired concentration.

Rye plants are grown in the greenhouse up to the two-leaf Stage attracted. At this stage the plants sprayed dripping wet with the active ingredient preparations. To The growth of all plants is measured for two weeks and the growth as a percentage of the growth of the control plants calculated. It means 100% growth Growth corresponding to that of the control plants and 0% the standstill of growth. Mark values over 100% a growth promotion.

In this test, the compounds according to the invention show (I-2) and (I-9) have a very good anti-growth effect.  

Example D Wheat growth

Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amounts of solvent and emulsifier and fill with Water to the desired concentration.

Wheat plants are grown in the greenhouse up to the two-leaf Stage attracted. At this stage the plants sprayed dripping wet with the active ingredient preparations. To The growth of all plants is measured for two weeks and the growth as a percentage of the growth of the control plants calculated. It means 100% growth growth corresponding to that of the control plants and 0% the standstill of growth. Mark values over 100% a growth promotion.

In this test, the compounds according to the invention show (I-2) and (I-9) have a very good anti-growth effect.  

Example E Cotton growth

Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amounts of solvent and emulsifier and fill with Water to the desired concentration.

Cotton plants are grown to the full in the greenhouse Unfolding of the fifth following sheet attracted. In this Stage the plants are dripping wet with the active ingredient preparations sprayed. After two weeks, everyone Plants measured the growth and growth in percent of the growth of the control plants. It 100% growth means growth corresponding to that of control plants and 0% growth arrest. Values above 100% characterize growth promotion, while values below 100% indicate growth inhibition.

In this test, the compounds according to the invention show (I-2) and (I-9) have a very good anti-growth effect.  

Example F Pyricularia test (rice) / protective

Solvent: 12.5 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amounts of solvent and dilute the concentrate with water and the specified amount of emulsifier on the desired concentration on.

To test for protective efficacy one splashes young rice plants with the active ingredient preparation up to Dripping wet. After the spray coating has dried on the plants with an aqueous spore suspension of Pyricularia oryzae inoculated. Then the Plant in a greenhouse at 100% rel. humidity and set up at 25 ° C.

The evaluation of the Disease.

The substances according to the invention show in this test (I-1), (I-3), (I-4), (I-5) and (I-18) are essential better efficacy than the comparison substances (F) and (G).  

Example G Sphearotheca test (cucumber) / protective

Solvent: 4.7 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amounts of solvent and emulsifier and diluted the concentrate with water to the desired concentration.

To test for protective efficacy one splashes young plants with the active ingredient preparation up to Dripping wet. After the spray coating has dried on the plants with conidia of the fungus Sphaerotheca fuliginea pollinated.

The plants are then at 23 to 24 ° C and at a relative humidity of approx. 75% in the greenhouse set up.

The evaluation of the Disease.

The compounds (I-2) and (I-3) according to the invention show a significantly better effectiveness in this test than the comparison substances (B) and (E).  

Example H Leptosphaeria nodorum test (wheat) / protective

Solvent: 100 parts by weight of dimethylformamide
Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amounts of solvent and emulsifier and diluted the concentrate with water to the desired concentration.

To test for protective efficacy one splashes dew dampens young plants with the active ingredient preparation. After the spray coating has dried on, the plants with a conid suspension of Leptosphaeria nodorum sprayed. The plants remain for 48 hours 20 ° C and 100% rel. Humidity in an incubation cabin.

The evaluation of the Disease.

In this test, the substances (I-2) according to the invention show (I-5) and (I-8) a much better effectiveness than the comparison substances (A) to (D).

Claims (8)

1. Cyclopropyl-hydroxyalkyl-azolyl derivatives of the formula in which
R for the remainder of the formulas and
X represents the groupings -CH₂-CH₂-, -CH = CH-, -O-CH₂- or -S-CH₂-, the heteroatom being connected to the aromatic or heteroaromatic radical when X is -O-CH₂- or -S-CH₂-,
or
R also for stands when X stands for -S-CH₂-,
as well as their acid addition salts and metal salt complexes. 2. Process for the preparation of cyclopropyl-hydroxyalkyl-azolyl derivatives of the formula in which
R for the remainder of the formulas and
X represents the groupings -CH₂-CH₂-, -CH = CH-, -O-CH₂- or -S-CH₂-, the heteroatom being connected to the aromatic or heteroaromatic radical when X is -O-CH₂- or -S-CH₂-,
or
R also for stands when X stands for -S-CH₂-,
as well as their acid addition salts and metal salt complexes,
characterized in that oxiranes of the formula in which
R and X have the meaning given above,
with 1,2,4-triazole of the formula in the presence of an acid binder and in the presence of a diluent and, if appropriate, in the presence of a catalyst and, if appropriate, then adding an acid or a metal salt to the compounds of the formula (I) thus obtained. 3. Fungicides and plant growth regulators, labeled by containing at least one Cyclopropyl-hydroxyalkyl-azolyl derivative of the formula (I) according to claim 1 or an acid addition salt or metal salt complex of a cyclopropyl hydroxyalkyl azolyl derivative of the formula (I).   4. Use of cyclopropyl-hydroxyalkyl-azolyl Derivatives of formula (I) according to claim 1 or of their acid addition salts and metal salt complexes to combat fungi and Regulation of plant growth. 5. Fungus control and regulation procedures of plant growth, characterized, that cyclopropyl-hydroxyalkyl Azolyl derivatives of the formula (I) according to Claim 1 or their acid addition salts or metal salt Complexes on the plants and / or their habitat deploys. 6. Process for the preparation of fungicides and plant growth regulating agents, characterized in that cyclopropyl-hydroxyalkyl-azolyl Derivatives of formula (I) according to claim 1 or their Acid addition salts or metal salt complexes with Extenders and / or surfactants mixed. 7. Oxiranes of the formula in which
R for the remainder of the formulas and
X represents the groupings -CH₂-CH₂-, -CH = CH-, -O-CH₂- or -S-CH₂-, the heteroatom being connected to the aromatic or heteroaromatic radical when X is -O-CH₂- or -S-CH₂-,
or
R also for is when X is -S-CH₂-. 8. Process for the preparation of oxiranes of the formula in which
R for the remainder of the formulas and
X represents the groupings -CH₂-CH₂-, -CH = CH-, -O-CH₂- or -S-CH₂-, the heteroatom being connected to the aromatic or heteroaromatic radical when X is -O-CH₂- or -S-CH₂-,
or
R also for stands when X stands for -S-CH₂-,
characterized in that cyclopropyl ketones of the formula in which
R and X have the meaning given above, either
α) with dimethyloxosulfonium methylide of the formula or
β) with dimethylsulfonium methylide of the formula in the presence of a diluent.