DE19517720A1 - New 1-benzyl-2-triazolyl-ethanol derivs. - Google Patents

Abstract

1-Benzyl-2-(1,2,4-triazol-1-yl)-ethanol derivs. of formula (I) and their acid-addn. salts and metal complexes are new: X = halo, 1-4C alkyl or 1-4C alkoxy; Y = CO or CHOH; Z = halo, 1-4C alkyl, 1-4C haloalkyl, 1-4C alkoxy, 1-4C haloalkoxy, NO2, or phenyl substd. by 0-3 halo atoms; m = 0-3; or adjacent Z+Z = opt. halogenated 3-4C alkylene in which 1-2 nonadjacent C atoms may be replaced by O.

Description

The present invention relates to new benzyl-cyclopropyl-carboxy-azoles Process for their preparation and their use as microbicides.

It has already become known that numerous hydroxyethyl azolyl derivatives have fun possess gicidal properties (cf. EP-OS 0 114 487 and EP-OS 0 117 578). So For example, 2- (2,4-dichlorophenyl) -1-cyclopropyl-1-oxo-3- (1,2,4-tri azol-1-yl) propan-2-ol and 2- (2,4-dichlorophenyl) -1-cyclopentyl-1-oxo-3- (1,2,4-tri Use azol-1-yl) propan-2-ol to combat fungi. The effect of this Fabrics are good, but in some cases allow for low application rates wish left.

There were now new benzyl-cyclopropyl-carboxy-azoles of the formula

in which
X represents hydrogen, halogen, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms,
Y for

stands,
Z for halogen, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 5 halogen atoms, alkoxy with 1 to 4 carbon atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 halogen atoms, nitro or optionally single to triple, similar or phenyl substituted differently by halogen and
m represents the numbers 0, 1, 2 or 3,
or
Z _{m represents} an ortho-permanently linked, optionally halogen-substituted alkylene group with 3 or 4 carbon atoms, in which one or two (non-adjacent) carbon atoms can be replaced by oxygen,
as well as their acid addition salts and metal salt complexes.

The substances according to the invention contain at least one asymmetrically substituted carbon atom. They can therefore occur in optical isomer forms. The The present invention relates to both the individual isomers and their Mixtures.

It was also found that benzyl-cyclopropyl-carboxy-azoles of the formula (I) and their acid addition salts and metal salt complexes are obtained when Oxirane derivatives of the formula

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

in the presence of an acid binder and in the presence of a diluent implemented and optionally the resulting benzyl-cyclopropyl-carboxy azoles of the formula

in which
X, Z and m have the meanings given above,
either

• α) reacted with complex hydrides in the presence of a diluent, or
• β) with aluminum isopropylate in the presence of a diluent puts,

and optionally to the compounds of formula (1) thus obtained an acid or metal salt is added.

Finally, it was found that the new benzyl-cyclopropyl-carboxy-azoles Formula (I) and its acid addition salts and metal salt complexes are very good have microbicidal properties and both in crop protection and in Material protection can be used.

Surprisingly, the substances according to the invention have a better micro bicidal activity as the most constitutionally similar, known compounds  same direction of action. The substances according to the invention thus exceed the 2- (2,4-dichlorophenyl) -1-cyclopropyl-1-oxo-3- (1,2,4-triazol-1-yl) prop-an-2-ol and that 2- (2,4-dichlorophenyl) -1-cyclopentyl-1-oxo-3- (1,2,4-traizol-1-yl) -pr-opan-2-ol regarding their fungicidal properties.

The benzyl-cyclopropyl-carboxy-azoles according to the invention are of the formula (I) generally defined.

X preferably represents hydrogen, fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, methoxy and ethoxy.
Y also preferably stands for

Z preferably represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, trichloromethyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, Trifluoromethoxy, difluoromethoxy, nitro or optionally single or double, similar or different phenyl substituted by fluorine and / or chlorine.
m preferably stands for the numbers 0, 1, 2 or 3. If in stands for 2 or 3, Z can stand for the same or different radicals.

It also says
Z _{m '} when m is 2, also preferably for an ortho-linked, optionally mono- to tetrasubstituted by fluorine and / or chlorine-substituted alkylene chain with 3 or 4 carbon atoms in which one or two (non-adjacent) carbon atoms have been replaced by oxygen can.

Preferred substances according to the invention are also addition products from acids and those benzyl-cyclopropyl-carboxy-azoles of the formula (I) in which X, Y, Z and have the meanings given as preferred.

The acids that can be added preferably include halogen water Substance acids, such as B. the hydrochloric acid and hydrobromic acid, ins especially hydrochloric acid, also phosphoric acid, nitric acid, Schwe  rock acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as e.g. B. acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, lemons acid, salicylic acid, sorbic acid and lactic acid and sulfonic acids, such as. B. p-toluenesulfonic acid, 1,5-naphthalenedisulfonic acid or camphorsulfonic acid, Saccharin and thiosaccharin.

Additionally preferred compounds according to the invention are addition products from salts of metals from II. to IV. main and I. and II. and IV. to VIII. Subgroup of the Periodic Table of the Elements and those benzyl cyclopropyl-carboxy-azoles of the formula (I) in which X, Y, Z and m are the be preferably have given meanings.

Here are salts of copper, zinc, manganese, magnesium, tin, iron and of nickel is particularly preferred. Anions of these salts come in Considering those derived from those acids that are too physiologically acceptable Lead 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 sulfur acid.

Examples of phenyl-cyclopropyl-carboxy-azoles of the formula (I) are those in the the following tables 1 and 2 listed substances.  

Table 1

Table 2

If 1- (1-chloro-cyclopropyl) -2- (4-methyl-benzyl) -1-oxo-2,3-epoxy is used propane and 1,2,4-triazole as starting materials, so the course of the Invention according to the process are illustrated by the following formula scheme:

If 1- (1-chloro-cyclopropyl) -2- (4-methyl-benzyl) -1-oxo-3- (1,2,4- triazol-1-yl) -propan-2-ol as starting material and sodium borohydride as Reducing agent, the course of the second stage of the invention Procedure can be illustrated by the following formula scheme:

The starting materials in carrying out the process according to the invention Formula (II) provides a general definition of the oxirane derivatives required. In this formula have X, Z and preferably those meanings that already in connection with the description of the substances of the invention mel (I) were preferably mentioned for these residues or this index.

The oxirane derivatives of the formula (II) have hitherto not been known. You leave are made by using ketones of the formula  

in which
X, Z and m have the meanings given above,
with hydrogen peroxide in the presence of an alkali metal hydroxide and in the presence of a diluent.

The in the preparation of oxirane derivatives of formula (II) according to the above The ketones required as starting materials are represented by the formula (IV) generally defined. In this formula, X, Z and preferably have those Meanings already in connection with the description of the Invention substances according to formula (I) preferably for these radicals or this index were called.

The ketones of formula (IV) are not yet known. You let yourself produce by using phenethyl ketones of the formula

in which
X, Z and m have the meanings given above,
either

• α) with bis (dimethylamino) methane of the formula (CH₃) ₂-CH₂-N (CH₃) ₂ (VI) in the presence of acetic anhydride or glacial acetic acid,

or

• β) with paraformaldehyde or formalin in the presence of a catalyst and in In the presence of a diluent.

The in the preparation of the ketones of formula (IV) according to the above procedure Phenethyl ketones required as starting materials are represented by the formula (V) generally defined. In this formula, X, Z and preferably have those Meanings already related to the description of the Substances of the formula (I) according to the invention preferably for these radicals or for this index was named.

The phenethyl ketones of the formula (V) are known or can be reduced produce known methods in principle (cf. EP-OS 0 298 332). So you get Phenethyl ketones of formula (V) by using aldehydes of formula

in which
Z and m have the meanings given above,
with methyl-cyclopropyl-ketones of the formula

in which
X has the meaning given above,
in the presence of a catalyst, such as. B. sodium hydroxide and in the presence of a diluent, such as. As ethanol, at temperatures between 10 ° C and 80 ° C and the resulting compounds of the formula

in which
X, Z and m have the meanings given above,
in the presence of a catalyst, such as. B. Raney nickel or palladium, and in the presence of a diluent, such as. As ethylene glycol dimethyl ether or thiodiglycol, hydrogenated at temperatures between 20 ° C and 120 ° C under a hydrogen pressure between 10 and 60 bar.

The in the implementation of the above process for the preparation of ketones Formula (IV) substances required as reaction components, namely bis- (Dimethylamino) methane of the formula (VI) or paraformaldehyde or formalin (aqueous formaldehyde solution with a formaldehyde content of 37%) known.

The reaction temperatures can be carried out when carrying out variant (α) The above process for the preparation of ketones of the formula (IV) within a larger range can be varied. Generally one works at temperatures between 20 ° C and 120 ° C, preferably between 30 ° C and 110 ° C.

Both when implementing variant (α) and variant (β) of The above process for the preparation of ketones of the formula (IV) is carried out in general under normal pressure. But it is also possible to increase or to work under reduced pressure.

When carrying out variant (α) of the above process for producing Ketones of the formula (IV) are placed on 1 mol of phenethyl ketone of the formula (V) in general 3 to 4 moles of bis (dimethylamino) methane of the formula (VI). The Refurbishment is carried out using customary methods.

Catalysts come in carrying out variant (β) of the above Process for the preparation of ketones of formula (IV) all for such  Implementations usual reaction accelerators into consideration. Preferably used bar are alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide.

As a diluent, variant (β) of the above can be used Process for the preparation of ketones of formula (IV) all for such Implementation of the usual inert, organic solvents. Preferably Alcohols such as methanol or ethanol can be used.

The reaction temperatures can be carried out when carrying out variant (β) The above process for the preparation of ketones of the formula (IV) within a certain range can be varied. Generally one works at Temperatures between 10 ° C and 40 ° C, preferably at room temperature.

When performing variant (β) of the above process for producing Ketones of the formula (IV) are used per mole of phenethyl ketone of the formula (V) generally 1.5 to 2.5 equivalents of paraformaldehyde or formalin and an equivalent amount of catalyst. - The processing takes place after usual methods.

In the preparation of oxirane derivatives of the formula (II) according to the above Ver driving hydrogen peroxide serves as a reaction component. Preferably used bar is a 30% aqueous hydrogen peroxide solution.

As alkali metal hydroxides come in the manufacture of oxirane derivatives Formula (II) according to the above method, preferably sodium hydroxide and Potassium hydroxide into consideration.

The diluents used in the manufacture of oxirane derivatives are Formula (II) according to the above method with water-miscible alcohols. Methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol.

The reaction temperatures in the production of oxirane derivatives Formula (II) according to the above method within a certain range can be varied. In general, temperatures between 0 ° C and 80 ° C, preferably between 10 ° C and 70 ° C.  

In the preparation of oxirane derivatives of formula (II) according to the above The procedure is generally carried out under normal pressure. It is also possible to work under increased or reduced pressure.

When carrying out the above process, 1 ket of ketone is used Formula (IV) generally 2 to 5 moles, preferably 2.5 to 4 moles Hydrogen peroxide and a catalytic amount of alkali metal hydroxide liquor on. The processing takes place according to usual methods. Generally you go so that the reaction mixture is mixed with water, then with one Water miscible organic solvent extracted, the combined organic phases in succession with aqueous potassium iodide solution and water washes and after the subsequent drying under reduced pressure constricts. The remaining residue may be removed by conventional methods existing impurities are freed.

As acid binders come when performing the first stage of The inventive method all the usual inorganic and organic bases in question. Alkali metal carbonates, such as sodium and Potassium carbonate, also alkali metal hydroxides, such as sodium and potassium hydroxide, also alkali metal alcoholates, such as sodium and potassium methylate and ethylate as well as potassium tert-butoxide, and furthermore lower tertiary alkyl amines, cyclo alkylamines and aralkylamines, such as in particular triethylamine.

As a diluent when performing the first stage The inventive method all usual inert organic solvents in Consideration. Nitriles, such as acetonitrile, are also preferably used, and aroma table hydrocarbons such as benzene, toluene and dichlorobenzene, also Formamides, such as dimethylformamide, and strongly polar solvents, such as dime thylsulfoxide and hexamethylphosphoric triamide.

The reaction temperatures can be carried out when carrying out the first stage of The method according to the invention can be varied over a wide range. in the generally one works at temperatures between 0 ° C and 130 ° C, preferably between 40 ° C and 120 ° C.  

One also works in the implementation of the method according to the invention general under normal pressure. However, it is also possible to increase or to work under reduced pressure.

When carrying out the first stage of the method according to the invention 1 mol of oxirane of the formula (II) is generally 1 to 4 mol of 1,2,4- Triazole of formula (III) and 0.3 to 3 moles of acid binder. The workup takes place according to usual methods. In general, you do that The reaction mixture is concentrated, the remaining residue in one with water absorbs little miscible organic solvent, washes with water and after drying. The remaining product can, if necessary undergo further cleaning processes.

This initially arises when the method according to the invention is carried out The benzyl-cyclopropyl-carboxy-azoles of the formula (Ia) can optionally in a second stage with the help of complex hydrides (variant α) or Aluminum isopropylate (variant β) can be reduced.

As complex hydrides come in performing the second stage of the inventive method (variant α) preferably sodium borohydride and Lithium aluminum hydride in question.

As a diluent when performing the second stage inventive method (variant α) all for such implementations usual inert, organic solvents into consideration. Preferably usable are alcohols, such as methanol, ethanol, isopropanol or butanol, and also Ether, such as diethyl ether or tetrahydrofuran, or water mixed with an alcohol.

The reaction temperatures can be carried out in the second stage of the inventive method (variant α) within a certain range can be varied. Generally one works at temperatures between -20 ° C and + 80 ° C, preferably between 0 ° C and + 60 ° C.

When performing the second stage of the method according to the invention (Variant α) is set on 1 mol of benzyl-cyclopropyl-carboxy-azole of the formula (Ia) in general an equivalent amount or an excess of com  complex hydride. The processing takes place according to usual methods. Generally I think you proceed in such a way that you concentrate the reaction mixture, the lead the residue is mixed with water, then several times with one with water extracted little miscible organic solvent, the combined organi phases dry and constrict.

As a diluent when performing the second stage inventive method (variant β) all usual for such reactions inert organic solvents. Are preferably usable Alcohols, such as isopropanol, and also aromatic hydrocarbons, such as Benzene.

The reaction temperatures can also be carried out when carrying out the second stage of the method according to the invention (variant β) varied over a wide range will. Generally one works at temperatures between 20 ° C and 120 ° C, preferably between 50 ° C and 100 ° C.

When performing the second stage of the method according to the invention (Variant β) is set on 1 mol of benzyl-cyclopropyl-carboxy-azole of the formula (Ia) generally an equivalent amount or an excess preferably 1 to 2 moles of aluminum isopropylate. The processing takes place after usual methods. The general procedure is to get the reak concentrated mixture, then with dilute mineral acid or with aqueous Alkali metal base added, then with a water-immiscible organic solvent extracted, the combined organic phases dry and constricts.

The benzyl-cyclopropyl-carboxy-azoles of the formula (I) can be converted into acid addition salts or metal salt complexes.

For the preparation of acid addition salts of the compounds of the formula (I) those acids that are already related are preferred with the description of the acid addition salts according to the invention as preferred Acids were called.

The acid addition salts of the compounds of formula (I) can in simpler Way according to usual salt formation methods, e.g. B. by loosening a connection  of formula (I) in a suitable inert solvent and adding the Acid, e.g. As hydrochloric acid can be obtained and in a known manner, for. B. by filtration, isolated and optionally by washing with an inert organic solvents can be cleaned.

For the preparation of metal salt complexes of the compounds of the formula (I) are preferably those salts of metals that are already in the Connection with the description of the metal salt grain according to the invention plexes were mentioned as preferred metal salts.

The metal salt complexes of the compounds of formula (I) can in simpler Be obtained by conventional methods, such. B. by solving the Metal salt in alcohol, e.g. B. ethanol and adding to compounds of Formula (I). You can metal salt complexes in a known manner, for. B. by Ab filter, isolate and if necessary clean by recrystallization.

The active compounds according to the invention have a strong microbicidal action and can be used to combat unwanted microorganisms such as fungi and Bacteria, used in crop protection and with material protection.

Fungicides are used in crop protection to combat Plasmodio phoromycetes, 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 Pseudoinonas lachrymans;
Erwinia species, such as Erwinia amylovora;
Pythium species, such as Pythium ultimum;
Phytophthora species, such as Phytophthora infestans;
Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara species, such as Plasmopara viticola;
Peronospora species, such as Peronospora pisi or P. brassieae;
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 control of the plant necessary concentrations allow treatment of upper earthly parts of plants, planting and seeds and the soil.

The active compounds according to the invention are particularly suitable for combating Pyricularia oryzae and Pellicularia sasakii on rice and for combating Cereal diseases such as Leptosphaeria nodorum, Cochliobolus sativus, Pyreno phora teres, Pseudocercosporella herpotrichoides, Erysiphe and Fusarium species. In addition, the substances according to the invention show a very good and broad in vitro Effect.

In material protection, the substances according to the invention can be used to protect technical materials against infestation and destruction by unwanted micro use organisms.  

In the present context, technical materials include non-living ones Understand materials that have been prepared for use in technology they are. For example, technical materials through fiction appropriate active ingredients are protected against microbial change or destruction adhesives, glues, paper and cardboard, textiles, leather, wood, Paints and plastic articles, cooling lubricants and other materials that are attacked or decomposed by microorganisms. As part of the materials to be protected are also parts of production facilities for example, cooling water circuits, called by multiplication of micro organisms can be affected. Within the scope of the present invention as technical materials are preferably adhesives, glues, papers and Cardboard boxes, leather, wood, paints, cooling lubricants and heat transfer called liquids, particularly preferably wood.

As microorganisms that break down or change the technical Materials can cause, for example, bacteria, fungi, yeast, algae and called mucus organisms. The ones according to the invention preferably act Active ingredients against fungi, in particular mold, wood-staining and wood destructive fungi (Basidiomycetes) and against mucous organisms and algae.

For example, microorganisms of the following genera may be mentioned:
Alternaria, such as Alternaria tenuis,
Aspergillus, such as Aspergillus niger,
Chaetomiuin, like Chaetomium globosum,
Coniophora, such as Coniophora puetana,
Lentinus, such as Lentinus tigrinus,
Penicillium, such as Penicillium glaucum,
Polyporus, such as Polyporus versicolor,
Aureobasidium, such as Aureobasidium pullulans,
Sclerophoma, such as Sclerophoma piyophila,
Trichoderma, like Trichoderma viride,
Escherichia, such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, such as Staphylococcus aureus.

The substances according to the invention can be converted into the customary formulations such as solutions, emulsions, suspensions, powders, foams, pastes, Granules, aerosols, very fine encapsulations in polymeric substances and in envelopes masses for seeds as well as ULV formulations.

These formulations are prepared in a known manner, e.g. B. by Ver mix the active ingredients with extenders, i.e. liquid solvents Pressurized liquefied gases and / or solid carriers, if necessary using surface-active agents, ie emulsifiers and / or Dispersing agents and / or foaming agents. In case of use of water as an extender can e.g. B. also organic solvents Auxiliary solvents can 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 carbons Hydrogen, 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, strongly polar solution agents such as dimethylformamide and dimethyl sulfoxide, and water; with ver liquid gaseous extenders or carriers are such liquids meant which are gaseous at normal temperature and pressure, e.g. B. aerosol propellants such as butane, propane, nitrogen and carbon dioxide; as fixed Carriers come into question: z. B. natural stone powder, such as kaolins, Clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates; as solid carriers for granules come into question: z. B. broken chene and fractionated natural rocks such as calcite, marble, pumice, sepiolite, Dolomite and synthetic granules from inorganic and organic flours as well as granules of organic material such as sawdust, coconut shells, corn pistons and tobacco stems; as an emulsifier and / or foam-generating agent come into question: z. B. non-ionic and anionic emulsifiers, such as poly oxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylaryl poly glycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersants come into question: z. B. lignin sulfite and methyl cellulose.  

In the formulations, adhesives such as carboxymethylcellulose, naturally Liche and synthetic powdery, granular or latex-shaped polymers used such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and 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. B. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalalo cyanine 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 weight Percent active ingredient preferably between 0.5 and 90%.

When used in crop protection, the active compounds according to the invention can be used as such or in their formulations also in a mixture with known fungicides, Bactericides, acaricides, nematicides or insecticides can be used so e.g. B. to broaden the spectrum of activity or to develop resistance bow. In some cases, synergistic effects also occur indicates that the mixture has a higher effect than the sum of the Effects of the individual components.

As a mixing partner come z. B. Consider the following substances:
Fungicides:
2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ′, 6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoximino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophen oxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
Dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fen propimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Futuberolosil, Futuberfosil , Furmecyclox,
Guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodion, Isoprothiolan, Kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil, Nickel-dimethyldithiocarbamate, Nitrothal-Isopropyl, Nuarimol,
Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyr azophos, pyrifenox, pyrimethanil, pyroquilon,
Quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, Tecloftalam, Tecnazen, Tetraconazole, Thiabendazole, Thicyofen, Thiophanat-methyl, Thirain, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Trifluminitole, Triflumolitone, Trifluminitole
Validamycin A, vinclozolin,
Zineb, ziram.

Bactericides:
Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, teclofta lam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:
Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alpha inethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, 4-bromo-2- (4-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluorine, bifenthrin, BPMC, brofenprox , Bromophos A, Bufencarb, Buprofezin, Buto carboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184 699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrinothrinhrhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrinhrofhrinhrinhrinhrinhrofhrinothrinhrhrinhrinhrhrinhrinhrofhrinothrinophrinothrinophrinothrinothrinophrinothrinophrinothrinophrinophrine , Cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethopro phos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothxinfox, Fufionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon
HCH, heptenophos, hexafluinuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,
Lambda cyhalothrin, lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Metamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, M 25, Nitenpyram
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhion, Pyrachlophhion, Pyrachlophhion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophion Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos,
RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomenhrononium, Triomenethriazonium, Tri
Vamidothione, XMC, xylylcarb, zetamethrin.

A mixture with other known active ingredients, such as herbicides or with Fertilizers and growth regulators are possible.

The active substances can be used as such, in the form of their formulations or in the form thereof prepared application forms such as ready-to-use solutions, suspensions, Wettable powders, pastes, soluble powders, dusts and granules will. The application is done in the usual way, e.g. B. by casting, Ver spraying, spraying, scattering, dusting, foaming, brushing etc. It it is also possible to use the ultra-low-volume method bring or the drug preparation or the drug itself into the soil to inject. The seeds of the plants can also be treated.

When treating parts of plants, the active substance concentrations can be in the application forms can be varied over a wide range. They are in the generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

In the seed treatment, amounts of active ingredient are generally from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g.

When treating the soil, active ingredient concentrations are from 0.00001 to 0.1 wt .-%, preferably from 0.0001 to 0.02 wt .-% required at the site of action Lich.

The means used to protect technical materials contain the Active ingredients in general in an amount of 1 to 95%, preferably from 10 to 75%.

The application concentrations of the active compounds according to the invention are directed according to the type and the occurrence of the microorganisms to be controlled and according to the composition of the material to be protected. The optimal use  quantity can be determined by test series. Generally the applications are dung concentrations in the range of 0.001 to 5 wt .-%, preferably 0.05 up to 1.0% by weight based on the material to be protected.

The effectiveness and spectrum of activity of the material according to the invention protection active ingredients to be used or the means that can be produced therefrom, Kon concentrates or more general wording can be increased if given if necessary, other antimicrobial compounds, fungicides, bactericides, Herbicides, insecticides or other active substances to increase the effectiveness spectrum or achieving special effects such. B. the additional protection be added by insects. These blends can have a broader impact have spectrum than the compounds of the invention. In many cases he keep synergistic effects, d. H. the effectiveness of the mixture is greater than the effectiveness of the individual components.

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

Manufacturing examples example 1

A mixture of 3 g (12 mmol) 1- (1-chlorocyclopropyl) -2- (4-methyl-benzyl) -1- oxo-2,3-epoxypropane, 0.45 g (4 mmol) potassium tert-butoxide, 2.5 g (36 mmol) 1,2,4-triazole and 30 ml of dimethylformamide is stirred at 80 ° C for 15 hours. The reaction mixture is then concentrated under reduced pressure. Man takes up the remaining residue in ethyl acetate, that washes resulting mixture with water, the organic phase dries over Sodium sulfate and concentrated under reduced pressure. The one that arises The residue is eluted with ethyl acetate: cyclohexane = 2: 1 Chromatographed silica gel. After concentrating the eluate under reduced pressure Pressure gives 1.5 g (40% of theory) of 1- (1-chloro-cyclopropyl) -2- (4-methyl-benzyl) -1-oxo-3- (1,2,4-triazol-1-yl) propan-2-ol.

1 H-NMR spectrum (200 MHz, CDCl₃, TMS)
δ = 1.3-1.7 (m, 4H); 2.3 (s, 3H); 3.19 (d, J = 14 Hz, 1H); 3.66 (d, J = 14 Hz, 1H); 4.28 (s. 1H); 4.38 (d, J = 15 Hz, 1H); 5.42 (d, J = 15 Hz, 1H); 7.08 (d, J = 8 Hz; 2H); 7.2 (d, J = 8 Hz, 2H); 7.86 (s, 1H); 8.12 (s, 1H) ppm.

Manufacture of starting substances

A solution of 4 g (17 mmol) 1- (1-chloro-cyclopropyl) -2- (4-methyl-benzyl) -1- oxo-2-propene in 60 ml methanol is stirred at 15 ° C with 6 ml (48 mmol) 30% hydrogen peroxide solution added. Then drop 2.2 ml Add 5 molar, aqueous sodium hydroxide solution and then stir for 3 hours at room temperature  temperature. The reaction mixture is poured onto water, and the resultant Mixture is extracted several times with ethyl acetate. The United organic phases are first with 3% aqueous potassium iodide solution and then washed with water. Then the organic phase over Dried sodium sulfate and then concentrated under reduced pressure. Man receives 3 g (70% of theory) of 1- (1-chloro-cyclopropyl) -2- (4- methyl-benzyl) -1-oxo-2,3-epoxypropane.

In a mixture of 11 g (50 mmol) 1- (1-chloro-cyclopropyl) -3- (4-methyl-phenyl) - 1-oxo-propane and 15.3 g (150 mmol) of bis (dimethylamino) methane are added Stir in 20 ml (180 mmol) of acetic anhydride at room temperature. When the addition is complete, the reaction mixture is first at 90 ° C for 1 hour stirred, then cooled to room temperature and poured onto ice water. The resulting mixture is extracted several times with ethyl acetate. The combined organic phases are successively with dilute, aqueous Washed sodium bicarbonate solution, then dried over sodium sulfate and concentrated under reduced pressure. This gives 10.5 g (90% of theory) of 1- (1-chloro-cyclopropyl) -2- (4-methyl-benzyl) -1-oxo-2- propen.

According to the method given in Example 1, the in following Table 3 substances of formula (I) produced.  

Table 3

Example 2

δ = 1.2-1.8 (m, 4H); 3.51 (d, J = 15 Hz, 1H); 3.83 (d, J = 15 Hz, 1H); 4.28 (d, J = 15 Hz, 1H); 5.5 (d, J = 15 Hz; 1H); 7.1-7.5 (m. 4H); 7.88 (s. 1H); 8.08 (s, 1H) ppm.

Example 3

δ = 1.4-1.7 (m, 4H); 3.41 (d, J = 14 Hz; 1H); 3.52 (d, J = 14 Hz, 1H); 4.28 (s. 1H); 4.32 (d, J = 15 Hz; 1H); 5.41 (d, J = 15 Hz; 1H); 7.1-7.3 (m. 4H); 7.85 (s. 1H); 8.1 (s, 1H) ppm.

Example 4

δ = 1.4-1.7 (m, 4H); 3.11 (d, J = 14 Hz; 1H); 3.72 (d, J = 14 Hz; 1H); 4.3 (s. 1H); 4.38 (d, J = 15 Hz; 1H); 5.4 (d, J = 15 Hz; 1H); 5.92 (s, 2H); 6.7-6.9 (m, 3H); 7.86 (s, 1H); 8.12 (s, 1H) ppm.

Example 5

δ = 1.3-1.7 (m, 4H); 3.17 (d, J = 15 Hz, 1H); 3.7 (d, J = 15 Hz; 1H); 4.3 (s. 1H); 4.4 (d, J = 15 Hz, 1H); 5.4 (d, J = 15 Hz, 1H); 6.9-7.1 (m, 2H); 7.2-7.4 (m, 2H); 7.87 (s, 1H); 8.12 (s, 1H) ppm.

Example 6

δ = 1.4-1.8 (m, 4H); 3.43 (d, J = 14 Hz6, 1H); 3.8 (d, J = 14 Hz, 1H); 4.38 (s, 1H); 4.28 (d, J = 15 Hz, 1H); 5.5 (d, J = 15 Hz, 1H); 7.15-7.25 (m, 2H); 7.35-7.45 (m, 2H); 7.87 (s, 1H); 8.08 (s, 1H) ppm.

Example 7

δ = 1.4-1.9 (m, 4H); 3.43 (d, J = 14 Hz, 1H); 3.8 (d, J = 14 Hz, 1H); 4.25 (d, J = 15 Hz, 1H); 5.5 (d, J = 15 Hz, 1H); 7.1-7.4 (m, 4H); 7.88 (s. 1H); 8.07 (s, 1H) ppm.  

Example 8

δ = 1.3-1.7 (m, 4H); 3.16 (d, J = 15 Hz, 1H); 3.67 (d, J = 15 Hz, 1H); 3.8 (s. 3H); 4.28 (s. 1H); 4.38 (d, J = 15 Hz, 1H); 5.41 (d, J = 15 Hz, 1H); 6.82 (d, J = 8 Hz, 2H); 7.25 (d, J = 8 Hz, 2H); 7.87 (s, 1H); 8.12 (s, 1H) ppm.

Example 9

δ = 1.3-1.7 (m, 4H); 3.17 (d, J = 15 Hz, 1H); 3.71 (d, J = 15 Hz, 1H); 4.32 (s, 1H); 4.41 (d, J = 15 Hz, 1H); 5.42 (d, J = 15 Hz, 1H); 7.2-7.4 (m, 4H); 7.78 (s. 1H); 8.12 (s, 1H) ppm.

Example 10

δ = 1.2-1.7 (m, 4H); 3.14 (d, J = 15 Hz, 1H); 3.71 (d, J = 15 Hz, 1H); 4.35 (s, 1H); 4.41 (d, J = 15 Hz, 1H); 5.4 (d, J = 15 Hz, 1H); 7.1-7.5 (m. 3H); 7.88 (s. 1H); 8.12 (s, 1H) ppm.

Example 11

δ = 1.3-1.8 (m, 4H); 3.18 (d, J = 14 Hz, 1H); 3.7 (d, J = 14 Hz, 1H), 4.3 (s, 1H); 4.4 (d, J = 15 Hz, 1H); 5.4 (d, J = 15 Hz, 1H); 7.2-7.4 (m, 4H); 7.86 (s, 1H); 8.13 (s, 1H) ppm.

Example 12

δ = 1.4-1.8 (m, 4H); 3.41 (d, J = 15 Hz, 1H); 3.74 (d, J = 15 Hz, 1H); 4.23 (d, J = 15 Hz, 1H); 4.37 (s, 1H); 5.48 (d, J = 15 Hz, 1H); 7.2-7.5 (m, 3H); 7.85 (s. 1H); 8.08 (s, 1H) ppm.

Example 13

δ = 0.8-1.2 (m, 4H); 2.2-2.5 (in, 1H); 3.22 (d, J = 14 Hz, 1H); 3.44 (d, J = 14 Hz, 1H); 4.25 (d, J = 15 Hz, 1H); 4.58 (s. 1H); 4.91 (d, J = 15 Hz, 1H); 7.2-7.5 (m, 4H); 7.87 (s, 1H); 8.09 (s, 1H) ppm.  

Examples of use Example A

Leptosphaeria nodorum test (wheat) / protective
Solvent: 10 parts by weight of N-methyl-pyrrolidone
Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether.

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the Active ingredient preparation in the specified application rate. After the The plants are sprayed with a spore suspension of Leptosphaeria sprayed nodorum. The plants remain at 20 ° C and 100% for 48 hours relative humidity in an incubation cabin.

The plants are grown in a greenhouse at a temperature of approx. 15 ° C and a relative humidity of approx. 80%.

Evaluation is carried out 10 days after the inoculation.

In this test, the active ingredient (I-2) according to the invention shows one Application rate of 250 g / ha an efficiency of 100%.  

Example B

Erysiphe test (barley) / protective
Solvent: 10 parts by weight of N-methyl-pyrrolidone
Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether.

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the Active ingredient preparation in the specified application rate. After the The plants are sprayed with spores from Erysiphe graminis f.sp. hordei pollinated.

The plants are grown in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of about 80% set up the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, the active compounds according to the invention (I-2), (I-6), (I-9) and (I-13) with an application rate of 250 g / ha an efficiency of 100%.  

Example C

Erysiphe test (wheat) / protective
Solvent: 10 parts by weight of N-methyl-pyrrolidone
Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether.

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the Active ingredient preparation in the specified application rate. After the The plants are sprayed with spores from Erysiphe graminis f.sp. tritici pollinated.

The plants are grown in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of about 80% set up the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, the active compounds according to the invention (I-2), (I-4), (I-6), (I-7), (I-9) and (I-13) with an application rate of 250 g / ha an efficiency of 100%.

Claims (13)

1. Benzyl-cyclopropyl-carboxy-azoles of the formula in which
X represents hydrogen, halogen, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms,
Y for stands,
Z for halogen, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 5 halogen atoms, alkoxy with 1 to 4 carbon atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 halogen atoms, nitro or optionally single to triple, similar or phenyl substituted differently by halogen and
m represents the numbers 0, 1, 2 or 3,
Z _{m represents} an ortho-permanently linked, optionally halogen-substituted alkylene group with 3 or 4 carbon atoms, in which one or two (non-adjacent) carbon atoms can be replaced by oxygen,
as well as their acid addition salts and metal salt complexes. 2. Benzyl-cyclopropyl-carboxy-azoles of the formula (I) according to Claim 1, in which
X for hydrogen, fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, methoxy and ethoxy,
Y for stands,
Z for fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, trichloromethyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, trifluoromethoxy, difluoromethoxy, Nitro or optionally mono- or disubstituted, identical or different phenyl substituted by fluorine and / or chlorine, and
m stands for the numbers 0, 1, 2 or 3, where Z can stand for the same or different radicals if in stands for 2 or 3, or if m stands for 2,
Z _m also represents an ortho-permanently linked alkylene chain with 3 or 4 carbon atoms, optionally monosubstituted to tetrasubstituted by fluorine and / or chlorine, in which one or two (not adjacent) carbon atoms can be replaced by oxygen. 3. A process for the preparation of benzyl-cyclopropyl-carboxy-azoles of the formula (I) according to claim 1 and of their acid addition salts and metal salt complexes, characterized in that oxirane derivatives of the formula in which
X, Z and have the meanings 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, the resulting benzyl-cyclopropyl-carboxy-azoles of the formula in which
X, Z and m have the meanings given above,
either

• α) reacted with complex hydrides in the presence of a diluent, or
• β) reacted with aluminum isopropylate in the presence of a diluent,

and optionally to the compounds of formula (I) thus obtained then an acid or metal salt is added. 4. Microbicidal agents, characterized by a content of at least a benzyl-cyclopropyl-carboxy-azole of the formula (I) according to claim 1 or on an acid addition salt or metal salt complex of a benzyl cyclopropyl-carboxy-azoles of formula (I).   5. Use of benzyl-cyclopropyl-carboxyazoles of the formula (I) according to Claim 1 or of their acid addition salts and metal salt Complexes as microbicides in crop protection and material protection. 6. Methods for combating undesirable microorganisms in the Plant protection and material protection, characterized in that one Benzyl-cyclopropyl-carboxy-azoles of the formula (I) according to Claim 1 or their acid addition salts or metal salt complexes on the micro organisms and / or their habitat. 7. Process for the preparation of microbicidal agents, thereby characterized in that benzyl-cyclopropyl-carboxy-azoles of the formula (I) according to claim 1 or their metal salt complexes or acid addition Salts mixed with extenders and / or surfactants. 8. Oxirane derivatives of the formula in which
X represents hydrogen, halogen, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms,
Z for halogen, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 5 halogen atoms, alkoxy with 1 to 4 carbon atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 halogen atoms, nitro or optionally single to triple, similar or phenyl substituted differently by halogen and
m represents the numbers 0, 1, 2 or 3, or
Z _{m represents} an ortho-permanently linked, optionally substituted by halogen alkylene group with 3 or 4 carbon atoms,
in which one or two (non-adjacent) carbon atoms can be replaced by oxygen. 9. A process for the preparation of oxirane derivatives of the formula (II) according to claim 8, characterized in that ketones of the formula in which
X, Z and m have the meanings given above,
with hydrogen peroxide in the presence of an alkali metal hydroxide and in the presence of a diluent. 10. Ketones of the formula in which
X represents hydrogen, halogen, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms,
Z for halogen, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 5 halogen atoms, alkoxy with 1 to 4 carbon atoms, haloalkoxy with 1 to 4 carbon atoms and 1 to 5 halogen atoms, nitro or optionally single to triple, similar or phenyl substituted differently by halogen and
m represents the numbers 0, 1, 2 or 3, or
Z _{m stands} for an ortho-permanently linked, optionally halogen-substituted alkylene group with 3 or 4 carbon atoms, in which one or two (non-adjacent) carbon atoms can be replaced by oxygen. 11. A process for the preparation of ketones of the formula (IV) according to claim 10, characterized in that phenethyl ketones of the formula in which
X, Z and have the meanings given above,
either

• α) with bis (dimethylamino) methane of the formula (CH₃) ₂-CH₂-N (CH₃) ₂ (VI) in the presence of acetic anhydride or glacial acetic acid,

or

• β) with paraformaldehyde or formalin in the presence of a catalyst and in the presence of a diluent.