GB2288396A - Cyclopropyl-halogenoethyl-azoles - Google Patents

Description

2288396 Cyclopropvl-halocenoethvl-azoles The present invention relates to

novel cyclopropyl -halogenoethyl-azoles, to a process for their preparation and their use as fungicides.

It has already been disclosed that certain hydroxy-azolyl derivatives possess fungicidal properties (cf. EP-O 438 686 and EP-A 0 123 160). For example, 1- (2 -chlorophenyl) -2 - (1methoxy-cycloprop-l-y1) -3- (1,2,4triazol-l-yl) -propan-2-ol is and 1-(2-chlorophenyl)-2-(1,2,4-triazol-l-yl-methyl)-3,3- dimethyl-butan-2-ol can be used to combat fungi. The action of these substances is good, but in many cases leave something to be desired at low application rates.

Novel cyclopropyl-halogenoethyl-azoles have now been found of the formula 1 57 2 R' C-O-C-R 1 U12 1 N, z N 11 11 0 (1) in which R1 represents alkyl, alkenyl, alkinyl, optionally alkylsubstituted cycloalkyl, optionally substituted aryl, Le A 30 290-Foreign countries ' - 1 optionally substituted aralkyl or substituted aralkenyl, optionally R 2 represents alkyl, halogenoalkyl, optionally substi- tuted aryl or optionally substituted aralkyl, X represents chlorine or bromine and represents nitrogen or a CH group, and their acid addition salts and metal salt complexes.

The substances according to the invention contain an asymmetrically substituted carbon atom. They may therefore be obtained in optical isomer forms. The present invention relates both to the individual isomers and to the mixtures thereof.

It has also been found that cyclopropyl-halogenoethyl- azoles of the formula (1) and their acid addition salts and metal salt complexes are obtained when oxiranes of the formula 0 CH2 1 N, z N 11 R 1 (11) 0 in which b R1 and Z have the meanings given above, Le A 30 290Foreign countries - 2 are reacted with acyl halides of the formula R 2_C_X 11 in which U (III) R 2 and X have the meanings given above, in the presence of an acid-binding agent and optionally in the presence of a diluent followed optionally by the addition of an acid or a metal salt onto the compounds of formula (1) obtained in this way.

is Finally it has been found that the novel cyclopropylhalogenoethylazoles of the formula (1) and their acid addition salts and metal salt complexes possess very good fungicidal properties.

Surprisingly the substances according to the invention exhibit a better fungicidal activity than the previously known compounds of the same general mode of action which are closest to them in terms of constitution.

A general definition of the cyclopropyl-halogenoethylazoles according to the invention is given by the formula (I).

R preferably represents straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched alkenyl having 2 to 8 carbon atoms, straight-chain or branched alkinyl having 2 to 8 carbon atoms, or represents cycloalkyl having 3 to 7 carbon atoms, it being possible for each of these cycloalkyl radicals Le A 30 290-Foreign countries ' 3 -- to be monosubstituted to trisubstituted by identical or different substituents consisting of alkyl having 1 to 4 carbon atoms, or is represents phenyl which may be monosubstituted to trisubstituted by identical or different substituents consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and/or cyano, or represents phenylalkyl having 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety, it being possible f or the phenyl moiety to be in each case monosubstituted to trisubstituted by identical or different substituents consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 Le A 30 290-Foreign countries ' 41 11 carbon atoms in the alkyl moiety, nitro and/or cyano, or is represents phenylalkenyl having 2 to 4 carbon atoms in the straight-chain or branched alkenyl moiety, it being possible for the phenyl moiety to be in each case monosubstituted to trisubstituted by identical or different substituents consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and/or cyano.

R 2 preferably represents straight-chain or branched alkyl having 1 to 6 carbon atoms, staight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms, or represents phenyl which may be monosubstituted to trisubstituted by identical or different substituents consisting of halogen, alkyl having 1 to 4 carbon atoms and/or halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, or represents phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety, it being possible for the phenyl moiety to be monosubstituted to trisubstituted by identical or different substituents consisting of halogen, alkyl having 1 to 4 carbon atoms and/or Le A 30 290-Foreign countries - halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms.

X also preferably represents chlorine or bromine.

is z also preferably represents a nitrogen or a CH group.

particularly preferably represents straight-chain or branched alkyl having 1 to 6 carbon atoms, straightchain or branched alkenyl having 2 to 6 carbon atoms, straight-chain or branched alkinyl having 2 to 6 carbon atoms, or cycloalkyl having 3 to 7 carbon atoms, it being possible for each of these radicals to be monosubstituted to trisubstituted by identical or different substituents consisting of methyl and/or ethyl, or represents phenyl which may be monosubstituted to trisubstituted by identical or different substituents consisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, chlorodif luoromethoxy, chlorodif luoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and/or cyano, or represents phenylalkyl having 1 to 3 carbon atoms in the straight-chain or branched alkyl moiety, it being possible for the phenyl moiety to be in each case monosubstituted to trisubstituted by identical or different substituents consisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, Le A 30 290-Foreign countries ' - 6 methoximinomethyl, cyano. or is 1-methoximinoethyl, nitro and/or represents phenylalkenyl having 2 to 4 carbon atoms in the straight-chain or branched alkenyl moiety, it being possible for the phenyl moiety to be in each case monosubstituted to trisubstituted by identical or different substituents consisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and/or cyano.

R 2 particularly preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms, straightchain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, or represents phenyl which may be monosubstituted to trisubstituted by identical or different substituents consisting of fluorine, chlorine, bromine, methyl, ethyl, isopropyl, n-propyl, trichloromethyl, trifluoromethyl, dichloromethyl and/or difluoromethyl, or represents phenylalkyl having 1 to 2 carbon atoms in the alkyl moiety, it being possible for the phenyl moiety to be monosubstituted to trisubstituted by identical or different substituents consisting of fluorine, chlorine, bromine, methyl, ethyl, isopropyl, n-propyl, trichloromethyl, trifluoromethyl, dichloromethyl and/or difluoromethyl.

also particularly preferably represents chlorine bromine.

Le A 30 290-Foreign countries 7 -- or Z also particularly preferably represents a nitrogen or a CH group.

Preferred compounds according to the invention are also addition products of acids and cyclopropyl-halogenoethyl- 1 2 azoles of the formula (I) in which R ' R ' X and Z have the meanings mentioned above as being preferred.

The acids which can be added on preferably include hydrohalic acids such as, for example, hydrochloric acid and hydrobromic acid, especially hydrochloric acid, and also phosphoric acid, nitric acid, sulphuric acid, mono-and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, and sulphonic acids such as, for example, p-toluenesulphonic acid, 115naphthalenedisulphonic acid or camphorsulphonic acid, and, furthermore, saccharin and thiosaccharin as well.

Other preferred substances according to the invention are addition products of salts of metals of main groups 11 to IV and subgroups 1 and 11 and IV to VIII on the Periodic Table of the Elements with cyclopropylhalogenoethyl-azoles 1 2 of the f ormula (1) in which R ' R ' X and Z have the meanings mentioned above as being preferred.

In this context salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred.

Suitable anions of these salts are those derived from acids which lead to physiologically compatible addition products. Particularly preferred among such acids in this connection are the hydrohalic acids such as, for example, hydrochloric acid and hydrobromic acid, and also phosphoric acid, nitric acid and sulphuric acid.

Le A 30 290-Foreign countries a Examples of substances according to the invention which may be mentioned are the cyclopropyl-halogenoethyl-azoles listed in the following table.

Table 1

X 1 57 2 R' C-O-C-R 1 11 U112 1 N z N 0 (1) Le A 30 290-Foreign countries ' 9 - Table 1 (Continuation) r-_ Ri 1 R 2 X z C41-i._n CH3 cl C4H9-t CH3 cl CH2 - C,-,= C,-12 - CH3 cl -C4Rg-n - CH3 cl CH - C4H9 - t -CH3 cl CH -C,-I2-CI-I=CH-C113 CII3 cl N -CH - - 2 C=CH -CH3 cl N -CH3 cl N CE3 cl N C113 cl N -()-CH 3 CH3 cl N cl CH3 cl N cl C 1 CH3 cl N Le A 30 290-Foreign countries - 10._ Table 1 (Continuation) R R2 CH3 -P-F F CH3 OCHF 2 CE3 -C4H._n C2H5 -C4H9-t C2H5 -C4H._n C2H5 C2H5 cl cl cl C2H5 cl -CH2 cl -CC13 cl -CH2 IL- cl X Br N Br N N N N Le A 30 290-Foreign countries Table 1 (Continuation) Ri R 2 X z cl cl N -CH2 cl -CH-0 cl N -CH2 -CHi--CH 2 0-ci - CC13 cl N -CHi--CH2 O-Cl - C2115 Br N -C-F C211S cl N F C2RE cl N -CH2-- 3-F -CH2-0-CH3 C2H5 cl N Le A 30 290-Foreign countries S z Table 1 (Continuation) Ri R 2 X z CH3 cl N -O-CF3 -CH3 cl N -CH2 O-Cl - CH3 cl N -CH 2-0 cl -CH3 cl N -CH 2 cl C113 cl N -CH 2 -0-F F -CH3 cl -CH 2 - 3-F - CH3 cl -CH--O-CH 3 22 Le A 30 290-Foreign countries 13 -- Table 1 (Continuation) R1 - CH3 -CH2 OCHF 2 - CE3 -CH20-CF, -CH2-P CE3 C17 3 -C113 -CH2 O-OCF, -CH cl _ C113 1-0- Uh3 - CH3 -CH 1 --Q UM3 Cl -CH cl - CH3 cl 1 -Q- 3 Cl cl N cl H cl N cl N cl N cl H N Le A 30 290-Foreign countries z f Table 1 (Continuation) R R 2 X CH3 -CH F 1-0 (J113 F CH3 -CH F 1-3- (A13 -CH CH3 - CH3 1 -0- UM3 -CH CF3 - CH3 1-0- UM3 - CE3 cl -CH--p 1 UH 3 OCHF2 -CH--OCF3 - CH3 1 UM3 - C113 -CH2-CH-O-Cl 2 z cl X cl N cl N cl N N cl N cl N Le A 30 290-Foreign countries is -- Table 1 (Continuation) RI R 2 X z -CH27CH2-0-F CH3 cl N CH3 cl N -CH2-CH2-0-CH3 CE3 cl N -CH27CH 2 cl -CH=CH-0 CE3 cl N -CH=CH C113 cl N -CH=CH -0----r-H 3 -CH3 cl N L-ii Le A 30 290-Foreign countries - 16- 1 z Table 1 (Continuation) R1 R2 -7 X z CH3 cl -CH=CH-O-F - CH3 cl -CH=CH-O---X--F3 -CH=CHO__OCF3 - CH3 cl - CH3 cl -CH=CH-P OCHF2 X N N N Using 3-(2-chlorobenzyl)-3-(1,2,4-triazol-l-yl-methyl)-2oxaspiro[2. 21pentane and acetyl chloride as starting materials and calcium oxide as acid-binding agent, the course of the process according to the invention can be illustrated with the following equation:

Le A 30 290-Foreign countries, - 17--- cl 0 -f '<1 O-CH 2 CH2 1 N, N N 1' + CHS-C-Cl 11 CaO z v cl CF1i- C- O-C-CH3 2 N ', N N 11 cl 0 A general definition of the oxiranes required as starting materials f or carrying out the process according to the invention is given by the formula (11). In this formula R1 and Z preferably have those meanings which have already been given as being preferred for these radicals in connection with the description of the substances of the formula (1) according to the invention.

Examples of oxiranes of the formula (11) which may be mentioned are the substances listed in the following Table 2.

Le A 30 290-Foreign countries z - 18 - Table 2

0 R 1 CH2 1 N 11 z Li N 1 Ri z -C4H.-n N -C4Eg-t N -CH2-CE=CE2 N -C4H._n CH -C4H9-t CH -CH2-CH=CH-CH3 N - CH2 - c ECH N CH3 cl Le A 30 290-Foreign countries ' - 19- Table 2 (Continuation) 11 1 -P-Cl cl N --0-F N -P-F F X --p OCHF2 N N -O-CF3 N - -0- cl 2 N Le A 30 290-Foreign countries - 20 - z Table 2 (Continuation) 1 RI 1z N -CH2 cl N -CH2_. 3- cl N --0-F -CH2 F N -CH2-- 3- F N -CH2--O-CH3 -CH 2 p N OCHF2 N CH27-0-CF3 1 Le A 30 290-Foreign countries - - 21 Table 2 (Continuation) -CH2--p CF3 N -CH2-0-OCF3 N -CH cl 1-0- f.;p13 m -CH-- 1 - Uri p 3 Cl K -CH cl 1;ti-p 3 cl N -CH F 1 -0- L;ri, X -CH F 1-3- c N Le A 30 290-Foreign countries - 22 1 Table 2 (Continuation) -CH CH3 1 -C- um 3 -CH CF3 1-0- UP13 N -CH --p 1 CH3 OCHF 2 m -CH OCF3 1-0- U1 3 m -CHi-CH 2-0-cl N Le A 30 290-Foreign countries 23 Table 2 (Continuation) 1 R 1 1 z -1 -CHI---CH 2-0- F X -CH,p-CH2 O-CH3 X CH:p-CH 2 X ---p cl -CH=CH-0 N -CH=CH-C-Cl N -CH=CH -0-CH3 N i i i i Le A 30 290-Foreign countries Table 2 (Continuation) 1 RI 1 z1 -CH=CH-O-F N -CH=CH-O-CF3 X -CH=CH -3-OCF3 X -CH=CH-P OCHF 2 N Le A 30 290-Foreign countries - 25 The oxiranes of the formula (11) have not been disclosed hitherto. They can be prepared in that cyclopropyl-hydroxyethyl-azoles of the formula OH 1 R' C C] 1 UM2 1 C N, z N 11 (IV) in which R1 and Z have the meanings given above, are reacted in the presence of strong bases and in the presence of a diluent.

using 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-2-hydroxy3-(1,2,4triazol-lyl) -propane as starting material and potassium tert-butylate as strong base, the course of the process for the preparation of oxiranes of the formula (11) can be illustrated with the following equation:

cl OH 1 SZcj KOC(CH CH----C d- 1 -HCI cl 0 CH2-fM CH2 1 N, N N 1' UM2 1 N C ' ', N N 11 Le A 30 290-Foreign countries - 26 - A general definition of the cyclopropyl-hydroxyethyl-azoles required as starting materials for the preparation of oxiranes of the formula (II) is given by the formula (IV). In this formula R1 and Z preferably have those meanings which have already been mentioned as being preferred for these radicals in connection with the description of the substances of the formula (1) according to the invention.

The'cyclopropyl-hydroxyethyl-azoles of the formula (IV) are known or can be prepared by methods which are known in principle (cf. EP-A 0 180 136, EP-A 0 297 345, EP-A 0 297 383, EP-A 0 298 332, EP-A 0 440 949 and EP-A 0 470 436).

Suitable bases for carrying out the process for the preparation of oxiranes of the formula (11) are all conventional strong inorganic and organic bases. Preferred possibilities for use are alkali metal alcoholates such as sodium methylate, sodium ethylate and potassium tertbutylate, and also alkali metal hydrides such as sodium hydride.

Suitable diluents for carrying out the process for the preparation of oxiranes of the formula (II) are all inert organic solvents which are customary for such reactions. Preferred possibilities for use are alcohols such as methanol, ethanol, propanol and tert-butanol, and also ethers such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, and, furthermore, aliphatic, cycloaliphatic and aromatic hydrocarbons such as pentane, hexane, cyclohexane, benzene, toluene and xylene.

When carrying out the process for the preparation of oxiranes of the formula (II) the reaction temperatures can be varied within a relatively wide range. The process is in general carried out at temperatures of between VC and 1000C, preferably between 200C and 800C.

Le A 30 290-Foreign countries 1 The process for the preparation of oxiranes of the formula (11) is generally carried out under atmospheric pressure. However, it is also possible to work under elevated or reduced pressure.

To carry out the process for the preparation of oxiranes of the formula (11) requires the use, per mole of cyclopropylhydroxyethyl-azole of the formula (111), of in general from 1 to 1. 5 equivalents of strong base. The product is worked up by conventional methods. The general procedure is to wash the reaction mixture with water, if desired after having diluted it beforehand with an organic solvent whose miscibility with water is poor, to dry and concentrate the organic phase and if desired to free the product which remains from any impurities which may be present, by conventional methods such as, for example, by chromatography.

A general definition of the acyl halides which are also required as starting materials for carrying out the process according to the invention for the preparation of cyclopropyl-halogenoethyl-azoles of the formula (1) is given by the formula (111). In this formula R 2 and X preferably have those meanings which have already been mentioned as being preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention.

The acyl halides of the formula (III) are known or can be prepared by known methods.

Acid-binding agents which are suitable for carrying out the process according to the invention are weak bases. Preferred possibilities for use are alkali metal carbonates and hydrogen carbonates, such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, and also alkaline earth metal Le A 30 290-Foreign countries - 28 - 1 oxides such as calcium oxide, and, furthermore, ammonium carbonate or ammonium hydrogen carbonate, and also tertiary amines such as triethylamine and pyridine.

Suitable diluents for carrying out the process according to the invention are all conventional apolar organic solvents. Preferred possibilities for use are aliphatic, cycloaliphatic or aromatic hydrocarbons such as pentane, hexane, cyclohexane, benzene, toluene and xylene, and also ethers such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, and, furthermore, halogenated hydrocarbons such as dichloromethane, as well. Where the acyl halide of formula (Ill) is a liquid component, it may function simultaneously as diluent provided it is employed in a sufficient excess.

When carrying out the process according to the invention the reaction temperatures can be varied within a relatively wide range. The process is in general carried out at temperatures of between OOC and 600C, preferably between 10C and 301C.

The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to work under elevated or reduced pressure.

To carry out the process according to the invention requires the use, per mole of oxirane of the formula (11), of in general from 1 to 2 mol, or else a larger excess, of acyl halide of the formula (Ill) and from 1 to 2 equivalents of acid-binding agent. The product is worked up by conventional methods. The general procedure is to wash the reaction mixture with water, if desired after having diluted it beforehand with an organic solvent whose miscibility with water is low, if desired in the presence of an alkali metal base, to dry and concentrate the organic phase and, if desired, to free the product which remains Le A 30 290-Foreign countries - 29 - from any impurities which may be present, by conventional methods, for example by chromatography.

The cyclopropyl-halogenoethyl-azoles of the formula (1) according to the invention can be converted into acid addition salts or metal salt complexes.

To prepare acid addition salts of the compounds of the formula (1), suitable acids are preferably those acids which have already been mentioned as being preferred in connection with the description of the acid addition salts according to the invention.

The acid addition salts of the compounds of the formula (1) can be obtained in a simple manner by conventional methods of forming salts, for example by dissolving a compound of the formula (1) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and can be isolated in a known manner, for example by filtration, and purified if desired by washing with an inert organic solvent.

For the preparation of metal salt complexes of the compounds of formula (1), suitable salts of metals are preferably those metal salts which have already been mentioned as being preferred in connection with the description of the metal salt complexes according to the invention.

The metal salt complexes of the compounds of the formula (I) can be obtained in a simple manner by conventional methods, for example by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to compounds of the formula (1). Metal salt complexes can be isolated in a known manner, for example by filtration, and can be purified if desired by recrystallization.

Le A 30 290-Foreign countries - 30 - The active compounds according to the:Invention have a strong microbicidal action and can be employed as fungicides.

Fungicides in plant protection are employed for combating Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Some causative organisms of fungal and bacterial diseases which come 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 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. 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; (conidia form: Drechslera, syn:

Helminthosporium); Cochliobolus species, such as Cochliobolus sativus; (conidia 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; Le A 30 290-Foreign countries - 31 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 and Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.

The good toleration, by plants, of the active compounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.

The active compounds according to the invention are particularly suitable for combating cereal diseases such as Erysiphe, Leptosphaeria and Fusarium, and for combating Plasmopara, Venturia and Podosphaera in fruit growing, viticulture and vegetable growing. They can also be employed against rice diseases such as pyricularia oryzae, and additionally possess a good and broad in vitro action.

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 capsules in polymeric substances and in coating' compositions for seeds, as well as UW formulations.

These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents, and/or foam-forming agents. In the case of the use of water as an extender, organic solvents such as alcohols Le A 30 290-Foreign countries - 32 can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkyInaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water. By liquefied gaseous extenders or carriers are meant liquids which are gaseous at ambient temperature and under atmospheric pressure, for example aerosol propellants, such as halogenated hydrocarbons such as butane, propane, nitrogen and carbon dioxide. As solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silicic acid, alumina and silicates. As solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks. As emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis products. As dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or Le A 30 290-Foreign countries 33 - latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper. cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%..

The active compounds according to the invention can be present in the formulations as a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order for example to widen the spectrum of action or to prevent the buildup of resistance. In many cases, synergistic effects are obtained.

Examples of suitable subtances for the mixtures are the following compounds.

Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 21,61-dibromo2-methyl-41-trifluoromethoxy-41-trifluoromethyl-1,3-thiazole-5carboxanilide; 2,6-dichloro-N-(4-trifluoromethylbenzyl)benzamide; (E)-2methoximino-N-methyl-2(2-phenoxyphenyl)-acetamide; 8-hydroxyquinoline sulphate; methyl (E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]phenyl}-3methoxyacrylate; methyl (E)-methoximino[alpha-(otolyloxy) -o-tolyll acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole, Le A 30 290-Foreign countries - 34 1 benalaxyl, bitertanol, buthiobate, calcium polysulphide, captafol, captan, carbendazim, carboxin, quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram, dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine, drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetylaluminium, fthalide, fuberidazole, furalaxyl, furmecyclox, guazatine, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione, isoprothiolane, kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine- copper and Bordeaux mixture, mancopper. mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxycarboxin, pefurazoate, penconazole, pencycuronf phosdiphen, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene (PCNB), sulphur and sulphur preparations, benodanil, benomyl, binapacryl, biphenyl ' blasticidin-S, bromuconazole, bupirimate.

Le A 30 290-Foreign countries - 35 tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclophos -methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, validamycin A, vinclozolin, zineb, ziram.

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furanecarboxylic acid, oxytetracyclin, probenazole, streptomycin, teclof talam, copper sulphate and other copper preparations.

Insecticides/Acaricides/Rematicides:

abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin, Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap, beta-cyf luthrin, bif enthrin, BPMC, brof enprox, bromophos Ai, bufencarb, buprofezin, butocarboxin, butylpyridaben, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, CGA 157 419, CGA 184 699, chloethocarb, chlorethoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton-M, demeton-S, demeton-S-methyl, diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton, edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox, ethoprophos, etrimphos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, Le A 30 290Foreign countries 36 fluazinam, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathiocarb, ECK, heptenophos, hexaflumuron, hexythiazox, imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion, ivemectin, lambda-cyhalothrin, lufenuron, malathion, mecarbam, mervinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled, NC 184, NI 25, nitenpyram, omethoate, oxamyl, oxydemethon M, oxydeprofos, parathion A, parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, phosphamdon, phoxim, pirimicarb, pirimiphos M, pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozin, pyrachlophos, pyradaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen, quinalphos, RE 5992, salithion, sebufos, silafluofen, sulfotep, sulprofos, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox, thlomethon, thionazin, thuringiensin, tralomethrin, triarathen, triazophos, triazuron, trichlorfon, triflumuron, trimethacarb, vamidothion, XMC, xylylcarb, zetamethrin.

A mixture with other known active compounds such as herbicides, or with fertilizers and growth regulators, is also possible.

The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They Le A 30 290-Poreign countries 37 - are used in the customary manner, for example by watering, spraying, atomizing, scattering, dusting, foaming, brushing on and the like. It is furthermore possible to apply the active compounds by the ultra-low volume method or to inject the active compound formulation or the active compound itself into the soil. The seeds of the plants can also be treated.

In the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, between 1 and 0.0001% by weight, preferably between 0.5 and 0. 001% by weight.

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

For the treatment of soil, active compound concentrations of 0. 00001 to 0. 1% by weight, pref erably 0. 0001 to 0. 02% by weight, are required at the place of action.

The preparation and the use of active compounds according to the invention are illustrated by the following examples.

Le A 30 290-Foreign countries 38 Preparation Examples Exam.ple 1 cl cl 1 S7 l-CHz--c O-C-CH 1 UM2 U 1 N r, ', N N 11 11 3 A mixture of 1.38 g (5 mmol) of 3-(2-chlorobenzyl)-3(1,2,4-triazol-l-ylmethyl)-2-oxa-spiro[2.2]pentane, 1 g of calcium oxide and 10 ml of acetyl chloride is stirred at 2VC for 47 hours. The reaction mixture is then concentrated under reduced pressure. The residue which remains is taken up in ethyl acetate, and the solution formed is washed with saturated aqueous sodium carbonate solution. The organic phase is dried over sodium sulphate and concentrated under reduced pressure. In this way 1.3 g (74 % of theory) of 2- (1-acetoxycyclopropyl) -2-chloro-l- (2chlorophenyl)-3-(1, 2,4-triazol-l-yl)-propane are obtained in the form of a solid substance of melting point 1331340C.

1H-NMR spectrum (200 MHz, CDC13. TMS):

(ppm) 0.8-1.2 (m, 4H); 2.15 (s, 3H); 3.5 (AB, 2E1); 4.6 (AB, 2H); 7.2-7.5 (m, 4H); 7.95 (s, 1H); 8.3 (s, 1H) Le A 30 290-Foreign countries -39 1 Preparation of starting substances Example 2 cl / 0 \ ",/CH2 CH-C -C", 1 6_ 1 CH2 k 1;m 2 N r, ' N N 11 A mixture of 3.12 g (10 mmol) of 2(1-chlorocyclopropyl) -l(2- chlorophenyl) -2-hydroxy-3(1,2,4-triazol-l-yl) -propane, 1.12 g (10 mmol) of potassium tert-butylate and 50 mI, of absolute tert-butanol is stirred at 600C for 25 hours. The reaction mixture is then diluted with ethyl acetate and washed several times with water. The organic phase is dried over sodium sulphate and concentrated under reduced pressure. 3.29 g of a crude product are obtained which is chromatographed over 300 g of silica gel using ethyl acetate as eluent. After the concentration of the eluate, 1.3 g (47 % of theory) of 3-(2-chlorobenzyl)-3-(1,2,4triazol- l- yl -methyl) -2-oxa-spiro [2.21 -pentane are obtained in the form of an oil.

1H-NMR spectrum (200 MHz, CDC13, TMS):

0.7-0.95 (m, 4W; 3.3 (s, 2H); 4.55 (AB, 2H); 7.2-7.4 (m, 4H); 7.9 (s, 11-1); 8.1 (s, 1H) ppm GC/MS (Ci): 2 7 6 (M + H', 10 0 %) Le A 30 290-Foreign countries - 40 Examnle 3 0 CH CH2 =CH-CHi--C-CH--C C 1 J1 1 ' CH 2 CH2 CH2 1 C N, N N 11 (11-2) A mixture of 1.34 g (5 ranol) of 6(1-chlorocyclopropyl) -6hydroxy-4methylene-7-(1,2,4-triazol-l-yl)-1-heptene, 0.56 g (5 mmol) of potassium tert-butylate and 30 mI, of absolute tert-butanol is stirred at 600C for 22 hours. The reaction mixture is then diluted with ethyl acetate and washed several times with water. The organic phase is dried over sodium sulphate and concentrated under reduced pressure. 1.1 g of a crude product are obtained which is chromatographed over 300 g of silica gel using ethyl acetate as eluent. After the concentration of the eluate, 0.8 g (70 % of theory) of 3-(2-methylene-pent-4-enyl)-3(1,2,4-triazol-l-ylmethyl)-2-oxa-spiro[2.2]pen tane isob- tained in the form of an oil.

1H-NMR spectrum (200 MHz, MC1.r TMS):

8 (Ppm) 0.8-1.1 (m, 4H); 2.45 (AB, 210 2.7 (AB, 2H); 4.55 (s, 2W; 5.0 (m, 4H); 5.8 (m, 1H); 7.95 (s, 1II); 8.15 (s, 1II) GC/MS (Ci): 232 (m + H', 100 %) Le A 30 290-Foreign countries - 41 - Example 4 / 0 \ /CH 2 C-CH----C,-C", 1 11 1 CH2 CH2 CH2 1 N, 1 N 9 (11-3) A mixture of 1.52 g (5 mmol) of 4-(1-chlorocyclopropyl)-4hydroxy-2-phenylS-(1,2,4-triazol-l-yl)1-pentene, 0.67 g (6 mmol) of potassium tertbutylate and 50 ml of absolute tetrahydrofuran is stirred at 400C for 5 hours. The reaction mixture is then diluted with ethyl acetate and washed several times with saturated aqueous sodium carbonate solution. The organic phase is dried over sodium sulphate and concentrated under reduced pressure. 1.3 g of a crude product are obtained which is chromatographed over 200 g of silica gel using ethyl acetate as eluent. After the concentration of the eluate, 0.5 g (37 % of theory) of 3- (2 - phenyl -prop- 1-en-3 -yl) -3- (1,2,4 - triazol - l-yl -methyl) 2-oxaspiro[2.2]pentane is obtained in the form of an oil.

GCIMS (Ci) : 2 6 8 (M + IT, 10 0 %) Le A 30 290-Foreign countries - 42 1 Ex=ple 5 / 0 CH2 CHS-C-CHi-C C", 1 11 1 CH2 CH 2 CH2 1 N l ' N N 11 (11-4) The compound of the formula (11-4) is also prepared by the method indicated in Example 4. The substance is obtained in the form of an oil.

GC/MS (Ci):

206 (M + W, 100 %) Le A 30 290-Foreign countries 43 - Use examples

Example A

Erysiphe test (barley)/protective 9 Solvent: 10 parts by weight of H-methyl-pyrrolidone Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether TO produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the application rate indicated.

After the spray coating has dried on, the plants are dusted with spores of Erysiphe graminis f.sp. hordei.

The plants are placed in a greenhouse at a temperature of about 20'C and a relative atmospheric humidity of about 80%, in order to promote the development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, at an application rate of 250 g/ha, the compound (I-1) according to the invention exhibits a degree of action of 100 %.

Le A 30 290-Foreign countries - 44 Exami)1e B Leptosphaeria nodorum test (wheat)/protective Solvent: 10 parts by weight of X-methyl-pyrrolidone Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is-mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the application rate indicated.

After the spray coating has dried on, the plants are sprayed with a spore suspension of Leptosphaeria nodorum. The plants remain for 48 hours in an incubation cabin at 200C and 100% relative atmospheric humidity.

The plants are placed in a greenhouse at a temperature of about 150C and a relative atmospheric humidity of about 80%.

Evaluation is carried out 10 days after the inoculation.

In this test, at an application rate of 250 g/ha, the compound (1-1) according to the invention exhibits a degree of action of 100 %.

Le A 30 290-Foreign countries - 45 It will of course be understood that the present invention has been described above purely by way of example, and that modifications of detail can be made within the scope of this invention.

Claims (1)

1. Patent Claims

   Cyclopropyl-halogenoethyl-azoles of the formula X 1 - 1 17 2 R c O-C-R 1 H UMZ 0 1 N C z N in which (I) R1 represents alkyl, alkenyl, alkinyl, optionally alkyl-substituted cycloalkyl, optionally substituted aryl, optionally substituted aralkyl or optionally substituted aralkenyl, R 2 represents alkyl, halogenoalkyl, optionally substituted aryl or optionally substituted aralkyl, X represents chlorine or bromine and Z represents a nitrogen atom or a CII group, and their acid addition salts and metal salt complexes.

   2.

   Cyclopropyl-halogenoethyl-azoles of the formula (1) according to Claim 1, in which RI represents straight-chain or branched alkyl havinpr 1 to 8 carbon atoms, straight-chain or branched Le A 30 290-Foreign countries alkenyl having 2 to 8 carbon atoms, straight-chain or branched alkinyl having 2 to 8 carbon atoms, or represents cycloalkyl having 3 to 7 carbon atoms, it being possible for each of these cycloalkyl radicals to be monosubstituted to trisubstituted by identical or different substituents consisting of alkyl having 1 to 4 carbon atoms, or represents phenyl which may be monosubstituted to trisubstituted by identical or different substituents consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or dif f erent halogen atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and/or cyano, or represents phenylalkyl having 1 to 4 carbon atoms in the straight-chain or branched alkyl-moiety, it being possible for the phenyl moiety to be in each case monosubstituted to trisubstituted by identical or different substituents consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to identical or different halogen atoms, halogeno- Le A 30 290-Foreign countries - 48 - 9 F alkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and/or cyano, or represents phenylalkenyl having 2 to 4 carbon atoms in the straight-chain or branched alkenyl moiety, it being possible for the phenyl moiety to be in each case monosubstituted to trisubstituted by identical or different substituents consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitro and/or cyanof, R 2 represents straight-chain or branched alkyl having 1 to 6 carbon atoms, staight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms, or represents phenyl which may be monosubstituted to trisubstituted by identical or different substituents consisting of halogen, alkyl having 1 to 4 carbon atoms and/or halogenoalkyl having 1 to 4 Le A 30 290-Foreign countries carbon atoms and 1 to 5 identical or different halogen atoms, or represents phenylalkyl having 1 to 4 carbon atoms In the alkyl moiety, it being possible for the phenyl moiety to be monosubstituted to trisubstituted by identical or different substituents consisting of halogen, alkyl having 1 to 4 carbon atoms and/or halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, X represents chlorine or bromine, and Z represents nitrogen or a CII group.

   Process for the preparation of cyclopropyl-halogenoethyl-azoles of the formula X 1 'RE7 2 R c O-C-R 1 11 CH2 1 N , z N 1' in which (1) R1 represents alkyl, alkenyl, alkinyl, optionally alkyl-substituted cycloalkyl, optionally substituted aryl, optionally substituted aralkyl or optionally substituted aralkenyl, Le A 30 290-Foreign countries J 7 R 2 represents alkyl, halogenoalkyl, optionally substituted aryl or optionally substituted aralkyl, X represents chlorine or bromine and Z represents a nitrogen atom or a CH group, and their acid addition salts and metal salt complexes, characterized in that oxiranes of the formula 0 R CH 2 1 N ' ', Z in which (11) RI and Z have the meanings given above, are reacted with acyl halides of the formula R 2_ C-X 11 0 in which (111) R 2 and X have the meanings given above, in the presence of an acid-binding agent and optionally in the presence of a diluent Le A 30 290-Foreign countries e followed optionally by the addition of an acid or a metal salt onto the compounds of formula (I) obtained in this way.

   4. Fungicidal compositions characterized in that they contain at least one cyclopropyl-halogenoethyl-azole of the formula (1) according to Claim 1 and/or an acid addition salt or metal salt complex of a cyclopropylhalogenoethyl-azole of the formula (1).

   Use of cyclopropyl-halogenoethyl-azoles of the formula (1) according to Claim 1 and/or of their acid addition salts and metal salt complexes for combating fungi.

   6. Method of combating fungi, characterized in that cyclopropylhalogenoethyl-azoles of the formula (1) according to Claim 1 and/or their acid addition salts and metal salt complexes are applied to the fungi andlor their habitat.

   Process for the preparation of fungicidal compositions, characterized in that cyclopropyl-halogenoethyl-azoles of the formula (1) according to Claim 1 and/or their acid addition salts or metal salt complexes are mixed with extenders and/or surfaceactive agents.

   8. Cyclopropyl-halogenoethyl-azoles according to Claim 1, as hereinbefore specifically identified.

   g. Process for the preparation of cyclopropylhalogenoethyl-azoles according to Claim 1, substantially as hereinbefore specifically described in Example 1.

   Le A 30-290-Foreicrn countries 11 10. Cyclopropyl-halogenoethyl-azoles according to Claim 1, whenever produced by the process of Claim 9.

   Method according to Claim 6, in which a cyclopropylhalogenoethyl-azole according to claim 8 or 10 is used.

   12. Process according to Claim 7, in which the cyclopropylhalogenoethylazole is a compound according to Claim 8 or 10.

   LeA 30 290 - Foreign Countries 53 -