WO1994029281A1

WO1994029281A1 - Cyclobutylazoles

Info

Publication number: WO1994029281A1
Application number: PCT/EP1994/001692
Authority: WO
Inventors: Hans-Ludwig Elbe; Ralf Tiemann; Stefan Dutzmann; Heinz-Wilhelm Dehne; Gerd Hänssler
Original assignee: Bayer Aktiengesellschaft
Priority date: 1993-06-07
Filing date: 1994-05-25
Publication date: 1994-12-22
Also published as: AU6971594A; DE4318916A1; EP0702676A1; JPH08511010A

Abstract

The invention concerns cyclobutylazoles of formula (I) in which R is optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl or aryl, X is a nitrogen atom or CH group and Z is a carbonyl or -CH(OH)- group, as well as their acid addition salts and metal-salts complexes. The invention also concerns a method of preparing such compounds and their use as pest-control agents for the protection of plants and materials.

Description

Cyclobutylazole

The invention relates to new cyclobutylazoles, a process for their preparation and their use as pesticides in crop protection and in the protective material.

It is already known that numerous azole derivatives have fungicidal properties (cf. EP-OS 0 054 865). For example, 2,2-dimethyl-1- (4-methylphenyl) -4- (1,2,4-triazol-l-yl) -heptan-3-one and 1- (4- Use chlorphenyl) -2,2-dimethyl-4- (l, 2,4-triazol-l-yl) -heptan-3-one to combat fungi. However, the action of these substances, in particular at low concentrations, is not entirely satisfactory in all areas of application.

There were now new cyclobutylazoles of the formula

in which

R represents in each case optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or aryl,

represents a nitrogen atom or a -CH group and Z represents a carbonyl group or a -CH (OH) group,

as well as their acid addition salts and metal salt complexes.

Those substances according to the invention in which Z represents a CH (OH) group contain at least one asymmetrically substituted carbon atom. They can therefore occur in optical isomer forms. The present invention relates both to the individual isomers and to their mixtures.

It has also been found that cyclobutylazoles of the formula (I) and their acid addition salts and metal salt complexes are obtained when azolylmethyl ketones of the formula

in which

R and X have the meanings given above,

with 1,3-dihalopropane compounds of the formula

Hal-CH ₂ -CH ₂ -CH ₂ -Hal (III)

in which

Shark represents halogen,

if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder and if appropriate the resulting cyclobutylazoles of the formula R

in which

R and X have the meanings given above,

reacted with a reducing agent, if appropriate in the presence of a diluent, and, if appropriate, an acid or a metal salt is added to the compounds of the formula (I) obtained in this way.

Finally, it was found that the new cyclobutylazoles of the formula (I) and their acid addition salts and metal salt complexes are very suitable for pest control and can be used both in crop protection and in material protection.

Surprisingly, the substances according to the invention have a much better fungicidal activity than 2,2-dimethyl-1- (4-methylphenyl) -4- (1,2,4-triazol-1-yl) -heptan-3-one and the l- (4-chlorophenyl) -2,2-dimethyl-4- (l, 2,4-triazol-l-yl) -heptan-3-one, which are constitutionally similar, known active substances of the same direction of action.

In addition, the new cyclobutylazoles of formula (I) are also interesting intermediates for the production of other crop protection agents. Thus, let those substances of the formula (I), in which a keto group is present, will be converted by ^"Uiaβetzung on the carbonyl function in oximes, oxime ethers, hydrazones and ketals. Those compounds of the formula (I) containing a CH (OH) -Group can be converted into corresponding ether, acyl or carbamoyl derivatives by reaction on the hydroxy group. The cyclobutylazoles according to the invention are generally defined by the formula (I).

X represents a nitrogen atom or a CH group.

Z represents a carbonyl group or a CH (OH) group.

R preferably represents straight-chain or branched alkyl having 1 to 12

Carbon atoms, straight-chain or branched alkenyl with 2 to 12 carbon atoms, straight-chain or branched alkynyl with 2 to 12 carbon atoms, straight-chain or branched alkoxyalkyl with 1 to 8 carbon atoms in the alkoxy part and 1 to 8 carbon atoms in the alkyl part, straight-chain or branched alkylthioalkyl with 1 to 8

Carbon atoms in the alkylthio part and 1 to 8 carbon atoms in the alkyl part, straight-chain or branched alkylsulfinylalkyl with 1 to 8 carbon atoms in the alkyl sulfinyl part and 1 to 8 carbon atoms in the alkyl part, straight-chain or branched alkylsulfonylalkyl with 1 to 8 carbon atoms in the alkylsulfonyl part and 1 to 8 carbon atoms in the

Alkyl part, straight-chain or branched alkoximinoalkyl with 1 to 8 carbon atoms in the alkoxy part and 1 to 8 carbon atoms in the alkyl part, straight-chain or branched hydroximinoalkyl with 1 to 8 carbon atoms, straight-chain or branched cyanoalkyl with 1 to 8 carbon atoms in the alkyl part, straight-chain or branched

Haloalkyl with 1 to 8 carbon atoms and 1 to 9 identical or different halogen atoms, straight-chain or branched haloalkoxyalkyl with 1 to 8 carbon atoms in the alkoxy part and 1 to 8 carbon atoms in the alkyl part and with 1 to 9 identical or different halogen atoms, straight-chain or branched halogen alkylthioalkyl with 1 to 8 carbon atoms in the alkylthio part and 1 to 8 carbon atoms in the alkyl part and with 1 to 9 identical or different halogen atoms, straight-chain or branched haloalkylsulfinylalkyl with 1 to 8 carbon atoms in the haloalkyl part and 1 to 8 carbon atoms in the alkyl part and with 1 up to 9 identical or different halogen atoms, straight-chain or branched haloalkylsulfonylalkyl having 1 to 8 carbon atoms in the haloalkyl part and 1 to 8 carbon atoms in the alkyl part and 1 to 9 identical or different halogen atoms, for straight-chain or branched halogeno alkenyl with 2 to 12 carbon atoms and 1 to 9 identical or different halogen atoms, straight-chain or branched halogenoalkynyl with 2 to 12 carbon atoms and 1 to 9 identical or different halogen atoms, for dioxolanylalkyl with 1 to 6 carbon atoms in the straight-chain or branched alkyl part, dithiolanylalkyl with 1 to 6 carbon atoms in the straight-chain or branched alkyl part, dioxanylalkyl with 1 to 6 carbon atoms in the straight-chain or branched alkyl part or for dithianylalkyl with 1 to 6 carbon atoms in the straight-chain or branched alkyl part.

R also preferably represents cycloalkylalkyl optionally having from one to five times, identical or different, substituted by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms, or optionally having from one to five times, identical or different by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms, substituted cycloalkylalkyl having 3 to 7 carbon atoms in the cycloalkyl part and 1 to 8 carbon atoms in the straight-chain or branched alkyl part.

R further preferably represents aryl having 6 to 10 carbon atoms,

Arylalkyl with 6 to 10 carbon atoms in the aryl part and 1 to 8 carbon atoms in the straight-chain or branched alkyl part, aryloxyalkyl with 6 to 10 carbon atoms in the aryl part and 1 to 8 carbon atoms in the straight-chain or branched alkyl part, arylthioalkyl with 6 to 10 carbon atoms in the aryl part and 1 up to 8 carbon atoms in the straight-chain or branched alkyl part, arylsulfinylalkyl with 6 to 10 carbon atoms in the aryl part and 1 to 8 carbon atoms in the straight-chain or branched alkyl part, arylsulfonylalkyl with 6 to 10 carbon atoms in the aryl part and 1 to 8 carbon atoms in the straight-chain or branched alkyl part , Aralkyloxyalkyl with 6 to 10 carbon atoms in the aryl part and in each case 1 to 8 carbon atoms in the individual straight-chain or branched alkyl parts, aralkylthioalkyl with 6 to 10 carbon atoms in the aryl part and in each case 1 to 8 carbon atoms in the individual straight-chain or branched alkyl parts, aralkylsulfinylalkyl having 6 to 10 carbon atoms in the aryl part and each having 1 to 8 carbon atoms in the individual straight-chain or branched alkyl parts or aralkylsulfonylalkyl having 6 to 10 carbon atoms in the aryl part and each having 1 to 8 carbon atoms in the individual straight-chain or branched alkyl parts, where each of the abovementioned radicals in the aryl part can be monosubstituted to triple, identical or differently substituted by halogen, cyano, nitro, straight-chain or branched alkyl, straight-chain or branched alkoxy, straight-chain or branched alkylthio, straight-chain or branched alkylsulfinyl or straight-chain or branched alkylsulfonyl each having 1 to 4 carbon atoms, straight-chain or branched haloalkyl, straight-chain or branched halogenoalkoxy, straight-chain or branched haloalkylthio, straight-chain or branched haloalkylsulf inyl or straight-chain or branched haloalkylsulfonyl each having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, straight-chain or branched alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy part, straight-chain or branched alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy part and 1 up to 4 carbon atoms in the alkyl part, optionally one to four times, identical or different by halogen-substituted dioxyalkylene with 1 to 3 carbon atoms, double-linked alkylidene with 3 to 8 carbon atoms, cycloalkyl with 3 to 7 carbon atoms, optionally single to triple, similar or different phenyl substituted by halogen and / or alkyl having 1 to 4 carbon atoms and / or optionally mono- to triple, identical or different by phenoxy substituted by halogen and / or alkyl having 1 to 4 carbon atoms.

particularly 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 alkynyl having 2 to 8

Carbon atoms, straight-chain or branched alkoxyalkyl with 1 to 6 carbon atoms in the alkoxy part and 1 to 6 carbon atoms in the alkyl part, straight-chain or branched alkylthioalkyl with 1 to 6 carbon atoms in the alkylthio part and 1 to 6 carbon atoms in the alkyl part, straight-chain or branched alkylsulfinylalkyl with 1 to 6 carbon atoms in the alkylsulfinyl part and 1 to 6 carbon atoms in the alkyl part, straight-chain or branched alkylsulfonylalkyl with 1 to 6 carbon atoms in the alkylsulfonyl part and 1 to 6 carbon atoms in the alkyl part, straight-chain or branched alkoximinoalkyl with 1 to 6 carbon atoms in the alkoxy part and 1 to 6 carbon atoms in the alkyl part, straight-chain or branched hydroximinoalkyl with 1 to 6 carbon atoms, straight-chain or branched cyanoalkyl with 1 to 6 carbon atoms in the alkyl part, straight-chain or branched haloalkyl 1 to 6 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, straight-chain or branched haloalkoxyalkyl with 1 to 6 carbon atoms in the alkoxy part and 1 to 6 carbon atoms in the alkyl part and 1 to 5 fluorine, chlorine and / or bromine atoms, straight-chain or branched haloalkylthioalkyl with 1 to 6 carbons toffatomen in the haloalkylthio part and 1 to 6 carbon atoms in the alkyl part and 1 to 5

Fluorine, chlorine and / or bromine atoms, straight-chain or branched haloalkylsulfinylalkyl having 1 to 6 carbon atoms in the haloalkyl part and 1 to 6 carbon atoms in the alkyl part and 1 to 5 fluorine, chlorine and / or bromine atoms, straight-chain or branched haloalkylsulfonylalkyl with 1 to 6 carbon atoms in the haloalkyl part and

1 to 6 carbon atoms in the alkyl part and 1 to 5 fluorine, chlorine and / or bromine atoms, for straight-chain or branched haloalkenyl with 3 to 8 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, straight-chain or branched haloalkynyl with 3 up to 8 carbon atoms and 1 to 5 fluorine, chlorine and / or bromine atoms, for dioxolanyl-alkyl with 1 to 4 carbon atoms in the straight-chain or branched alkyl part, dithiolanylalkyl with 1 to 4 carbon atoms in the straight-chain or branched alkyl part, dioxanylalkyl with 1 to 4 Carbon atoms in the straight-chain or branched alkyl part or for dithianylalkyl having 1 to 4 carbon atoms in the straight-chain or branched alkyl part.

furthermore particularly preferably represents cycloalkyl having 3 to 6 carbon atoms substituted by fluorine, chlorine, bromine and / or straight-chain or branched alkyl having 1 to 3 carbon atoms, the same or different. R furthermore particularly preferably represents cycloalkylalkyl having 3 to 6

Carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the straight-chain or branched alkyl part, where the cycloalkyl part can be monosubstituted to triple, identical or differently substituted by fluorine, chlorine, bromine and / or alkyl having 1 to 3 carbon atoms.

R furthermore particularly preferably represents aryl having 6 or 10 carbon atoms,

Arylalkyl with 6 or 10 carbon atoms in the aryl part and 1 to 6 carbon atoms in the straight-chain or branched alkyl part, aryloxyalkyl with 6 or 10 carbon atoms in the aryl part and 1 to 6 carbon atoms in the straight-chain or branched alkyl part, arylthioalkyl with 6 or 10 carbon atoms in the Aryl part and 1 to 6 carbon atoms in the straight-chain or branched alkyl part, arylsulfinylalkyl with 6 or 10 carbon atoms in the aryl part and 1 to 6 carbon atoms in the straight-chain or branched alkyl part, aryl sulfonyl alkyl with 6 or 10 carbon atoms in the aryl part and 1 to 6 carbon atoms in the straight-chain or branched alkyl part, aralkyloxyalkyl with 6 or 10 carbon atoms in the aryl part and in each case 1 to 6 carbon atoms in the individual straight-chain or branched alkyl parts, aralkylthioalkyl with 6 or 10 carbon atoms in the aryl part and in each case 1 to 6 carbon atoms in the individual straight-chain or branched alkyl part s, aralkylsulfynylalkyl with 6 or 10 carbon atoms in the aryl part and in each case 1 to 6 carbon atoms in the individual straight-chain or branched alkyl parts or aralkylsulfonylalkyl with 6 or 10 carbon atoms in the aryl part and in each case 1 to 6 carbon atoms in the individual straight-chain or branched Alkyl parts, each of the aforementioned

The rest in the aryl part can be substituted by up to three times, in the same way or differently

Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, propane -l, 3-diyl, butane-1,4-diyl, pentane-l, 5-diyl, dimethylpropane-l, 3-diyl,

Tetram ethylpropan-l, 3-diyl, dimethylbutane-1,4-diyl, tetramethylbutane-1,4-diyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trifluoromethyl, dichlorofluoromethyl, difluorochloromethyl, difluoromomomethyl, Trichloromethyl, fluoromethyl, difluoromethyl, trifluoroethyl, tetrafluoroethyl, trifluorochloroethyl, pentafluoroethyl, trifluoromethoxy, difluoromethoxy, fluoromethoxy, dichlorofluoromethoxy, difluorochloromethoxy, difluorobluoromethoxy, trichloromethoxy, trifluoromethoxy, trifluoromethyl

Pentachlorethoxy, trifluoromethylthio, difluoromethylthio, fluoromethylthio, difluorochloromethylthio, dichlorofluoromethylthio, difluoroethylthio, difluoro- bromomethylthio, trichloromethylthio, trifluoroethylthio, tetrafluoroethylthio, pentafluoroethylthio, Trifluorchlorethylthio, Trifluordichlorethylthio, penta- chloroethylthio, methylsulphinyl, trifluoromethylsulphinyl, Dichlorfluorme- thylsulfinyl, thylsulfinyl Difluorchlormethylsulfinyl, fluoromethylsulfinyl, Difiuorme-, Methylsulfonyl, trifluoromethylsulfonyl, dichlorofluoromethylsulfonyl, difluorochloromethylsulfonyl, fluoromethylsulfonyl, difluoromethylsulfonyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl, ethoximinoymethyl, difluoromethyl

Tetrafluorodioxyethylene, trifluorodioxyethylene, difluorodioxyethylene, dioxymethylene, dioxyethylene or each optionally mono- to trisubstituted, identically or differently, by methyl, fluorine and / or chlorine-substituted phenyl or phenoxy.

very particularly preferably represents straight-chain or branched alkyl having 1 to 7 carbon atoms, straight-chain or branched alkenyl having 2 to 7 carbon atoms, straight-chain or branched alkynyl having 2 to 7 carbon atoms, straight-chain or branched methoxyalkyl, straight-chain or branched dimethoxyalkyl, straight-chain or branched trimethoxyalkyl, straight-chain or branched methylthioalkyl, straight-chain or branched dimethylthioalkyl, straight-chain or branched trimethylthioalkyl, straight-chain or branched methylsulfinylalkyl, straight-chain or branched methylsulfonylalkyl, straight-chain or branched hydroxyliminoalkyl or straight-chain methoximinoalkyl or straight-chain or branched methoximinoalkyl, straight-chain or branched in each case 3 to 6 carbon atoms in the alkyl part, for straight-chain or branched haloalkyl, straight-chain or branched halomethoxyalkyl, straight-chain or branched haloethoxyal alkyl, each straight-chain or branched halomethylthioalkyl, halomethylsulfite nylalkyl or halomethylsulfonylalkyl each having 1 to 3 fluorine, chlorine and / or bromine atoms and each having 2 to 7 carbon atoms in the alkyl part, and also for straight-chain or branched haloalkenyl or haloalkynyl each having 3 to 7 carbon atoms and 1 to 3 fluorine, chlorine - and / or bromine atoms.

R also very particularly preferably represents dioxolanylalkyl,

Dithiolanylalkyl, dioxanylalkyl or dithianylalkyl each having 1 to 3 carbon atoms in the straight-chain or branched alkyl part

or for cycloalkyl with 3 to 6 which is optionally monosubstituted to trisubstituted, identically or differently, by fluorine, chlorine, bromine and / or methyl

Carbon atoms,

or for cycloalkylalkyl in the cycloalkyl part which is optionally mono- to trisubstituted, identically or differently, by fluorine, chlorine, bromine and / or methyl and has 3 to 6 carbon atoms in the cycloalkyl part and 1 to 3 carbon atoms in the straight-chain or branched alkyl part.

Finally, R very particularly preferably represents phenyl, α-naphthyl or β-naphthyl, where each of these radicals can be substituted once to three times, in the same way or differently

Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthiσ; Ethylthio,

Propane-l, 3-diyl, butane-1,4-diyl, pentane-l, 5-diyl, dimethylpropane-l, 3-diyl, tetram ethylpropane-1, 3-diyl, dimethylbutane-1, 4-diy 1, Tetramethylbutan-1,4-diyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trifluoromethyl, dichlorofluoromethyl, difluorochloromethyl, difluoromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoroethyl, tetrafluoroethyl,

Trifluorochloroethyl, pentafluoroethyl, trifluoromethoxy, difluoromethoxy, fluoromethoxy, dichlorofluoromethoxy, difluorochloromethoxy, difluorobromomethoxy,, trichloromethoxy, trifluorethoxy, tetrafluoroethoxy, pentafluoroethoxy, trifluorochloroethoxy, trifluorochloroethoxy, trifluorochloroethoxy, trifluorochloroethoxy, trifluorochloroethoxy, trifluorochloroethoxy, trifluorochloroethoxy, trifluorochloroethoxy, trifluorochloroethoxy, trifluorochloroethyl, trifluoromethyl Difluorochloromethylthio, dichlorofluoromethylthio, difluoroethylthio, Difiuor- bromomethylthio, trichloromethylthio, trifluoroethylthio, tetrafluoro ethylthio, pentafluoroethylthio, Trifluorchlorethylthio, Trifluordichlorethylthio, penta- chloroethylthio, methylsulphinyl, trifluoromethylsulphinyl, Dichlorfluorme- thylsulfinyl, Difluorchlormethylsulfinyl, fluoromethylsulfinyl, Difluorme- thylsulfinyl, methylsulfonyl, trifluoromethylsulfonyl, sulfonyl Dichlorfluormethyl- , Difluorochloromethylsulfonyl, fluoromethylsulfonyl, difluoromethylsulfonyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl, ethoximinoethyl, difluorodioxymethylene, tetrafluorodioxyethylene, trifluorodioxyethylene or different, dichlorodioxyethylene, difluodioxyethylene, difluodioxyethylene, difluodioxyethylene or difluodioxyethylene, Fluorine and / or chlorine substituted phenyl or phenoxy

and also stands

very particularly preferred for a radical of the formula

- Ar (Y) - CH ₂ -

orin

Ar, Ar ¹ and Ar ² independently of one another represent phenyl, α-naphthyl or β-naphthyl, where each of these aryl radicals can be monosubstituted to trisubstituted, identical or different,

Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, Propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, dimethylpropane-1,3-diyl, tetramethylpropane-1,3-diyl, dimethylbutane-1,4-diyl, tetramethylbu tan- 1,4-diyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trifluoromethyl, dichlorofluoromethyl, difluorochloromethyl, difluorobromomethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoroethyl, tetrafluoroethyl,

Trifluorochloroethyl, pentafluoroethyl, trifluoromethoxy, difluoromethoxy, fluoromethoxy, dichlorofluoromethoxy, difluorochloromethoxy, difluorobromomethoxy, trichloromethoxy, trifluorethoxy, tetrafluorethoxy, pentafluoroethoxy, trifluorochloroethoxy, trifluoromethoxy, trifluoromethyl, trifluoromethyl

Difluorochloromethylthio, dichlorofluoromethylthio, difluoroethylthio, difluoro- bromomethylthio, trichloromethylthio, Trifiuorethylthio, tetrafluoroethyl thio, pentafluoroethylthio, Trifluorchlorethylthio, Trifluordichlorethylthio, penta- chloroethylthio, methylsulphinyl, trifluoromethylsulphinyl, Dichlorfluorme- thylsulfinyl, Difluorchlormethylsulfinyl, fluoromethylsulfinyl, Difluorme- thylsulfinyl, methylsulfonyl, Trifiuormethylsulfonyl, sulfonyl Dichlorfluormethyl- , Difluorchlormethylsulfonyl, fluoromethylsulfonyl, Difluorme- thylsulfonyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, Eth oximinomethyl, methoximinoethyl, ethoximinoethyl, difluorodioxymethylene, tetrafluorodioxyethylene, Trifluordioxyethylen, Difluordioxyethylen, methylene dioxy, dioxyethylene or in each case optionally mono- to trisubstituted by identical or different methyl, Fluorine and / or chlorine substituted phenyl or phenoxy,

Y, Y ¹ and Y ² independently of one another for oxygen, sulfur, sulfinyl, sulfonyl or for one of the groups -CH ₂ -; -O-CH ₂ -; -CH ₂ -O-;

-O-CH ₂ -CH ₂ -; -S (O) _q -CH ₂ -; -CH ₂ -S (O) _r - or -S (O) _s -CH ₂ -CH ₂ -

m, n and p each represent 0 or 1 and

q, r and s each represent a number 0, 1 or 2.

Preferred compounds according to the invention are also addition products of acids and those cyclobutylazoles of the formula (I) in which the substituents tuenten R, X and Z have the meanings that have already been mentioned preferably for these substituents.

The acids that can be added preferably include hydrohalic acids, e.g. Hydrochloric acid and hydrobromic acid, especially hydrochloric acid, also phosphoric acid, nitric acid, sulfuric acid, mono-, bi- and trifunctional carboxylic acids and hydroxycarboxylic acids, such as e.g. Acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, sulfonic acids such as e.g. p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid and saccharin or thiosaccharin.

In addition, preferred substances according to the invention are addition products from salts of metals of the II. To IV. Main and of I. and II. And IV. To VIII. Subgroup of the periodic table of the elements and those cyclobutylazoles of the formula (I) in which R, X and Z have the meanings which have preferably already been mentioned for these substituents.

Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred. Anions of these salts are those which are derived from acids which lead to environmentally compatible addition products. Particularly preferred such acids in this connection are the hydrohalic acids, e.g. hydrochloric acid and hydrobromic acid, nitric acid and sulfuric acid.

If 1 - (4-bromophenyl) -2,2-dimethyl-4- (1, 2,4-triazol-1-yl) = butan-3-one and 1,3-dibromopropane are used as starting materials, the course can be changed of the process according to the invention are illustrated by the following formula:

If 1 - [3 - (4-bromophenyl) -2,2-dimethyl-1-oxo-prop-1-yl] - 1 - (1, 2,4-triazol-l-yl) -cyclobutane is used as Starting material and sodium borohydride as reducing agent, the course of the second stage of the process according to the invention can be illustrated by the following formula:

Formula (II) provides a general definition of the azolyl methyl ketones required as starting compounds for carrying out the process according to the invention. In this formula, R and X preferably represent those meanings which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula (I) according to the invention. The azolyl methyl ketones of the formula (II) are known or can be prepared by processes which are known in principle (cf. EP-OS 0 054 865).

The 1,3-dihalopropane compounds which are further required as starting materials for carrying out the process according to the invention are represented by the formula (III) generally defined. In this formula (III), shark is preferably chlorine or bromine. 1,3-Dihalopropane compounds of the formula (III) are generally known compounds of organic chemistry.

Inert organic solvents are suitable as diluents for carrying out the 1st stage of the process according to the invention. Aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, are preferably usable. Ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides, such as N, N-dimethylformamide, N, N-dimethyl-acetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide or sulfoxides, such as dimethyl sulfoxide.

All conventional inorganic or organic acids are used as acid binders when carrying out the first stage of the process according to the invention

Bases in question. Alkaline earth or alkali metal hydrides are preferably usable,

-hydroxides, -amides, -alcoholates, -acetates, -carbonates or -hydrogencarbonate and

Ammonium compounds, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

The 1st stage of the process according to the invention can optionally also be carried out in a two-phase system, such as water / toluene or water / dichloromethane, if appropriate in the presence of a suitable phase transfer catalyst. Examples of such catalysts are: tetra-butylammonium iodide, tetrabutylammomum bromide, tetrabutylammonium chloride, tributyl-methylphosphonium bromide, trimethyl-Ci ₃ / C ₁₅ -alkylarnmonium chloride, trimethyl-C ₁₃ / C ₁₅ -alkylammonium bromide, dibenzyl-dimethyl-ammonium-ammonium fat, dimethyl-C ₁₂ / C ₁₄ -alkyl-benzylammonium chloride, dimethyl-C ₁₂ / C ₁₄ -alkyl-benzylammonium bromide, tetrabutylammonium hydroxide, triethylbenzylammonium chloride, methyltrioctylammonium chloride, trimethylbenzylammonium chloride, 15-crown-5 or 18-crown-6-crown-6 Tris- [2- (2-methoxyethoxy) ethyl] amine.

The reaction temperatures can be varied over a wide range when carrying out the 1st stage of the process according to the invention. In general, temperatures between 0 ° C and + 150 ° C, preferably at temperatures between 20 ° C and + 120 ° C.

The first stage of the process according to the invention is usually carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

To carry out the first stage of the process according to the invention, 1.0 to 3.0 mol, preferably 1.0 to 1.5 mol, of 1,3-dihalopropane compound of the formula are generally employed per mol of azolyl methyl ketone of the formula (II) (III) and optionally 3.0 to 6.0 mol, preferably 2.0 to 3.0 mol, of an acid binder. The reaction is carried out, worked up and isolated from the reaction products by customary methods.

The second stage of the process according to the invention is carried out in the presence of a suitable reducing agent. As such, customary reducing agents which can be used for carbonyl group reduction are suitable. Complex hydrides such as lithium aluminum hydride or sodium borohydride or also aluminum alcoholates, such as aluminum isopropylate, are preferably used.

Suitable diluents for carrying out the second stage of the process according to the invention are conventional organic solvents, depending on the reducing agent used. Aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, petroleum ether, hexane, cyclohexane, ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; or alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomers ethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

The reaction temperatures can be varied over a wide range when carrying out the second stage of the process according to the invention. In general, depending on the reducing agent used, temperatures between -30 ° C. and + 150 ° C., preferably at temperatures between 0 ° C. and + 100 ° C.

The second stage of the process according to the invention is usually carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

To carry out the second stage of the process according to the invention, 1.0 to 5.0 mol, preferably 1.0 to 2.0 mol, of reducing agent are generally employed per mol of cyclobutylazole of the formula (Ia). The reaction is carried out, worked up and isolated in each case by the reaction products using customary methods.

The cyclobutylazoles of the formula (I) according to the invention can be converted into acid addition salts or metal salt complexes.

For the preparation of acid addition salts of the compounds of formula (I), preference is given to those acids which have already been mentioned as preferred acids in connection with the description of the acid addition salts according to the invention.

The acid addition salts of the compounds of the formula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and in a known manner, for example by filtration, isolated and, if necessary, cleaned by washing with an inert organic solvent. - 15th

For the preparation of metal salt complexes of the compounds of formula (I), preference is given to those salts of metals which have already been mentioned as preferred metal salts in connection with the description of the metal salt complexes according to the invention.

The metal salt complexes of the compounds of formula (I) can be obtained in a simple manner by conventional methods, e.g. by dissolving the metal salt in alcohol, e.g. Ethanol and adding to compounds of formula (I). Metal salt complexes can be prepared in a known manner, e.g. by filtering, isolating and, if necessary, cleaning by recrystallization.

The end products of the formula (I) are purified using customary methods, for example by column chromatography or by recrystallization.

The characterization is carried out using the melting point or, in the case of non-crystallizing compounds, using the refractive index or proton nuclear magnetic resonance spectroscopy (1H-NMR).

The active compounds according to the invention have a strong action against pests and can be used to control unwanted harmful organisms. The active ingredients are suitable for use as crop protection agents, in particular as fungicides in crop protection and in material protection.

Fungicidal agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Some pathogens of fungal diseases which come under the generic names listed above may be mentioned as examples, but not by way of limitation: Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans; Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis; Plasmopara species, such as, for example, Plasmopara viticola; Peronospora species, such as, for example, Peronospora pisi or Peronospora brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea; Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or Pyrenophora graminea (conidial form: Drechslera, synonym: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechslera, synonym: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae; Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum; Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae;

Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases allows treatment of above-ground parts of plants, of propagation stock and seeds and of the soil.

The active compounds according to the invention can be particularly successful in combating diseases in fruit and vegetable cultivation, such as, for example, against the pathogen of apple scab (Venturia inaequalis) or against the pathogen of cucumber mildew (Sphaerotheca fuliginea) or against the pathogen of apple mildew (Podosphaera leucotricha) or against the pathogen of the real vine mildew (Uncinula necator) or for combating Cereal diseases such as, for example, against the causative agent of broken wheat stalk (Pseudocercosporella herpotrichoides) or against the causative agent of powdery mildew (Erysiphe graminis) or against the causative agent of barley mesh spot disease (Pyrenophora teres) or against the causative agent of cotyledon weus (brown spot disease) sativus) or against the pathogen causing brown furs in wheat (Septoria nodorum) or against Fusarium species or for combating rice diseases, such as, for example, against the pathogen causing rice fever disease (Pyricularia oryzae) or against the pathogen causing rice stalk disease (Pellicularia sasakii). In addition, the active compounds according to the invention have good in vitro activity and also show plant growth-regulating activity.

In the protective material, the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.

In the present context, technical materials are to be understood as non-living materials that have been prepared for use in technology. For example, technical materials which are to be protected against microbial change or destruction by active substances according to the invention, adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which are attacked by microorganisms or can be decomposed. In the context of the materials to be protected, parts of production plants, for example cooling water circuits, may also be mentioned which can be impaired by the multiplication of microorganisms. In the context of the present invention, technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids, particularly preferably wood.

Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can break down or change the technical materials. The active compounds according to the invention preferably act against fungi, in particular mold, wood-staining and wood-destroying fungi (Basidiomycetes) and against mucus organisms and algae. For example, microorganisms of the following genera may be mentioned:

Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger, Chaetomium, such as Chaetomium globosum, Coniophora such as Coniophora puetana, Lentinus, such as Lentinus tigrinus, Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor, Aureulomaid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasidasid, Aureobasid Sclerophoma pityophilla, Trichoderma, such as Trichoderma viride, Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonas aeruginosa, Staphylococcus, such as Staphylococcus aureus.

Depending on their respective physical and / or chemical properties, the active compounds can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV Cold and warm mist formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes, or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or Glycol and its ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethyl formamide or dimethyl sulfoxide, as well as water; Liquefied gaseous extenders or carriers mean those liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; Solid carrier materials are suitable: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates; Solid carriers for granules are possible: for example broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; Possible emulsifying and / or foaming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; The following may be used as dispersants: for example lignin sulfite waste liquor and methyl cellulose.

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

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

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

When used in crop protection as such or in their formulations, the active compounds can also be mixed with known fungicides, bactericides,

Acaricides, nematicides or insecticides can be used, for example To broaden the spectrum of activity or to prevent the development of resistance. In some cases, synergistic effects also occur, which means that the effectiveness of the mixtures is higher than the sum of the effectiveness of the individual components.

For example, the following substances can be used as mixing partners.

Fungicides:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4 ^l -trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyano-phenoxy) 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, dichlorophen, diclobutrazole, dicloflomolanidol, dicloflomolanidolol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, dicloflomolanidol, diclofolomidol, dicloflolonidol, dicloflomolonidol, dicloflolomolonidol , Dinocap, Diphenylamine, Dipyrithione, Ditalimfos, Dithianon, Dodine, Drazoxolon, Edifenphos, Epoxyconazole, Ethirimol, Etridiazole,

Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Fuberilafil, Fuberri Furmecyclox, guazatine, hexachlorobenzene, hexaconazole, hymexazole, imazalil, imibenconazole, iminoctadine, Iprobefos (IBP), iprodione, isoprothiolan, kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper oxychloride, copper sulfate mixture , Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol,

Methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil,

Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,

Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin, Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin,

Probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb,

Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon,

Quintozen (PCNB),

Sulfur and sulfur preparations, tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen,

Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon,

Triadimenol, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforin,

Triticonazole,

Validamycin A, vinclozolin, zineb, ziram

Bactericides:

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

Insecticides / acaricides / nematicides:

Abamectin, Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin, Bacillus thuringiensis, Bendiocentyl, Bethrin Bifin, Buthrin Carbob, Benfuracarbens Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 41 9, CGA 1 84699, Chloethocarb, Chl orethoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clofenthrin, Clocenthrinflin, Clocythrinflin, Clocenthrin Flin , 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, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox,

Ethoprophos, Etrimphos,

Fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,

Fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate,

Fipronil, fluazinam, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathiocarb,

HCH, Heptenophos, Hexafiumuron, Hexythiazox,

Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin,

Lamda-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, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos,

Promecarb, Propaphos, Propoxur, Prothiofos, Prothiophos, Prothoat, Pymetrozin,

Pyraclophos, Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen,

Pyriproxyfen,

Quinalphos, RH 5992,

Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,

Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos,

Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox,

Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron, Trichlorfon, Triflumuron, Trimethacarb,

Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin.

A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible. When used in crop protection, the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to prepare the active ingredient or the like Inject active ingredient into the soil yourself. The seeds of the plants can also be treated.

When using the substances according to the invention as fungicides, the application rate can be varied within a substantial range depending on the type of application. The active substance concentrations in the treatment of parts of plants in the use forms are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%. In the seed treatment, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required. When treating the soil, active ingredient concentrations are from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0 , 02% by weight required at the site of action.

The microbicidal agents used to protect industrial materials generally contain the active compounds in an amount of 1 to 95% by weight, preferably 10 to 75% by weight.

When used in the protective material, the application concentrations of active substances according to the invention depend on the type and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimal amount can be determined by test series. In general, the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.

The active compounds according to the invention can also be used in a mixture with other known active compounds when used in material protection. For example, the following active ingredients may be mentioned: benzyl alcohol mono- (poly) hemiformal and other formaldehyde-releasing compounds, benzimide azolyl methyl carbamates, tetramethyl thiuram disulfide, zinc salts of dialkyl dithiocarbamates, 2,4,5,6-tetrachloroisophthalonitrile, thiazolyl benzapto-2-benzoimidazole-benzolidazolido-benzolimidazol-benzapto-benzimidazol-benzapto-benzimidazol-benzapto-benzimidazol-benzapto-benzimidazol-2 -Thiocyanatomethylthiobenzthiazol, methylene bisthiocyanate, phenol derivatives such as 2-phenylphenol, (2,2'-dihydroxy-5,5'-dichloro) -diphenylmethane and 3-methyl-4-chlorophenyl, organo-tin compounds, trihalomethylthio compounds such as folpet, fluorfolpet, dichlofluanid.

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

Preparation Examples:

Example 1:

1st stage:

To a mixture of 10.0 g (0.031 mol) l- (4-bromophenyl) -2,2-dimethyl-4- (l, 2,4-triazol-l-yl) -butan-3-one and 3, 8 g (0.068 mol) of potassium carbonate in 50 ml of dimethyl sulfoxide and 10 ml of water are added dropwise at room temperature with stirring, 6.9 g (0.034 mol) of 1,3-dibromopropane, the reaction temperature increasing. When the addition is complete, the mixture is stirred at 70 ° C. for 10 hours. For working up, the reaction mixture is cooled to room temperature, mixed with 200 ml of water and extracted with ethyl acetate. The organic phase is washed with water, dried and concentrated under reduced pressure. The residue is purified by chromatography on silica gel (eluent: diethyl ether).

4.9 g (44% of theory) of l- [3- (4-bromophenyl) -2,2-dimethyl-l-oxo-prop-l-yl] -l- (l, 2,4- triazol-l-yl) -cyclobutane as an oil with a refractive index n ^ ⁰ = 1.5578.

Example 2:

2nd stage:

To a solution of 2.9 g (0.008 mol) of l- [3- (4-bromophenyl) -2,2-dimethyl-l-oxo-prop-l-yl] -l- (l, 2,4-triazole -l-yl) -cyclobutane in 30 ml of methanol, a solution of 0.08 g (0.0022 mol) of sodium borohydride in 2,000 ml of water is added at room temperature with stirring. When the addition is complete, the mixture is stirred at room temperature for 2 hours. For working up, the reaction mixture is concentrated under reduced pressure. The residue is taken up in dichloromethane. The resulting solution is washed with water, dried and again concentrated under reduced pressure.

2.9 g (100% of theory) of l- [3- (4-bromophenyl) -2,2-dimethyl-l-hyddrrooxxyy - pprroojp: -l-yl] -l- (l, 2,4-triazol-l-yl) -cyclobutane as an oil with a refractive index n °

= 1.5547.

The following cyclobutylazoles of the formula (Ib) are obtained in a corresponding manner and in accordance with the general information on the preparation:

Table 1

Table 1 (continued)

E.g. no. R physical properties

IH)

Table 1 (continued)

E.g. no. R physical properties

22 OH ¹ H NMR ^*) : 7.6 (IH); 7.71 (IH)

Br- // w _ -C I H -

23 o 1H-NMR ^*) :

»7.89 (IH); 8.24 (IH)

// w - JJ -

Table 1 (continued)

⁾ The 1H-NMR spectra were recorded ₆₎ with tetramethylsilane (TMS) as inne¬ rem standard in deuterochloroform (CDC1 ₃₎ or hexa-deutero-dimethylsulfoxide (DMSO-d. The chemical shift is given as a δ value in ppm.

Examples of use:

In the following examples of use, the compounds listed below were used as reference substances:

2,2-dimethyl-1 - (4-methylphenyl) -4- (1,2,4-triazol-1-yl) -heptan-3-one

1 - (4-chlorophenyl) -2,2-dimethyl-4- (1, 2,4-triazol-1-yl) -heρtan-3-one (both known from EP-OS 0 054 865)

Example A:

Erysiphe test (barley) / protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkyl aryl 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 efficacy, young plants are sprayed with the preparation of active compound as dewy. After the spray coating has dried on, the plants are covered with spores from Erysiphe graminis fsp. hordei pollinated.

The plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80% in order to promote the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, the substances according to the invention listed in Examples 6, 8, 10, 11, 12 and 14 show an efficiency of 100% at an active ingredient concentration of 250 ppm in the spray liquid, while the comparison substance (A) has an efficiency of 88%. Table A:

Erysiphe test (barley) / protective

Active ingredient Efficiency in% of the untreated control with an active ingredient concentration in the spray liquor of 250 ppm

Known: (A) 88

According to the invention:

Table A: (continued)

Erysiphe test (barley) / protective

(14) 100

Example B

Leptosphaeria nodorum test (wheat) / protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkyl aryl polyglycol ether

To test for protective efficacy, young plants are sprayed with the active ingredient preparation, dew-moist. After the spray coating has dried on, the plants are sprayed with a spore suspension of Leptosphaeria nodorum. The plants remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 48 hours.

The plants are placed 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 substances according to the invention listed in Examples 1-5 and 7-14 at an active substance concentration of 250 ppm in the spray liquid show an efficiency of over 80%, while the comparison substances (A) and (B) have no effect or have an efficiency of 25%. Table B

Leptosphaeria nodorum test (wheat) / protective

Known: (A)

According to the invention:

Table B: (continued)

Leptosphaeria nodorum test (wheat) / protective

Table B: (continued)

Leptosphaeria nodorum test (wheat) / protective

Example C

Pellicularia test (rice) / protective

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether

To produce a suitable preparation of active compound, a part by weight of active compound is mixed with the stated amounts of solvent and the concentrate is diluted to the desired concentration with water and the stated amount of emulsifier.

To test its effectiveness, young rice plants are sprayed in the 3 to 4-leaf stage with the preparation of the active ingredient until it drips. The plants remain in the greenhouse until the spray coating has dried on. The plants are then inoculated with Pellicularia sasakii and placed in a greenhouse at 25 ° C. and a relative atmospheric humidity of 100%.

The disease infestation is evaluated 5 to 8 days after the inoculation.

In this test, the substances according to the invention listed in Examples 2, 4, 6, 10 and 12 show an efficiency of 100% at an active ingredient concentration of 0.025% in the spray liquid, while the comparison substance (A) has no effect.

Table C:

Pellicularia test (rice) / protective

Efficiency in% of the untreated control at an active ingredient concentration of 0.025%

Known: (A)

According to the invention:

Table C: (continued)

Pellicularia test (rice) / protective

Example D

Pyricularia test (rice) / protective

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether

To test for protective efficacy, young rice plants are sprayed with the preparation of active compound to runoff. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae.

The plants are then placed in a greenhouse at 25 ° C. and a relative atmospheric humidity of 100%.

The disease infestation is evaluated 4 days after the inoculation.

In this test, the substances according to the invention listed in Examples 2, 4, 6, 10 and 12 show an efficiency of over 70% at an active ingredient concentration of 0.025% in the spray liquid, while the comparison substance (A) has no effect. Table D

Pyricularia test (rice) / protective

Known: (A) 0

According to the invention:

Table D: (continued)

Pyricularia test (rice) / protective

OCF I (10) 89

Example E:

Uncinula test (vine) / protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether

To produce a suitable preparation of active compound, a 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 active compound preparation to runoff. After the spray coating has dried on, the plants are dusted with conidia of the Uncinula necator fungus.

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

Evaluation is carried out 14 days after the inoculation.

In this test, the substances according to the invention listed in Examples 1-4, 7-10, 12 and 14 show an efficiency of over 90% at an active ingredient concentration of 10 ppm in the spray liquid.

Table E:

Uncinula test (vine) / protective

Active ingredient Efficiency in% of the untreated control with an active ingredient concentration of 10 ppm

According to the invention: (1) 99

Table E: (continued)

Uncinula test (vine) / protective

Example F

Podosphaera test (apple) / protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether

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

The plants are then placed in a greenhouse at 23 ° C. and a relative humidity of approx. 70%.

Evaluation is carried out 10 days after the inoculation.

In this test, the substances according to the invention listed in Examples 1, 3, 4 and 8-14 show an efficiency of over 90% at an active substance concentration of 10 ppm in the spray liquid.

Table F:

Podosphaera test (apple) / protective

According to the invention: (1) 100

Table F: (continued)

Podosphaera test (apple) / protective

Example G

The minimum inhibitory concentrations (MIC) of active substances according to the invention are determined to demonstrate the activity against fungi:

An agar made from wort and peptone is mixed with active substances according to the invention in concentrations of 0.1 mg / 1 to 5,000 mg / 1. After the agar solidifies, it is contaminated with pure cultures of the test organisms listed in the table. After two weeks of storage at 28 ° C and 60 to 70% relative humidity, the MIC is determined. MIC is the lowest concentration of active ingredient at which no growth occurs due to the type of microbe used.

In this test, the compound according to the invention listed in Example 14 shows a very good inhibitory effect on Penicillium brevicaule, Chaetomium globosum and Aspergillus niger.

Table G

MIC values in mg / 1 with the action of substances on fungi

Test organisms

Active ingredient Penicillium Chaetomium Aspergillus brevicaule globosum niger

Example H

Ri esenkoloni e-test

To demonstrate the effectiveness against wood-destroying Basidiomycetes, it is determined what percentage inhibitory effect is achieved in giant colonies of certain species that are treated with the respective active ingredients. For this purpose, an agar is prepared using malt extract and active ingredient formulations of certain concentrations are added. After the agar has solidified, inoculate with well overgrown cylindrical agar pieces which have a diameter of 5 mm. The treated agar preparations are left to stand at a temperature of 27 ° C. for 7 days and the diameter of the colonies formed is then measured. Untreated control plates serve as a reference, the determined values are expressed in percent. 0% means that there is no inhibitory effect, 100% means complete inhibition of growth.

In this test, the compound according to the invention listed in Example 14 shows a 100% inhibitory effect on Coriolus versicolor at a concentration of 20 ppm.

Table H

Giant colony test

Active ingredient concentration percentage in agar inhibitory activity in ppm in Coriolus versicolor

(Control)

According to the invention: 20

100

Claims

Cyclobutylazoles of the formula

in which

R represents optionally substituted alkyl, alkenyl, alkynyl,

Cycloalkyl or aryl,

X represents a nitrogen atom or a CH group and

Z represents a carbonyl group or a -CH (OH) group,

as well as their acid addition salts and metal salt complexes.

2. Cyclobutylazoles of formula (I) according to claim 1, in which

R for straight-chain or branched alkyl with 1 to 12 carbon atoms, straight-chain or branched alkenyl with 2 to 12 carbon atoms, straight-chain or branched alkynyl with 2 to 12 carbon atoms, straight-chain or branched alkoxyalkyl with 1 to 8 carbon atoms in the alkoxy part and 1 to 8 carbon atoms in the alkyl part, straight-chain or branched alkylthioalkyl with 1 to 8 carbon atoms in the alkylthio part and 1 to 8 carbon atoms in the alkyl part, straight-chain or branched alkylsulfinylalkyl with 1 to 8 carbon atoms in the alkyl sulfinyl part and 1 to 8 carbon atoms in the alkyl part, straight-chain or branched alkylsulfonylalkyl with 1 to 8 carbon atoms in the alkylsulfonyl part and 1 to 8 carbon atoms in the alkyl part, straight-chain or branched alkoximinoalkyl with 1 to 8 carbon atoms in the alkoxy part and 1 to 8 carbon atoms in the alkyl part, straight-chain or branched hydroximinoalkyl with 1 to 8 carbon atoms, straight-chain or branched cyanoalkyl with 1 to 8 carbon atoms in the alkyl part, straight-chain or branched haloalkyl with 1 to 8 carbon atoms and 1 to 9 identical or different halogen atoms, straight-chain or branched Hai ogenalkoxy alkyl with 1 to 8 carbon atoms in the alkoxy part and 1 to 8 carbon atoms in the alkyl part and with 1 to 9 identical or different halogen atoms, straight-chain or branched haloalkylthioalkyl with 1 to 8 carbon atoms in the alkylthio part and 1 to 8 carbon atoms in the alkyl part and with 1 to 9 identical or different halogen atoms, straight-chain or branched haloalkylsulfinylalkyl with 1 to 8 carbon atoms in the haloalkyl part and 1 to 8 carbon atoms in the alkyl part and with 1 to 9 identical or different halogen atoms, straight-chain or branched halogenoalkylsulfonylalkyl with 1 to 8 carbon atoms in the haloalkyl part and 1 to 8 carbon atoms in the alkyl part and 1 to 9 identical or different halogen atoms, for straight-chain or branched haloalkenyl having 2 to 12 carbon atoms and 1 to

9 identical or different halogen atoms, straight-chain or branched haloalkynyl having 2 to 12 carbon atoms and 1 to 9 identical or different halogen atoms, for dioxolanyl alkyl having 1 to 6 carbon atoms in the straight-chain or branched alkyl part, dithiolanylalkyl having 1 to 6 carbon atoms in the straight-chain or branched alkyl part, dioxanylalkyl having 1 to 6 carbon atoms in the straight-chain or branched alkyl part or represents dithianylalkyl having 1 to 6 carbon atoms in the straight-chain or branched alkyl part,

or

R for optionally up to five times, the same or different

Halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms substituted cycloalkylalkyl having 3 to 7 carbon atoms or for cycloalkylalkyl substituted by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms, optionally substituted by one to five times, identically or differently 3 to 7 carbon atoms in the cycloalkyl part and 1 to 8 carbon atoms in the straight-chain or branched alkyl part,

or

R for aryl with 6 to 10 carbon atoms, arylalkyl with 6 to 10 carbon atoms in the aryl part and 1 to 8 carbon atoms in the straight-chain or branched alkyl part, ar loxyalkyl with 6 to 10 carbon atoms in the aryl part and 1 to 8 carbon atoms in the straight-chain part or branched alkyl part, arylthioalkyl with 6 to 10 carbon atoms in the aryl part and 1 to 8 carbon atoms in the straight-chain or branched alkyl part, arylsulfinylalkyl with 6 to 10 carbon atoms in the aryl part and 1 to 8 carbon atoms in the straight-chain or branched alkyl part, arylsulfonylalkyl with 6 to 10 carbon atoms in the aryl part and 1 to 8 carbon atoms in the straight-chain or branched alkyl part, aralkyloxyalkyl with 6 to 10 carbon atoms in the aryl part and in each case 1 to 8 carbon atoms in the individual straight-chain or branched alkyl parts, aralkylthioalkyl with 6 to 10 carbon atoms in the Aryl part and in each case 1 to 8 carbon atoms in the individual straight-chain or branched alkyl parts, aralkylsulfinylalkyl with 6 to 10 carbon atoms in the aryl part and in each case 1 to 8 carbon atoms in the individual straight-chain or branched alkyl parts or aralkylsulfonyl alkyl with 6 to 10 carbon atoms in the aryl part and each has 1 to 8 carbon atoms in the individual straight-chain or branched alkyl parts, where each of the abovementioned radicals in the aryl part can be monosubstituted to triple, identical or differently substituted by halogen, cyano, nitro, straight-chain or branched alkyl, straight-chain or branched alkoxy, straight-chain or branched alkylthio, straight-chain or branched alkylsulfinyl or straight-chain or branched alkylsulfonyl each having 1 to 4 carbon atoms, straight-chain or branched haloalkyl, straight-chain or branched haloalkoxy, straight-chain or branched shark ogenalkylthio, g straight-chain or branched haloalkylsulfinyl or straight-chain or branched haloalkylsulfonyl each having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, straight-chain or branched alkoxy carbonyl having 1 to 4 carbon atoms in the alkoxy part, straight-chain or branched alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy part and 1 to 4 carbon atoms in the alkyl part, optionally one to four times, identical or different, halogen-substituted dioxyalkylene with 1 to 3 carbon atoms, double-linked alkylene with 3 to 8 carbon atoms, cycloalkyl with 3 to 7 carbon atoms, phenyl optionally substituted one to three times, identically or differently by halogen and / or alkyl having 1 to 4 carbon atoms, and / or phenoxy optionally substituted one to three times, identically or differently by halogen and / or alkyl having 1 to 4 carbon atoms. 3. Process for the preparation of cyclobutylazoles of the formula

in which

R represents optionally substituted alkyl, alkenyl, alkynyl,

Cycloalkyl or aryl,

X represents a nitrogen atom or a CH group and

Z represents a carbonyl group or a -CH (OH) group,

and of their acid addition salts and metal salt complexes, characterized in that

Azolyl-methyl-ketones of the formula

in which

R and X have the meanings given above,

with 1,3-dihalopropane compounds of the formula Hal-CH ₂ -CH ₂ -CH ₂ -Hal (III)

in which

Shark represents halogen,

if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder and if appropriate the resulting cyclobutylazoles of the formula

in which

R and X have the meanings given above,

reacted with a reducing agent, if appropriate in the presence of a diluent, and, if appropriate, then adding an acid or a metal salt to the compounds of the formula (I) thus obtained.

Pesticide, characterized by a content of at least one cyclobutylazole of the formula (I) according to claim 1 or an acid addition salt or metal salt complex of a cyclobutylazole of the formula (I). 5. Use of cyclobutylazoles of the formula (I) according to Claim 1 or of their acid addition salts and metal salt complexes for controlling pests in crop protection and in material protection.

6. A method of combating pests in crop protection and in material protection, characterized in that cyclobutylazoles of the formula (I) according to claim 1 or their acid addition salts or metal salt complexes are applied to the pests and / or their habitat.

7. A process for the preparation of pesticides, characterized in that cyclobutylazoles of the formula (I) according to Claim 1 or their acid addition salts or metal salt complexes are mixed with extenders and / or surface-active substances.