EP1389191A1 - Heterocyclyl phenyl benzyl ethers used as fungicides - Google Patents

Abstract

The invention relates to novel heterocyclyl phenyl benzyl ethers of formula (I), wherein R represents methoxy carbonyl, methylaminocarbonyl or 5,6-dihydro-1,4,2-dioxazine-3yl, R1 represents alkyl, R2 represents hydrogen or alkyl and Het represents optionally substituted tetrazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,3-oxazolyl, 1,3-thiazolyl, pyridyl or pyrimidyl. The invention also relates to a method for the production of said ethers and to the use thereof for controlling harmful organisms.

Description

 HETEROCYCLYPHENYL-BENZYL ETHER AS A FUNGI ZIDE

The invention relates to new heterocyclylphenyl benzyl ethers, a process for their preparation and their use for controlling harmful organisms.

Certain compounds with a similar substitution pattern and their fungicidal activity have already been disclosed (see, for example, WO 95/04728, WO 99/46246, WO 97/14693, WO 00/53585). However, the action of these previously known compounds is not entirely satisfactory in all areas of application, especially at low application rates and concentrations.

The new heterocyclylphenyl benzyl ethers of the general formula (I) have now been found

in which

R represents methoxycarbonyl, methylaminocarbonyl or 5,6-dihydro-l, 4,2-dioxazin-3-yl,

R ^{1 represents} alkyl,

R-2 represents hydrogen or alkyl and

Het stands for optionally substituted tetrazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,3-oxazolyl, 1,3-thiazolyl, pyridyl or pyrimidyl. For the definitions of the symbols given in the formulas, collective terms are used which are generally representative of the following substituents:

Halogen: fluorine, chlorine, bromine and iodine, especially fluorine or chlorine;

Alkyl: saturated, straight-chain or branched hydrocarbon chains, unless specified otherwise, preference is given to hydrocarbon chains with 1 to 6 carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, Pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3- Methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl 1-1-methylpropyl and 1-ethyl-2-methylpropyl;

Haloalkyl: straight-chain or branched alkyl groups with 1 to 4 carbon atoms (as mentioned above), in which case the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms as mentioned above, for example C ₁ -C ₂ -haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl,

Fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2- difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;

Alkoxy: straight-chain or branched alkyl groups with 1 to 4 or 10 carbon atoms (as mentioned above) which are bonded to the skeleton via an oxygen atom (-O-);

Alkenyl: unsaturated, straight-chain or branched hydrocarbon radicals with 2 to

10 carbon atoms and a double bond in any position, e.g. C2-Cö-alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1- Methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3 - Methyl 1-butenyl, l-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, l-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl

3-butenyl, l, l-dimethyl-2-propenyl, 1,2-dimethyl-l-propenyl, l, 2-dimethyl-2-propenyl, 1-ethyl-l-propenyl, l-ethyl-2- propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4- Methyl-l-pentenyl, l-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyl- 3-pentenyl, 3-

Methyl-3-pentenyl, 4-methyl-3-pentenyl, l-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, l, l- Dimethyl-2-butenyl, 1,1-dimethyl 1-3-butenyl, 1,2-dimethyl-l-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3 -Dimethy 1-1 -butenyl, l, 3-dimethyl-2-butenyl, l, 3-dimethyl-3-butenyl, 2,2-dimethy 1-3 -butenyl, 2,3-dimethyl-l-butenyl, 2 , 3-dimethyl-3-butenyl, 3,3-dimethyl

1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl- 2-butenyl, 2-ethyl-3-butenyl, l, l, 2-trimethyl-2-propenyl, l-ethyl-l-methyl-2-propenyl, l-ethyl-2-methyl-l-propenyl and l- Ethyl 2-methyl-2-propenyl;

Alkynyl: straight-chain or branched hydrocarbon groups with 2 to 10 carbon atoms and a triple bond in any position, for example C2-C6-alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1- Methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 3 - Methyl 1-butynyl, 1,1-dimethyl 1-2 propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl -2-pentynyl, l-methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4 pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, l, l-dimethyl-2-butynyl, 1,1-dimethyl 1-3 -butinyl, l, 2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-l-butynyl, l-ethyl-2-butynyl, l-ethyl-3-butynyl, 2-ethyl-3-butynyl and l-ethyl-l- methyl-2-propynyl. Furthermore, it was found that the new heterocyclylphenyl benzyl ethers of the general formula (I) are obtained if

a) benzyl halides of the formula (II),

in which

R has the meaning given above and

X represents halogen,

with a substituted phenol of the general formula (III),

in which

Rl, R2 and Het have the meanings given above,

if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor, or if

b) heterocyclylphenyl benzyl ether of the formula (I) with R in its meaning as methoxycarbonyl with methylamine, if appropriate in the presence of a diluent, or if c) benzyloxyphenyl nitriles of the general formula (IV)

in which

R, Rl and R ^ have the meanings given above,

with an alkali metal azide, if appropriate in the presence of a diluent, or if

d) Heterocyclylphenyl benzyl ether of formula (I) with Het in its meaning as tetrazolyl with alkylating agents, such as iodomethane, dimethyl sulfate or bromoethane, optionally in the presence of a diluent and optionally in the presence of an acid acceptor.

Finally, it was found that the new heterocyclylphenyl benzyl ethers of the general formula (I) have a strong action against harmful organisms, in particular a very strong fungicidal action. Harmful organisms are understood to mean in particular microorganisms and animal pests.

The compounds according to the invention can optionally be present as mixtures of various possible isomeric forms, in particular of stereoisomers, such as, for example, E- and Z-. Both the E and the Z isomers and any mixtures of these isomers are claimed. R preferably represents methoxycarbonyl, methylaminocarbonyl or 5,6-dihydro-1,4,2-dioxazin-3-yl.

Rl preferably represents alkyl having 1 to 4 carbon atoms.

R2 preferably represents hydrogen or alkyl having 1 to 4 carbon atoms.

Het preferably represents tetrazolyl optionally substituted by alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms, alkenyl or alkynyl each having 2 to 4 carbon atoms.

Het also preferably represents 1,2,4-oxadiazolyl, 1,3 which is optionally substituted by alkyl or alkoxy each having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms, alkenyl or alkynyl each having 2 to 4 carbon atoms , 4-oxadiazolyl, 1,3,4-thiaziazyl, 1,3-oxazolyl or 1,3-thiazolyl.

Het also preferably represents pyridyl or pyrimidyl optionally substituted by halogen, alkyl or alkoxy each having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms, alkenyl or alkynyl each having 2 to 4 carbon atoms.

R particularly preferably represents methoxycarbonyl, methylaminocarbonyl or 5,6-dihydro-l, 4,2-dioxazin-3-yl.

Rl particularly preferably represents methyl.

R2 particularly preferably represents hydrogen or methyl. Het particularly preferably represents tetrazolyl optionally substituted by methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, trifluoromethyl, allyl or propargyl.

Het also particularly preferably represents 1,2,4- which is optionally substituted by methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, difluoromethyl, trifluoromethyl, allyl or propargyl. Oxadiazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,3-oxazolyl or 1,3-thiazolyl.

Het is also particularly preferably optionally fluorine, chlorine, bromine,

Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, difluoromethyl, trifluoromethyl, allyl or propargyl substituted pyridyl or pyrimidyl.

The general or preferred radical definitions given above apply both to the end products of the formula (I) and correspondingly to the starting materials or intermediates required in each case for the preparation.

The radical definitions specified for these radicals in the respective combinations or preferred combinations of radicals are independently replaced by radical definitions of other preferred ranges, irrespective of the respectively specified combination of the radicals.

Formula (II) provides a general definition of the benzyl halides required as starting materials for carrying out process a) according to the invention. In this

Formula (II) preferably or in particular has the meaning which has already been stated as preferred or as particularly preferred for R in connection with the description of the compounds of the formula (I) according to the invention. X represents halogen, preferably chlorine or bromine. The starting materials of the formula (II) are known and can be prepared by known processes (compare, for example, WO 99/46263, WO 99/19311, WO 98/17653, WO 97/21686, WO 96/07635, EP 254426) ,

Formula (III) provides a general definition of the substituted phenols which are furthermore required as starting materials for carrying out process a) according to the invention. In this formula (III), R, R-2 and Het preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or as particularly preferred for R1, R 1 and Het were specified.

The starting materials of formula (III) are new and also the subject of the present application.

You will get one

e) alkoxyphenols of the general formula (V)

in which

Rl, R ^ and Het have the meanings given above and

R3 represents alkyl or optionally substituted benzyl, in the presence of a Lewis acid such as boron tribromide, optionally in the presence of a diluent such as methylene chloride.

Formula (V) provides a general definition of the alkoxyphenols required as starting materials for carrying out process e) according to the invention. In this formula (V), R, R2 and Het preferably or in particular have those meanings which have already been given as preferred or as particularly preferred for R, R2 and Het in connection with the description of the compounds of the formula (I) according to the invention. R3 represents alkyl or optionally substituted benzyl, preferably methyl, ethyl, benzyl or chlorobenzyl.

The starting materials of formula (V) are new and also the subject of the present application.

You will get one

f) benzonitriles of the formula (VI)

in which

R and R ^ have the meanings given above, and

R ^{4 represents} hydrogen or alkyl

with an alkali metal azide, such as sodium azide, optionally in the presence of a diluent, such as dimethylforma- mid, and if appropriate in the presence of a further reaction auxiliary or if one

g) amidoximes of the formula (VII)

in which

Rl, R2 and R ^ have the meanings given above,

with an orthoester of formula (VIII)

R ⁴ -C (OR ⁵ ) ₃ (VIII), in which

R ^{4 represents} alkyl and

R ^{5 represents} alkyl,

optionally in the presence of a diluent, or if one

h) Boronic acids of the formula (IX) in which

Rl, R ^, and R3 have the meanings given above,

with a halogen heterocycle of Fonnel (X),

Het-Y (X) in which

Het has the meaning given above and

represents halogen,

optionally in the presence of a diluent, such as dimethoxyethane, optionally in the presence of a catalyst, preferably a palladium complex, such as tetrakis (triphenylphosphine) palladium (O), optionally in the presence of an acid acceptor, such as aqueous sodium carbonate solution, or if you

Alkoxyphenols of the general formula (V) with Het in its meaning as tetrazolyl with alkylating agents, such as iodomethane, dimethyl sulfate or bromoethane, optionally in the presence of a diluent, such as acetonitrile and optionally in the presence of an acid acceptor, such as potassium carbonate. R ⁴ and R ⁵ are preferably C _r C ₄ alkyl.

R ⁴ and R ⁵ are particularly preferably methyl or ethyl.

Formula (VI) provides a general definition of the benzonitriles required as starting materials for carrying out process f) according to the invention. In this formula (VI), Rl, R-2 and R- preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (V) according to the invention, are preferred or particularly preferred for R, R2 and R. ^ were specified.

The starting materials of the formula (VI) are known and can be prepared by known processes (compare, for example, US 5464848).

The alkali metal azides which are furthermore required as starting materials for carrying out process f) according to the invention are commercially available synthetic chemicals.

Formula (VII) provides a general definition of the amidoximes required as starting materials for carrying out process g) according to the invention. In this formula (VII), I, R2 and R ^ preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (V) according to the invention, are preferred or as particularly preferred for R1, R2 and R. ^ were specified.

They are obtained (process j) if the alkoxybenzonitriles of the formula (VI) already described in connection with process f) are reacted with hydroxylamine or acid addition complexes thereof, optionally in the presence of a diluent.

Hydroxylamine and its salts are commercially available synthetic chemicals. Formula (VIII) provides a general definition of the orthoesters required as starting materials for carrying out process g) according to the invention. In this formula (VIII) R ^{4 is} alkyl, preferably methyl or ethyl and R ^ is alkyl, preferably methyl or ethyl.

The orthoesters of the formula (VIII) are commercially available synthetic chemicals.

Formula (IX) provides a general definition of the boronic acids required as starting materials for carrying out process h) according to the invention. In this formula (IX), R, R ^ and R3 preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (V) according to the invention, are preferred or as particularly preferred for R, R-2 and R3 were specified.

Process h) Boronic acids of the formula (IX) are known and can be prepared according to known processes

Methods are produced (compare, for example, WO 96/16934 or WO 99/51568).

Formula (X) provides a general definition of the halogen heterocycles required as starting materials for carrying out process h) according to the invention. In this formula (X), Y represents halogen, preferably chlorine or bromine.

Halogen heterocycles of the formula (X) are known and can be prepared by known methods (compare, for example, DE 3228147).

The alkoxyphenols of the general formula (V) with Het in its meaning as tetrazolyl which are required as starting materials for carrying out process i) according to the invention can be prepared by process f).

The alkylating agents, such as iodomethane, dimethyl sulfate or bromoethane, which are further required as starting materials for carrying out process i) according to the invention, are commercially available synthetic chemicals. The heterocyclylphenyl benzyl ethers of the formula (I) with R in its meaning as methoxycarbonyl which are required as starting materials for carrying out process b) according to the invention are compounds according to the invention and can be prepared by processes a), c) or d).

The methylamine which is also required as starting material for carrying out process b) according to the invention is a commercially available synthetic chemical.

Formula (IV) provides a general definition of the benzyloxyphenyl nitriles required as starting materials for carrying out process c) according to the invention. In this formula (IV), R, R and R ^ preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred for R, and R ^ were specified.

The benzyloxyphenyl nitriles of the general formula (IV) are not yet known and are also the subject of the present invention as new substances.

They can be obtained (method k) by using the hydroxybenzonitriles

Formula (XI)

in which

Rl and R ^ have the meanings given above, with the benzyl halides of the formula (II) described in connection with process a), if appropriate in the presence of a diluent such as acetonitrile and if appropriate in the presence of an acid acceptor such as potassium carbonate.

Formula (XI) provides a general definition of the hydroxybenzonitriles required as starting materials for carrying out process k) according to the invention. In this formula (VI), R and R ^ preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred for

R and R2 were specified.

The starting materials of the formula (XI) are known and can be prepared by known processes (see, for example, US Pat. No. 5,464,848).

The heterocyclylphenyl benzyl ethers of the formula (I) with Het in its meaning as tetrazolyl which are required as starting materials for carrying out process d) according to the invention are compounds according to the invention and can be obtained by process a) or c).

The alkylating agents, such as iodomethane, dimethyl sulfate or bromoethane, which are also required as starting materials for carrying out process d) according to the invention, are commercially available synthetic chemicals.

Suitable diluents for carrying out processes a) and d) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride,

Dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Ketones such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

Processes a) and d) according to the invention are optionally carried out in the presence of a suitable acid acceptor. All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, Sodium carbonate, potassium carbonate, potassium hydrogen carbonate or sodium hydrogen carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-

Methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can be varied within a substantial range when carrying out processes a) and d) according to the invention. In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 20 ° C to 80 ° C.

To carry out process a) according to the invention for the preparation of the compounds of the formula (I), 1 mol per mole of the benzyl halide of the formula (II) is used in generally 0.2 to 5 mol, preferably 0.5 to 2 mol, of the substituted phenol of the formula (III).

To carry out the process d) according to the invention for the preparation of the compounds of the formula (I), per mol of the heterocyclylphenylbenzyl ether is used

Formula (I) with Het in its meaning as tetrazolyl is generally 0.2 to 5 mol, preferably 0.5 to 2 mol, of alkylating agent.

Suitable diluents for carrying out process b) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides, such as

dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

The reaction temperatures can be varied within a substantial range when carrying out process b) according to the invention. In general, temperatures from -20 ° C to 120 ° C, preferably at temperatures from 0 ° C to 80 ° C. To carry out process b) according to the invention for the preparation of the compounds of the formula (I), 1 to 1.5 mol, preferably 1.1 to 1.3 mol, of methylamine are generally employed per mol of the heterocyclylphenylbenzyl ether of the formula (I).

Suitable diluents for carrying out process c) according to the invention are all inert, polar organic solvents. These preferably include nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Sulfoxides, such as

Dimethyl sulfoxide or sulfones such as sulfolane.

The reaction temperatures can be varied within a substantial range when carrying out process c) according to the invention. In general, temperatures from 20 ° C to 200 ° C, preferably at temperatures of

50 ° C to 150 ° C.

To carry out process c) according to the invention for the preparation of the compounds of the formula (I), 1 to 10 mol, preferably 1 to 5 mol, of azide are generally employed per mol of the compounds of the formula (IV).

Suitable diluents for carrying out process e) according to the invention are halogenated hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane.

The reaction temperatures can be varied within a substantial range when carrying out process e) according to the invention. In general, temperatures from -50 ° C to 50 ° C, preferably at temperatures from -20 ° C to 25 ° C. To carry out process e) according to the invention for the preparation of the compounds of the formula (III), generally 0.4 to 2 mol, preferably 0.5 to 1.5 mol, of Lewis acid are used per mol of the compounds of the formula (V).

As Lewis acids for carrying out process e) according to the invention

Boron tribromide is particularly preferred.

Suitable diluents for carrying out process f) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,

1,2-diethoxyethane or anisole; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

The reaction temperatures can be carried out when carrying out the process according to the invention

Process f) can be varied over a wide range. In general, temperatures from 50 ° C to 150 ° C, preferably at temperatures from 80 ° C to 120 ° C. To carry out process f) according to the invention for the preparation of the compounds of the formula (V), 1 to 3 mol, preferably 1.5 to 2 mol, of alkali metal azide are generally employed per mol of the compounds of the formula (VI).

To carry out process f) according to the invention for the preparation of the compounds of the formula (V), 1 to 3 mol, preferably 1.5 to 2 mol, of a reaction auxiliary are used per mol of the compounds of the formula (VI).

Ammonium salts, preferably trialkylammonium salts, particularly preferably triethylammonium chloride or ammonium chloride, are used in particular as reaction auxiliaries for carrying out process f) according to the invention.

The diluent for carrying out process g) according to the invention is preferably the orthoester of the formula (VIII).

The reaction temperatures can be varied within a substantial range when carrying out process g) according to the invention. In general, temperatures from 80 ° C to 160 ° C, preferably at temperatures from 90 ° C to 150 ° C.

Suitable diluents for carrying out process h) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as

Chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-di ethoxyethane, 1,2-diethoxyethane or anisole; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxy ethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

The reaction temperatures can be varied within a substantial range when carrying out process h) according to the invention. In general, temperatures from 0 ° C to 120 ° C, preferably at temperatures from 20 ° C to 100 ° C.

To carry out the process h) according to the invention for the preparation of the compounds of the formula (V), 0.9 to 1.2 mol, preferably 1.0 to 1.1 mol, of the compound of the formula are generally employed per mol of the compounds of the formula (IX) (X) a.

Suitable palladium compounds which can be used as catalyst in process h) according to the invention are, for example, bis (dibenzalacetone) palladium, palladium acetate, palladium dichloride, palladium dibromide, palladium trifluoroacetate, palladium diphosphine halide and acetate complexes such as

Palladium (triρhenylphosphin) acetate. Tetrakis (triphenylphosphine) palladium is preferred.

Process h) according to the invention is optionally carried out in the presence of a suitable acid acceptor. All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide , Potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, potassium hydrogen carbonate,

Sodium bicarbonate or ammonium carbonate, as well as tertiary amines, such as for example trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundec ). Sodium carbonate is preferably used as the acid acceptor for carrying out process h) according to the invention.

Suitable diluents for carrying out process i) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene,

Toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol,

Methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

The reaction temperatures can be varied within a substantial range when carrying out process i) according to the invention. In general, temperatures from 0 ° C to 100 ° C, preferably at temperatures from 20 ° C to 80 ° C.

To carry out process i) according to the invention for the preparation of the compounds of the formula (V), per mole of the compounds of the formula (V) with Het in its meaning as tetrazolyl, generally 0.9 to 1.5 mol, preferably 1 to 1.1 mol, of alkylating agent.

Process i) according to the invention is optionally carried out in the presence of a suitable acid acceptor. All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, Potassium hydroxide, sodium carbonate, potassium carbonate, potassium hydrogen carbonate or sodium hydrogen carbonate and tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethyl-a iline, N, N-dimethyl-benzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N , N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

Suitable diluents for carrying out process j) according to the invention are alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol , Diethylenglykolmonomethylether, Diethylenglykolmonoethylether, their mixtures with water or pure water into consideration. Ethanol is preferred.

The reaction temperatures can be varied within a substantial range when carrying out process j) according to the invention. In general, temperatures from 0 ° C to 100 ° C, preferably at temperatures from 20 ° C to 80 ° C.

To carry out process j) according to the invention for the preparation of the compounds of the formula (VII), 1 to 2 mol, preferably 1 to 1.1 mol, of hydroxylamine or acid addition complexes thereof are generally employed per mol of the compounds of the formula (VI). Suitable diluents for carrying out process k) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as

Chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

The reaction temperatures can be varied within a substantial range when carrying out process k) according to the invention. In general, temperatures from 0 ° C to 100 ° C, preferably at temperatures from 20 ° C to 80 ° C.

To carry out process k) according to the invention and to prepare the compounds of the formula (IV), generally 1.1 to 1.3 mol, preferably 1.0 to 1.1 mol, of compounds of the compound are employed per mole of the compounds of the formula (XI)

Formula (II).

The processes according to the invention are generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure - generally between 0.1 bar and 10 bar. The reaction is carried out, worked up and isolated according to generally customary methods (see also the preparation examples).

The following examples serve to explain the invention. However, the invention is not limited to the examples.

The substances according to the invention have a strong microbicidal action and can be used to control unwanted microorganisms, such as fungi and bacteria, in crop protection and in material protection.

Fungicides can be used to protect plants against Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

Some pathogens of fungal and bacterial are exemplary but not limiting

Diseases that fall under the generic names listed above:

Xanthomonas species, such as, for example, Xanthomonas campestris pv. Oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv. Lachrymans; Erwinia species, such as, for example, Erwinia amylovora;

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;

Bremia species, such as, for example, Bremia lactucae; Peronospora species, such as, for example, Peronospora pisi or P. 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 P. graminea

(Conidial form: Drechslera, Syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus

(Conidial form: Drechslera, Syn: Helminthosporium); Uromyces species, such as, for example, Uromyces appendiculatus;

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

Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;

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 active compounds according to the invention also have a strong strengthening effect

Plants on. They are therefore suitable for mobilizing the plant's own defenses against attack by unwanted microorganisms.

Plant-strengthening (resistance-inducing) substances are to be understood in the present context as substances which are able to

Defense system of plants to stimulate the treated plants subsequent inocolation with undesirable microorganisms develop extensive resistance to these microorganisms.

In the present case, undesirable microorganisms are understood to mean phytopathogenic fungi, bacteria and viruses. The substances according to the invention can therefore be used to protect plants against attack by the named pathogens within a certain period of time after the treatment. The period within which protection is brought about generally extends from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active compounds.

The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases permits 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 used with particularly good success in combating cereal diseases, for example against Erysiphe species, and for diseases in wine, fruit and vegetable cultivation, for example against Sphaerotheca species.

The active compounds according to the invention are also suitable for increasing the crop yield. They are also less toxic and have good plant tolerance.

If appropriate, the active compounds according to the invention can also be used in certain concentrations and application rates as herbicides, for influencing plant growth and for controlling animal pests. If appropriate, they can also be used as intermediates and precursors for the synthesis of further active compounds.

According to the invention, all plants and parts of plants can be treated. Under

Plants are understood here as all plants and plant populations desired and unwanted wild plants or crops (including naturally occurring crops). Cultivated plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which can or cannot be protected by plant breeders' rights. Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

The treatment of the plants and plant parts according to the invention with the active substances takes place directly or by acting on their environment, habitat or

Storage room according to the usual treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, scattering, spreading and, in the case of propagation material, in particular seeds, furthermore by single- or multi-layer coating.

In material protection, 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 that are to be protected against microbial change or destruction by active substances according to the invention can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials that can be attacked or decomposed by microorganisms , Parts of production plants, for example, are also part of the materials to be protected Cooling water circuits, called, 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 cause degradation or a change in the technical materials. The active compounds according to the invention preferably act against fungi, in particular molds, wood-coloring and wood-destroying fungi

(Basidiomycetes) and against mucous organisms and algae.

For example, microorganisms of the following genera may be mentioned:

Altemaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, like Chaetomium globosum,

Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus, Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

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 the customary formulations, such as

Solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, Fine encapsulation in polymeric materials and in coating compositions for seeds, as well as ULV cold and warm mist formulations.

These formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as

Xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water. Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. Possible solid carriers are: e.g. natural rock meals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock meals, such as highly disperse silica, aluminum oxide and silicates. The following are suitable as solid carriers for granules: e.g. 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 stems. Possible emulsifiers and / or foaming agents are: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. As dispersants come in

Question: eg lignin sulfite liquor and methyl cellulose. Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also 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%.

The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the spectrum of activity or to prevent the development of resistance. In many cases, synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components.

The following connections can be considered as mixed partners:

fungicides:

Aldimorph, Ampropylfos, Ampropylfos Potassium, Andoprim, A ilazin, Azaconazol, Azoxystrobin,

Benalaxyl, benodanil, benomyl, benzamacril, benza acrylic-isobutyl, bialaphos,

Binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate, Calcium polysulfide, capsimycin, captafol, captan, carbendazim, carboxin, carvone, quinomethionate (quinomethionate), chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cypodaminazol, cypodaminazol, cypodinconol, cypodinconol

Debacarb, dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazol-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithorphoxinodonine, dithorphononodine

Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,

Famoxadone, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone,

Fluazinam, flumetover, fluoromid, fluquinconazole, flurprimidol, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-alminium, fosetyl sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, fefazamidecyclox, furconazolox, furconazoloxis, furconazoloxis,

guazatine,

Hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, imibenconazole, iminoctadine, iminoctadineal besilate, iminoctadine triacetate,

Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovaledione, Iprovalicarb,

Kasuga ycin, Kresoxim-methyl, copper preparations such as: copper hydroxide, copper phthalate, copper oxychloride, copper sulfate, copper oxide, oxy-copper and

Bordeaux mixture, Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,

Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,

Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,

Paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphene, pimaricin, piperalin,

Polyoxin, polyoxorim, probenazole, prochloraz, procymidon, propamocarb, propanosine sodium, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,

Quinconazole, quintozen (PCNB), quinoxyfen,

Sulfur and sulfur preparations, spiroxamines,

Tebuconazole, Tecloftalam, Tecnazen, Tetcyclacis, Tetraconazole, Thiabendazole, Thicyofen, Thifluzamide, Thiophanate-methyl, Thiram, Tioxymid, Tolclofos-methyl,

Tolylfluanid, Triadimefon, Triadimenol, Triazbutil, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triflumizol, Triforin, Triticonazol, Trifloxystrobin,

uniconazole

Validamycin A, vinclozolin, viniconazole,

Zarilamid, Zineb, Ziram as well

Dagger G, OK-8705, OK-8801, α- (l, 1-dimethylethyl) -ß- (2-phenoxyethyl) - 1 H-1, 2,4-triazole-1-ethanol, α- (2,4-dichlo henyl) -ß -fluoro-b-propyl-1H- 1, 2,4-triazole-1-ethanol, - (2,4-dichlorophenyl) -ß-methoxy-a-methyl-1H- 1, 2,4-triazole-1 - ethanol, α- (5-methyl-l, 3-dioxan-5-yl) -ß - [[4- (trifluoromethyl) phenyl] methylene] -lH-l, 2,4-triazol-1-ethanol,

(5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (lH-l, 2,4-triazol-l-yl) -3-octanone,

(E) -a- (methoxyimino) -N-methyl-2-phenoxy-phenylacetamide,

1 - (2,4-dichlorophenyl) -2- (1 H- 1, 2,4-triazole-1-yl) -ethanone-O- (phenylmethyl) -oxime, 1 - (2-methyl-1-naphthalenyl) -lH-pyrrole-2,5-dione, l- (3,5-dichlorophenyl) -3- (2-propenyl) -2,5-pyrrolidinedione, l - [(diiodomethyl) sulfonyl] -4-methyl-benzene , l - [[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] - lH-imidazole,

1 - [[2- (4-chloro-phenyl) -3-phenyloxiranyl] methyl] - 1H- 1, 2,4-triazole, l- [l- [2 - [(2,4-dichlorophenyl) methoxy] - phenyl] -ethenyl] -lH-imidazole, l-methyl-5-nonyl-2- (phenylmethyl) -3-pyιolidinol,

2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1, 3-thiazole-5-carboxanilide,

2,6-dichloro-5- (methylthio) -4-pyrimidinyl thiocyanate,

2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide, 2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,

2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,

2 - [(1-methylethyl) sulfonyl] -5- (trichloromethyl) - 1, 3, 4-thiadiazole,

2 - [[6-Deoxy-4-O- (4-O-methyl-ß-D-glycopyranosyl) -aD-glucopyranosyl] -amino] -4- methoxy-lH-pyrrolo [2,3-d] pyrimidine- 5-carbonitrile, 2-aminobutane,

2-bromo-2- (bromomethyl) -pentandinitril,

2-chloro-N- (2,3-dihydro-l, l, 3-trimethyl-lH-inden-4-yl) -3-pyridine carboxamide,

2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) -acetamide,

2-phenylphenol (OPP), 3,4-dichloro-l- [4- (difluoromethoxy) -phenyl] -lH-pyrrole-2,5-dione,

3,5-dichloro-N- [cyano [(l-methyl-2-propynyl) -oxy] -methyl] -benzamide, 3 - (1,1-dimethylpropyl-1-oxo-1 H-indene-2-carbonitrile, 3- [2- (4-chlorophenyl) -5-ethoxy-3-isoxazolidinyl] pyridine, 4-chloro-2- cyan-N, N-dimethyl-5- (4-methylphenyl) -IH-imidazole-l-sulfonamide, 4-methyl-tetrazolo [l, 5-a] quinazolin-5 (4H) -one, 8-hydroxyquinoline sulfate,

9H-xanthene-9-carboxylic acid 2 - [(phenylamino) carbonyl] hydrazide, bis- (l-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) -oxy] -2,5-thiophene dicarboxylate, cis-l- (4-chloro-phenyl) -2- (lH-l, 2,4-triazol-l-yl) cycloheptanol, cis-4- [3- [4- (l, l-dimethylpropyl) phenyl- 2-methylpropyl] -2,6-dimethyl-morpholine hydrochloride,

Ethyl - [(4-chlorophenyl) azo] cyanoacetate,

potassium bicarbonate,

Methantetrathiol sodium salt,

Methyl l- (2,3-dihydro-2,2-dimethyl-lH-inden-l-yl) -lH-imidazole-5-carboxylate, methyl-N- (2,6-dimethylphenyl) -N- (5 -isoxazolylcarbonyl) -DL-alaninate,

Methyl-N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate, N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) - acetamide, N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide, N- (2-chloro-4-nitrophenyl) -4-methyl-3- nitro-benzenesulfonamide, N- (4-cyclohexylphenyl) -l, 4,5,6-tetrahydro-2-pyrimidinamine,

N- (4-hexylphenyl) -l, 4,5,6-tetrahydro-2-pyrimidinamine, N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) - acetamide, N- (6-methoxy) -3-pyridinyl) cyclopropanecarboxamide, N- [2,2,2-trichloro-l - [(chloroacetyl) amino] ethyl] benzamide, N- [3-chloro 4,5-bis- (2-propynyloxy) -phenyl] -N'-methoxy-methanimidamid,

N-formyl-N-hydroxy-DL-alanine sodium salt,

O, O-Diethyl- [2- (dipropylamino) -2-oxoethyl] ethylphosphoraιrιidothioate, O-Methyl-S-phenyl-phenylpropylphosphoramidothioate, S-Methyl-1, 2,3-benzothiadiazol-7-carbothioate, spiro [2H] - 1 -B enzopyran-2, 1 '(3' H) -isobenzofuran] -3 '-one, 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, Acephate, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb, Alpha-cypermethrin, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin,

Azamethiphos, Azinphos A, Azinphos M, Azocyclotin,

Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Betacyfluthrin, Bifenazate, Bifenthrin, Bioethanomethrin

Biopermethrin, BPMC, Bromophos A, Bufencarb, Buprofezin, Butathiofos, Butocarboxim, Butylpyridaben,

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloetho- carb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos,

Chloφyrifos, Chloφyrifos M, Chlovaporthrin, Cis-Resmethrin, Cispermethrin, Clocythrin, Cloethocarb, Clofentezine, Cyanophos, Cycloprene, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazine

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon,

Dichlorvos, diflubenzuron, dimethoate, dimethylvinphos, diofenolan, disulfoton, docusat-sodium, doenapyn,

Eflusilanate, Emamectin, Empenthrin, Endosulfan, Entomopfthora spp., Esfenvalerate, Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos, Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fipronil, Fluazuron, Flubrocythrinate, Flucycloxuron, Floxthrinofonate, Fufenoxthhronate, Fufenoxthhronate, Fufronoxinophonate, Fufenoxin, Fufone - carb,

granulosis

Halofenozide, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene,

Imidacloprid, isazofos, isofenphos, isoxathion, ivermectin,

nucleopolyhedroviruses

Lambda cyhalothrin, lufenuron

Malathion, Mecarbam, Metaldehyde, Methamidophos, Metharhician anisopliae, Metharhician flavoviride, Methidathione, Methiocarb, Methomyl, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Monocrotophos,

Naled, Nitenpyram, Nithiazine, Novaluron

Omethoate, Oxamyl, Oxydemethon M

Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat,

Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propoxur, Prothiofos, Prothoat, Pymetrozine, Pyraclofos, Pyresmethrin, Pyrethrum, Pyridaben, Pyridathion, Pyrimfenifen, Pyrimfenifen

quinalphos, ribavirin

Salithion, Sebufos, Silafluofen, Spinosad, Sulfotep, Sulprofos,

Tau-fluvalinate, Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Temivinphos, Terbufos, Tetrachlorvinphos, Theta-cyper-methrin, Thiamethoxam, Thiapronil, Thiatriphosiodalinoxinoxalinoxinoxaline, Tri Triazamates, triazophos, triazuron, trichlophenidines, trichlorfon, triflumuron,

trimethacarb,

Vamidothion, Vaniliprole, Verticillium lecanii

YI 5302

Zeta-cypermethrin, zolaprofos

(1 R-cis) - [5 - (Phenylmethyl) -3-furanyl] -methyl-3 - [(dihy dro-2-oxo-3 (2H) -furanylidene) -methyl] -2,2-dimethylcyclopropanecarboxylate

(3-phenoxyphenyl) methyl 2,2,3,3-tetramethylcyclopropane decarboxylate l - [(2-chloro-5-thiazolyl) methyl] tetrahydro-3,5-dimethyl-N-nitro-l, 3,5-triazine -2 (lH) - imine

2- (2-Chloro-6-fluoφhenyl) -4- [4- (l, l-dimethylethyl) phenyl] -4,5-dihydro-oxazole 2- (acetyloxy) -3-dodecyl-1, 4-naphthalenedione

2-chloro-N - [[[4- (l-phenylethoxy) phenyl] amino] carbonyl] -benzamide

2-chloro-N - [[[4- (2,2-dichloro-l, l-difluoroethoxy) -phenyl] -amino] -carbonyl] -benzamide

3-methylphenyl propylcarbamate

4- [4- (4-ethoxyphenyl) -4-methylpentyl] -l-fluoro-2-phenoxy-benzene 4-chloro-2- (l, l-dimethylethyl) -5 - [[2- (2,6- dimethyl-4-phenoxyρhenoxy) ethyl] thio] -

-pyridazinone 3 (2H) 4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) -pyridazinone

4-chloro-5 - [(6-chloro-3-pyridinyl) methoxy] -2- (3,4-dichloφhenyl) -3 (2H) -pyridazinone

Bacillus thuringiensis strain EG-2348 benzoic acid [2-benzoyl-l- (l, l-dimethylethyl) hydrazide

Butanoic acid 2,2-dimethyl-3- (2,4-dichloφhenyl) -2-oxo-l-oxaspiro [4.5] dec-3-en-4-yl ester

[3 - [(6-chloro-3-pyridinyl) methyl] -2-thiazolidinylidene] -cyanamide

Dihydro-2- (nitromethylene) -2H-1,3-thiazine-3 (4H) -carboxaldehyde ethyl- [2 - [[1,6-dihydro-6-oxo-1- (phenylmethyl) -4-pyridazinyl] oxy ] ethyl] carbamate

N- (3,4,4-trifluoro-l-oxo-3-butenyl) -glycine

N- (4-Chloφhenyl) -3- [4- (difluoromethoxy) phenyl] -4,5-dihydro-4-phenyl-lH-pyrazol-

1-carboxamide

N- [(2-chloro-5-thiazolyl) methyl] -N'-methyl-N "-nitro-guanide N-methyl-N '- (1-methyl-2-propenyl) -1, 2-hydrazinedicarbothioamide

N-methyl-N'-2-propenyl-1, 2-hydrazine dicarbothioamide

O, O-diethyl [2- (dipropylamino) -2-oxoethyl] -ethylphosphoramidothioat

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

In addition, the compounds of formula (I) according to the invention also have very good antifungal effects. They have a very broad spectrum of antimycotic effects, in particular against dermatophytes and shoots, mold and diphasic fungi (e.g. against Candida species such as Candida albicans,

Candida glabrata) and Epidermophyton floccosum, AspergiUus species such as Aspergillus niger and Aspergillus fbmigatus, Trichophyton species such as Trichophyton mentagrophytes, Microsporon species such as Microsporon canis and audouinii. The list of these fungi is in no way a limitation of the detectable mycotic spectrum, but is only of an explanatory nature.

The active compounds can be used as such, 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 are used in the usual way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.

When using the active compounds according to the invention as fungicides, the application rates can be varied within a relatively wide range, depending on the type of application.

In the treatment of parts of plants, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g l a. In the case of seed treatment, the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In the treatment of the soil, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

For insecticides and fungicides:

As already mentioned above, all plants and their parts can be treated according to the invention. In a preferred embodiment, plant species and plant cultivars and their parts occurring wildly or obtained by conventional organic breeding methods, such as crossing or protoplast fusion, are treated. In a further preferred embodiment, transgenic plants and plant cultivars which may be obtained by genetic engineering methods Combination with conventional methods have been obtained (Genetic Modified Organisms) and their parts treated. The term "parts" or "parts of plants" or "plant parts" was explained above.

Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention. Plant cultivars are understood to mean plants with new properties (“traits”) which have been grown both by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, breeds, bio and genotypes.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, growing season, nutrition), the treatment according to the invention can also cause superadditive ("synergistic") effects. For example, reduced application rates and / or widening of the activity spectrum and / or an increase in the action of the substances and agents which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or workability of the harvested products, which go beyond the effects to be expected.

The preferred transgenic (genetically engineered) plants or plant cultivars to be treated according to the invention include all plants which have received genetic material through the genetic engineering modification, which gives these plants particularly advantageous valuable properties (“traits”). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to water or soil salt content, increased flowering performance, easier harvesting,

Acceleration of ripeness, higher crop yields, higher quality and / or higher Nutritional value of the harvested products, higher shelf life and / or workability of the harvested products. Further and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or viruses, and an increased tolerance of the plants to certain herbicidal active ingredients. Examples of transgenic plants are the important cultivated plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybeans, potatoes , Cotton and rapeseed are particularly highlighted. The traits are particularly emphasized as the increased defense of the plants against insects by toxins arising in the plants, in particular those which are caused by the genetic material from Bacillus Thuringenisis (eg by the genes CryΙA (a), CryIA (b ), CryΙA (c), CryllA, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF as well as their combinations) are produced in the plants (hereinafter "Bt plants"). The properties ("traits") also particularly emphasize the increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. The properties (“traits”) which are particularly emphasized are the increased tolerance of the plants to certain herbicides

Active substances, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (e.g. "PAT" gene). The genes imparting the desired properties (“traits”) can also occur in combinations with one another in the transgenic plants. Examples of "Bt plants" are corn varieties, cotton varieties, soy varieties and potato varieties that are sold under the trade names YIELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard® ( Cotton), Nucoton® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants are maize varieties, cotton varieties and soy varieties that are sold under the trade names Roundup Ready® (tolerance to glyphosate e.g. maize,

Cotton, soy), Liberty Link® (tolerance to phosphinotricin, e.g. rapeseed), IMI® (tolerance to hnidazolinone) and STS® (tolerance to sulfonylureas such as maize). The herbicide-resistant plants (conventionally bred to herbicide tolerance) include the varieties sold under the name Clearfield® (eg maize). Of course, these statements also apply to those that will be developed in the future or will come onto the market in the future

Plant varieties with these or future-developed genetic properties ("traits").

The plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the active compound mixtures according to the invention. The preferred ranges given above for the active substances or mixtures also apply to the treatment of these plants. Plant treatment with the compounds or mixtures specifically listed in the present text should be particularly emphasized.

Manufacturing examples:

example 1

( 1 )

Procedure a)

A mixture of 2 g (0.0105 mol) of 5- (3-methyl-4-hydroxyphenyl) tetrazole, 1.7 g (0.0126 mol) of potassium carbonate, 4.1 g (0.014 mol) of 2-bromomethyl-phenylglyoxylic acid methyl ester-O-methyloxime (for production see, for example, EP 420091) and 80 ml of acetonitrile is heated under reflux for 18 hours. Then the reaction mixture is suctioned off through Celite and washed with acetonitrile. The filtrate is evaporated in vacuo, the residue is triturated with diisopropyl ether and suction filtered. 4.1 g (99% of theory) of 2- [4- (2-methyl-tetrazol-5-yl) -2-methyl-phenoxy] methyl-methyl-phenylglyoxylate-O-methyloxime are thus obtained in the form of a colorless one Powder with the logP (pH 2) = 3.08 (content according to HPLC: 98%).

Example 2

(2) Method b)

3.2 g (0.008 lmol) (2E) -2- (methoxyimino) -2- (2 - {[2-methyl-4- (2-methyl-2H-tetrazol-5-yl) phenoxy] methyl} phenyl) methyl acetate are dissolved in 60 ml of methanol and mixed with 7 ml of a 40% solution of methylamine in water. The mixture is left to stand at room temperature overnight and the is then distilled Solvent in a vacuum. 3.1 g (97% of theory) of 2- [4- (2-methyl-tetrazol-5-yl) -2-methylphenoxy] methylphenylglyoxylic acid N-methylamide-O are thus obtained -methyloxime as a colorless powder with the logP (pH 2) = 2.58 (content according to HPLC: 95%).

Example 3

(3) Method a) A mixture of 0.8 g (3.9 mmol) of 5-ethyl-3- (3-methyl-4-hydroxyphenyl) -l, 2,4-oxadiazole, 0.65 g (4, 7 mmol) potassium carbonate, 1.4 g (3.9 mmol) methyl 2-bromomethylphenylglyoxylate-O-methyloxime (for preparation see eg EP 420091) and 30 ml acetonitrile is heated under reflux for 18 hours. Then the reaction mixture is suctioned off through Celite and washed with acetonitrile. The filtrate is evaporated in vacuo, the residue is triturated with diisopropyl ether and suction filtered. This gives 1.1 g (68% of theory) of 2- [4- (5-ethyl-l, 2,4-oxadiazol-3-yl) -2-methylphenoxy] methyl-phenyl-glyoxylic acid methyl ester-O-methyloxime in the form of a colorless powder with the logP (pH2) = 3.80 (content according to HPLC: 96.5%).

Example 4

( ⁴ ) Method b)

0.6 g (1.47 mmol) of 2- [4- (5-ethyl-l, 2,4-oxadiazol-3-yl) -2-methylρhenoxy] methylphenylglyoxylate methyl-O-methyloxime are dissolved in 50 ml of methanol dissolved and mixed with 1.5 ml of a 40% solution of methylamine in water. The mixture is left to stand at room temperature overnight and the solvent is then distilled off in vacuo. The residue is triturated with a mixture of petroleum ether and diisopropyl ether and the product is filtered off with suction. This gives 0.55 g (92% of theory) of 2- [4- (5-ethyl-l, 2,4-oxadiazol-3-yl) -2-methylphenoxy] methyl-phenylglyoxylic acid-N-methylamide -O-methyloxime as a colorless powder with the logP (pH2) = 3.24 (content according to HPLC: 96%).

Example 5

(5) Method a)

A mixture of 0.6 g (2.3 mmol) 3-trifluoromethyl-5- (3-methyl-4-hydroxyphenyl) -l, 2,4-thiadiazole, 0.5 g (3.5 mmol) potassium carbonate , 0.8 g (2.3 mmol) 2-bromomethyl-ρhenylglyoxylsäuremethylester-O-methyloxime (for production see e.g. EP 420091) and 50 ml of acetonitrile is stirred at 50 ° C for 18 hours. Then the reaction mixture is suctioned off through Celite and washed with acetonitrile. The filtrate is evaporated in vacuo, the residue is triturated with a mixture of petroleum ether and diisopropyl ether and suction filtered. This gives 0.8 g (74% of theory) of 2- [4- (3-trifluoromethyl-1,2,4-thiadiazol-5-yl) -2-methylphenoxy] methyl-methylphenylglyoxylate-O-methyloxime in the form of a colorless powder with the logP (pH2) = 4.62 (content according to HPLC: 96.5%).

Example 6

(6) Method b)

0.5 g (1.07 mmol) of 2- [4- (3-trifluoromethyl-l, 2,4-thiadiazol-5-yl) -2-methylphenoxy] methyl-methyl-phenylglyoxylic acid methyl ester-O-methyloxime are dissolved in 50 ml of methanol dissolved and mixed with 1 ml of a 40% solution of methylamine in water. The mixture is left to stand at room temperature overnight and the solvent is then distilled off in vacuo. The residue is mixed with about 50 ml of water and extracted twice with 30 ml of ethyl acetate. The organic phases are dried over magnesium sulfate and evaporated in vacuo. This gives 0.5 g (99% of theory) of 2- [4- (3-trifluoromethyl-1,2,4-thiadiazol-5-yl) -2-methylphenoxy] methylphenylglyoxylic acid-N-methylamide-O -methyloxime as a colorless powder with the logP (pH2) = 4.08 (content according to HPLC: 95%).

Analogous to Examples 1 to 6 and in accordance with the information in the general process descriptions, those listed in Table 1 below are given

Obtaining compounds of formula (I).

Table 1

# stands for the point of attachment to the phenyl ring

*) The logP values were determined in accordance with EEC Directive 79/831 Annex V.

A8 by HPLC (gradient method, acetonitrile / 0.1% aqueous phosphoric acid)

Production of intermediates of formula (V)

Example V-l

Procedure f)

A mixture of 26.6 g (0.18 mol) of 3-methyl-4-methoxybenzonitrile (for preparation see, for example, US Pat. No. 5,464,848), 49.6 g (0.36 mol) of triethylammonium chloride, 23.4 g ( 0.36 mol) sodium azide and 80 ml dimethylformamide is heated under reflux for 18 hours. The solvent is then distilled off in vacuo, 150 ml of a solution of sodium hydroxide in water (5% strength) are added to the residue and the mixture is extracted with petroleum ether. The aqueous phase is filtered through activated carbon and then adjusted to pH 3 with concentrated aqueous hydrochloric acid. The precipitated product is suctioned off and washed with water. This gives 33.8 g (99% of theory) of 5- (3-methyl-4-methoxyphenyl) tetrazole with a purity of about 98% (HPLC) and a logP (pH2) of 1.51.

Example V-2

Procedure i)

A mixture of 11 g (0.0578 mol) of 5- (3-methyl-4-methoxyphenyl) tetrazole, 11.3 g (0.082 mol) of potassium carbonate, 11.6 g (0.082 mol) of iodomethane and 120 ml of acetonitrile turns 18 Stirred at 60 ° C for hours. Then 250 ml of water are added and the mixture is extracted 3 times with ethyl acetate. The organic phases are washed with water, dried over sodium sulfate and evaporated in vacuo. 10.9 g of a product are obtained which, according to HPLC analysis, consists of approx. 67% of the desired 2-methyl-5- (3-methyl-4-methoxy-phenyl) -tetrazole (logP (pH2) = 2.38 ) and about 32% consists of the isomeric l-methyl-5- (3-methyl-4-methoxyphenyl) tetrazole. According to method i), the following are also obtained:

Example V-3

logP (pH2) 3.78

Example V-4

logP (pH2) 2.75

Example V-5

logP (pH2) 2.12 Example V-6

logP (pH2) 3.24

Example V-7

logP (pH2) 2.51

Example V-8

Procedure g)

A mixture of 3 g (0.017 mol) of 3-methyl-4-methoxy-benzamide oxime and 15 ml of triethyl orthopropionate is boiled under reflux for 18 hours. The volatile components are then distilled off in vacuo, the residue is dissolved in ethyl acetate and the solution is shaken with 5% sodium hydroxide solution and water. The organic phase is dried and evaporated in vacuo. This gives 1.6 g of a yellow oil which, according to HPLC, consists of 73% of the desired product (logp (pH2) = 3.19). Example V-9

Procedure h)

1.24 is added at room temperature to a solution of 0.57 g (3 mmol) of 3-trifluoromethyl-5-chloro-l, 2,4-thiadiazole (preparation see DE 3 228 147 for example) in 20 ml of 1,2-dimethoxyethane g (4.5 mmol) 3-methyl-4- (4-chlorobenzyloxy) phenylboronic acid and 50 mg tetrakis (triphenylphosphine) palladium (0). Then 4.8 ml of a 2M solution of sodium carbonate in water are added and the mixture is heated at 80 ° C. for 4 hours and then stirred overnight at room temperature. After adding about 100 ml of water, the reaction mixture is extracted twice with 50 ml of ethyl acetate each time. The organic phases are dried over sodium sulfate and evaporated in vacuo. This leaves 1.5 g of a product which, according to HPLC analysis, consists of approx. 67% 3-trifluoromethyl-5- [3-methyl-4- (4-chlorobenzyloxy) phenyl] -1, 2,4- thiadiazole exists (logP (pH2) = 5.78).

Production of precursors of formula (III)

Example III-1

Compound III- la Compound III- lb Procedure e)

A solution of 10.7 g (0.0524 mol) of the mixture of 1- and 2-methyl-5- (3-methyl-4-methoxyphenyl) tetrazole obtained in b) in 150 ml of anhydrous methylene chloride is added dropwise 15.8 g (0.0629 mol) of boron tribromide at room temperature. After the end of the exothermic reaction, stirring is continued for 3 hours at room temperature and then another 7.9 g (0.0315 mol) of boron tribromide are added. The mixture is stirred for 18 hours at room temperature, then the solvent is distilled off in vacuo and the residue is mixed with 300 ml of a saturated solution of sodium bicarbonate in water. After adding 100 ml of water, the precipitated solid is filtered off and washed with water. The desired product is separated off by silica gel chromatography (methylene chloride-ethyl acetate 5: 1). This gives 5.3 g (53%) of 2-methyl-5- (3-methyl-4-hydroxyphenyl) tetrazole in the form of a colorless powder with the logP (pH2) = 1.45 (content according to HPLC: 99% ).

Furthermore, 2.5 g (25%) of isomeric l-methyl-5- (3-methyl-4-hydroxyphenyl) tetrazole are obtained in the form of a colorless powder with the logP (ρH2) = 1.04 (content according to HPLC: 97 %).

Example III-2

Procedure e)

0.6 ml is added dropwise at room temperature to a solution of 0.9 g (4.1 mmol) of 5-ethyl-3- (3-methyl-4-methoxyphenyl) -l, 2,4-oxadiazoline in 40 ml of anhydrous methylene chloride (6.1 mmol) boron tribromide. The mixture is stirred for 3 hours at room temperature and then another 0.7 ml (7.1 mmol) of boron tribromide are added. The mixture is stirred for 18 hours at room temperature, then the solvent is distilled in Vacuum off and the residue with 30 ml of a saturated solution of sodium hydrogen carbonate in water. After adding 10 ml of water, the precipitated solid is suctioned off and washed with water. This gives 0.85 g of 5-ethyl-3- (3-methyl-4-hydroxyphenyl) -l, 2,4-oxadiazole as a colorless powder with the logP (pH2) = 2.08 (content according to HPLC 96%) ,

Example III-3

Process e) 0.55 ml (5.5 mmol) of boron tribromide is added dropwise to a solution of 1.4 g (3.6 mmol) of the crude product obtained under a) in 50 ml of anhydrous methylene chloride at room temperature. The mixture is stirred at room temperature for 18 hours, then the solvent is distilled off in vacuo and 30 ml of a saturated solution of sodium hydrogen carbonate in water are added to the residue. After adding 10 ml of water, the precipitated solid is suctioned off and washed with water. The

The product is triturated with petroleum ether and suction filtered. This gives 0.6 g of 3-trifluoromethyl-5- (3-methyl-4-hydroxyphenyl) -1, 2,4-thiadiazole as a colorless powder with the logP (pH2) = 3.10 (content according to HPLC 78% ).

According to method e), the following are also obtained: Example III-4

logP (pH2) 2.54

Example IH-5

logP (pH2) 1.81

Example III-6

logP (pH2) 1.41 Example III-7

logP (pH2) 2.18

Example III-8

logP (pH2) l, 75

Production of intermediate products of the formula (VH)

Example VII-1

Procedure j)

A mixture of 9.5 g (0.065 mol) of 3-methyl-4-methoxybenzonitrile (preparation see, for example, US 5 464 848), 9 g (0.13 mol) of hydroxylamine hydrochloride, 17.9 g (0.13 mol) of potassium carbonate and 80 ml of ethanol is refluxed for 18 hours. The solvent is then distilled off in vacuo, the residue is triturated with 50 ml of water, filtered off with suction and washed with water. The product is triturated with ethyl acetate, suction filtered and washed with ethyl acetate. 6.4 g of 3-methyl-4-methoxy-benzamidoxime (55%) are thus obtained as an almost colorless powder with the logP (pH2) = 0.36 (content according to HPLC 95%).

applications

Example A

Erysiphe test (wheat) / protective

Solvent: 25 parts by weight of N, N-dimethylacetamide

Emulsifier: 0.6 part 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 in the stated application rate.

After the spray coating has dried on, the plants are covered with spores from Erysiphe graminis f.sp. tritici 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. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the substances according to the invention listed in Examples (11, 2) show an efficiency of 98% or more at an application rate of 250 g / ha. Example B

Sphaerotheca test (cucumber) / protective

Solvent: 24.5 parts by weight of acetone

24.5 parts by weight of dimethylacetamide emulsifier: 1 part 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 activity, young plants are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Sphaerotheca fuliginea. The plants are then placed in the greenhouse at about 23 ° C. and a relative atmospheric humidity of about 70%.

Evaluation is carried out 7 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of

100% means that no infection is observed.

In this test, the substances according to the invention listed in Examples (8, 9, 10) show an efficiency of 97% or more at an application rate of 100 g / ha.

Claims

claims

1. Compounds of the general formula (I)

in which

R represents methoxycarbonyl, methylaminocarbonyl or 5,6-dihydrol, 4,2-dioxazin-3-yl,

Rl represents alkyl,

R2 represents hydrogen or alkyl and

Het represents optionally substituted tetrazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,3-oxazolyl, 1,3-thiazolyl, pyridyl or pyrimidyl.

2. Compounds of formula (I), according to claim 1, characterized in that

R represents methoxycarbonyl, methylaminocarbonyl or 5,6-dihydrol, 4,2-dioxazin-3-yl,

Rl represents alkyl with 1 to 4 carbon atoms,

R ^{2 represents} hydrogen or alkyl having 1 to 4 carbon atoms, Het stands for tetrazolyl optionally substituted by alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms, alkenyl or alkynyl each having 2 to 4 carbon atoms

for 1,2,4-oxadiazolyl, 1,3,4, optionally substituted by alkyl or alkoxy each having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms, alkenyl or alkynyl each having 2 to 4 carbon atoms -Oxadiazolyl, 1,3,4-

Thiadiazolyl, 1,3-oxazolyl or 1,3-thiazolyl is or

for optionally by halogen, alkyl or alkoxy each having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms, alkenyl or alkynyl each having 2 to 4

Carbon atoms substituted pyridyl or pyrimidyl.

3. Compounds of formula (I) according to claim 1, characterized in that

R represents methoxycarbonyl, methylaminocarbonyl or 5,6-dihydrol, 4,2-dioxazin-3-yl,

Rl represents methyl,

R represents hydrogen or methyl,

Het stands for tetrazolyl optionally substituted by methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, trifluoromethyl, allyl or propargyl for 1,2,4-oxadiazolyl, 1,3 which is optionally substituted by methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, difluoromethyl, trifluoromethyl, allyl or propargyl , 4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,3-oxazolyl or 1,3-thiazolyl or

represents pyridyl or pyrimidyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, difluoromethyl, trifluoromethyl, allyl or propargyl.

4. Compounds of the general formula (III)

in which

Rl, R2 and Het have the meanings given in claim 1.

5. Compounds of the general formula (IV)

in which

R, Rl and R ^{2 have} the meanings given in claim 1.

, Compounds of the general formula (V)

in which

Rl, R2 and Het have the meanings given in claim 1 and

R- * "represents alkyl or optionally substituted benzyl.

7. A process for the preparation of compounds of general formula (I) as defined in claim 1, characterized in that

a) compounds of the formula (II),

R has the meanings given in claim 1 and

X represents halogen,

with a substituted phenol of the general formula (III),

Rl, R xmd Het have the meanings given above,

if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor, or

b) reacting compounds of formula (I) with R in their meaning as methoxycarbonyl with methylamine, optionally in the presence of a diluent, or

c) compounds of the general formula (IV)

R, Rl and R2 have the meanings given above,

with an alkali metal azide, if appropriate in the presence of a diluent, or

d) heterocyclylphenyl benzyl ether of the formula (I) with Het in its meaning as tetrazolyl with alkylating agents, such as, for example Iodomethane, dimethyl sulfate or bromoethane, if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor.

8. Agents for combating harmful organisms containing extenders and / or carriers and optionally surface-active substances, characterized by a content of at least one compound as defined in claims 1 to 3.

9. A method for controlling harmful organisms, characterized in that compounds as defined in claims 1 to 3 or agents as defined in claim 8 are allowed to act on harmful organisms and / or their habitat.

10. Use of compounds as in claims 1 to 3 and of

Agents as defined in claim 8 for controlling harmful organisms.

11. A process for the preparation of agents as defined in spoke 8, characterized in that compounds as defined in claims 1 to 3 are used with extenders and / or carriers and / or surface-active agents.