EP0973728A1

EP0973728A1 - Acrylic acid phenylester derivatives

Info

Publication number: EP0973728A1
Application number: EP98913599A
Authority: EP
Inventors: Herbert Gayer; Peter Gerdes; Ralf Tiemann; Klaus Stenzel
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1997-03-11
Filing date: 1998-02-26
Publication date: 2000-01-26
Also published as: DE19709874A1; WO1998040351A1; AU6824398A; JP2001514639A

Abstract

The invention relates to novel acrylic acid phenylester derivatives, several methods for the production and the use thereof as fungicides, as well as to novel intermediate products and several methods for the production thereof.

Description

Phenyl acrylate derivatives

The invention relates to new acrylic acid phenyl ester derivatives, several processes for their preparation and their use as fungicides, and to new intermediates and several processes for their production.

It has already been known that certain benzoic acid phenyl ester derivatives, which are constitutionally similar to the acrylic acid phenyl ester derivatives described below, have fungicidal properties (see, for example, EP-A-178 826). For example,

Use benzoic acid 2- (2-methoxy-1-methoxycarbonyl-vinyl) -phenyl ester to combat fungi. The fungicidal activity of this compound is good, but in some cases leaves something to be desired at low application rates.

The new acrylic acid phenyl ester derivatives of the general formula (I) have now been found

in which

G for a single bond, alkanediyl optionally interrupted by heteroatoms (but the carbon atom to which R * is bonded is always linked to a carbon atom of the alkanediyl chain) or a group

pation stands,

wherein R ^{3 represents} hydrogen or in each case optionally substituted alkyl or cycloalkyl,

Rl represents hydrogen, cyano or in each case optionally substituted alkyl or cycloalkyl,

R2 represents hydrogen or in each case optionally substituted alkyl or cycloalkyl,

Z for optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl,

Cycloalkenyl, aryl or heterocyclyl

In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkanediyl, alkenyl or alkynyl, also in combination with heteroatoms, such as in alkoxy, alkylthio or alkylamino, are each straight-chain or branched

Alkyl or alkanediyl chain interrupted by more than one hetero atom, these can be the same or different. If an alkyl or alkanediyl chain is interrupted by more than one oxygen atom, two oxygen atoms are not directly adjacent

Halogen generally represents fluorine, chlorine, bromine or iodine, and also pseudohalogens, such as, for example, cyano, preferably fluorine, chlorine, bromine or cyano, in particular fluorine or chlorine

Aryl stands for aromatic, mono- or polycyclic hydrocarbon rings, such as phenyl, naphthyl, anthranyl, phenanthryl, preferably phenyl or naphthyl, especially phenyl

Heterocyclyl stands for saturated or unsaturated, as well as aromatic, ring-shaped compounds, in which at least one ring member contains a hetero atom, ie an atom other than carbon. If the ring contains several heteroatoms, these can be the same or different. Heteroatoms are preferably oxygen, nitrogen or sulfur form the annular connections with others carbocyclic or heterocyclic, fused or bridged rings together form a polycyclic ring system. Mono- or bicyclic ring systems are preferred, in particular mono- or bicyclic aromatic ring systems.

Cycloalkyl stands for saturated, carbocyclic, ring-shaped compounds which optionally form a polycyclic ring system with other carbocyclic, fused or bridged rings.

Furthermore, it was found that the new acrylic acid phenyl ester derivatives of the general formula (I) can be obtained if (process a) 2- (2-hydroxyphenyl) -3-methoxyacrylic acid methyl ester (II)

with an acrylic acid halide of the general formula (III)

in which

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

X represents halogen,

if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor. It has been found that the new phenyl acrylates of the general formula (I) have a very strong fungicidal activity

The compounds according to the invention can optionally be present as mixtures of various possible isomeric forms, in particular stereoisomers, such as, for example, E and Z, or optical isomers. Both the E and the Z isomers, the individual enantiomers and the racemates , as well as any mixtures of these isomers

The present application preferably relates to acrylic acid phenyl ester derivatives of the formula (I),

in which

R1 represents hydrogen, cyano or alkyl having 1 to 6 carbon atoms optionally substituted by halogen or alkoxy having 1 to 4 carbon atoms or cycloalkyl having 3 to 8 carbon atoms optionally substituted by halogen, alkyl or alkoxy each having 1 to 4 carbon atoms,

R2 represents hydrogen or alkyl having 1 to 6 carbon atoms optionally substituted by halogen or alkoxy having 1 to 4 carbon atoms or cycloalkyl having 3 to 8 carbon atoms optionally substituted by halogen, alkyl or alkoxy each having 1 to 4 carbon atoms,

G for a single bond, optionally interrupted by one or two heteroatoms alkanediyl with 1 to 5 chain links (but the carbon atom to which R ^ is bound always with a carbon atom of

Alkanediyl chain is connected) or a grouping stands,

wherein R ³ for hydrogen or for each optionally by halogen or

Alkoxy with 1 to 4 carbon atoms substituted alkyl with 1 to 6

Represents carbon atoms or cycloalkyl having 3 to 8 carbon atoms optionally substituted by halogen, alkyl or alkoxy each having 1 to 4 carbon atoms,

for optionally single or multiple, the same or different

Halogen, cyano, hydroxy, amino, -C4-alkoxy, -C -C4-alkylthio, CJ-C4-alkylsulfinyl or C j -C4-alkylsulfonyl (each of which may be by

Halogen can be substituted) substituted alkyl having 1 to 8 carbon atoms;

for alkenyl or alkynyl, each optionally substituted by halogen, each having up to 8 carbon atoms;

or for phenyl, naphthyl, cycloalkyl or cycloalkenyl, each of which is optionally mono- or polysubstituted in the same or different ways, each having 3 to 8 carbon atoms or for heterocyclyl having 3 to 7 ring members, at least one of which is for oxygen, sulfur or nitrogen and optionally one or two more represents nitrogen, the possible substituents preferably being selected from the following list: halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl;

in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms;

each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms; in each case straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;

in each case straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 1 1 identical or different halogen atoms;

in each case straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl or alkylsulfonyloxy, each having 1 to 6 carbon atoms in the individual alkyl parts;

each optionally mono- or polysubstituted, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, in each case doubly linked alkylene or Dioxyalkylene, each having 1 to 6 carbon atoms;

Cycloalkyl of 3 to 8 carbon atoms;

Heterocyclyl or heterocyclyl-methyl, each with 3 to 7 ring members, of which 1 to 3 are identical or different heteroatoms - in particular nitrogen, oxygen and / or sulfur -

A 'or a grouping ₂

wherein

A 'for alkyl with 1 to 4 carbon atoms or cycloalkyl with 1 to 6

Carbon atoms stands and -> -

7 represents optionally substituted by cyano, alkoxy, alkylthio, alkylamino, dialkylamino or phenyl alkyl having 1 to 4 carbon atoms, alkenyl or alkynyl each having 2 to 4 carbon atoms.

The present application relates in particular to compounds of the formula (I)

in which

R represents hydrogen, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, trifluoroethyl, cyclopropyl, cyclobutyl,

R ^{2 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, trifluoroethyl, cyclopropyl, cyclobutyl,

G for a single bond, methanediyl, 1, 1-ethanediyl, 1,2-ethanediyl, 1,1-, 1,2-, 1,3- or 2,2-propanediyl, 1,1-, 1,2-, 1 , 3-, 1,4-, 2,2-, 2,3-butanediyl or 1,1-, 1,2- or l, 3- (2-methyl-propanediyl), -O-CH2- (where Z with the oxygen

atom is connected), or a grouping ^N ° ^R3

wherein R ^{3 represents} hydrogen or optionally substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl

Z for phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, oxazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,4- Oxadiazolyl, 1,3,4-oxadiazolyl, pyridinyl, pyrimidyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl or 5,6-dihydro-l, 4,2-dioxazinyl, where the possible substituents are preferably selected from the list below: Fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i- propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluorethoxy, difluoromethylthio, trifluoromethylthio, trifluoromethyloxy, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl

each optionally monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, methyl, trifluoromethyl or ethyl and in each case doubly linked methylenedioxy, ethylenedioxy

Al or a grouping of _{2 sts}

in which

A ^{1 represents} methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl or cyclobutyl and

7 for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, allyl, propargyl, but-2-en-l-yl, 2-methyl-prop-l-en- 3-yl, cyanomethyl,

Methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, methylthioethyl, ethylthioethyl, dimethylaminomethyl, dimethylaminoethyl, methylaminomethyl, methylaminoethyl or benzyl.

The present application also relates in particular to compounds of the formula (I)

in which

Rl for hydrogen, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,

Trifluoromethyl, trifluoroethyl, cyclopropyl, cyclobutyl, R ^{2 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, trifluoroethyl, cyclopropyl, cyclobutyl,

G for a single bond or -O-CH ₂ - (where Z is with the oxygen atom

connected) or in particular for a grouping stands

wherein

R ^{3 represents} hydrogen or optionally up to three times by fluorine,

Chlorine, bromine, methoxy, ethoxy (which are each optionally substituted by fluorine and / or chlorine) substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,

for each one optionally up to six times by fluorine, chlorine,

Bromine, methoxy, ethoxy, phenyl (which may be replaced by fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n - or i-propoxy, difluoromethoxy or trifluoromethoxy is substituted), methyl, ethyl, n- or i-propyl substituted cyclopropyl, cyclobutyl, cyclopentyl or

Cyclohexyl;

Z for each, if necessary, single to triple, identical or different

Chlorine fluorine, bromine, cyano, hydroxy, amino, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfmyl, methylsulfonyl, ethylsulfonyl, difluoromethoxy, trifluorethoxy, difluoromethylthioiflormifluoromethyllifluoromethyltrifluoromethyl Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl; for each optionally single to triple, identical or different, chlorine, fluorine or bromine, substituted vinyl, allyl or propargyl; or

for phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1,2 oxazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3 2,4-oxadiazolyl, 1,3,4-oxadiazolyl, pyridinyl, pyrimidyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl or 5, 6-dihydro-l, 4,2-dioxazinyl, where the possible substituents are preferably selected from the list below:

Fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfmyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluorethoxy, difluoromethylthio, trifluoromethylthio, trifluoromethyloxy, trifluoromethyloxy, trifluoromethyloxy, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl

AI or a grouping ₂

in which

A * represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl or cyclobutyl and

ß7 for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, allyl, propargyl, but-2-en-l-yl, 2-methyl-prop-l-en- 3-yl, cyanomethyl,

Methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methyl - II - thiomethyl, ethylthiomethyl, methylthioethyl, ethylthioethyl, dimethylaminomethyl, dimethylaminoethyl, methylaminomethyl, methylaminoethyl or benzyl.

A particularly preferred group of compounds according to the invention are those

Compounds of the formula (I),

in which

Rl represents cyclopropyl or in particular methyl,

R ^{2 represents} hydrogen,

G represents a single bond or -O-CH2- (where Z is connected to the oxygen atom),

Z represents 1,2-oxazolyl or in particular phenyl which is optionally monosubstituted to trisubstituted in the same or different ways, the possible substituents preferably being selected from the list below: fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl , Difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, methoxycarbonyl, ethoxycarbonyl,

each optionally monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, methyl, trifluoromethyl or ethyl, in each case twice linked methylendioxy, ethylenedioxy

or a grouping in which

A represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl or cyclobutyl and

A ² for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, allyl, propargyl, but-2-en-l-yl, 2-methyl-prop-l-ene -3-yl, cyanomethyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, methylthioethyl, ethylthioethyl, dimethylaminomethyl, dimethylaminoethyl, methylaminomethyl, methylaminoethyl or benzyl.

Another particularly preferred group of compounds according to the invention are those compounds of the formula (I)

in which

Rl represents cyclopropyl or in particular methyl,

R ^{2 represents} hydrogen,

G for a grouping stands,

wherein

R ^{3 represents} methyl,

Z represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, trifluoroethyl, methoxymethyl, methylthiomethyl or methylsulfonylmethyl, Vinyl, dichlorovinyl, allyl, propargyl, cyclopropyl, methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or

is in each case optionally monosubstituted to trisubstituted, identically or differently, 1,2-oxazolyl or in particular phenyl, where the possible

Substituents are preferably selected from the list below:

Fluorine, chlorine, bromine, cyano, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl, trifluoromethyloxycarbonyl, ethyl

each up to fourfold, if necessary, the same or different

Fluorine, chlorine, methyl, trifluoromethyl or ethyl substituted, in each case double linked methylenedioxy, ethylenedioxy

or a grouping

in which

AI is methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl or cyclobutyl and

A ² for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, allyl,

Propargyl, but-2-en-l-yl, 2-methyl-prop-l-en-3-yl, cyanomethyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, methylthioethyl, ethylthioethyl, dimethylaminomethyl, dimethylaminoethyl, Methylaminomethyl, methylaminoethyl or benzyl. - II - The general or residual 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 given for these radicals in the respective combinations or preferred combinations of radicals are independently replaced by corresponding radical definitions of other preferred ranges, regardless of the combination specified in each case

The 2- (2-hydroxyphenyl) -3-methoxyacrylic acid methyl ester required as starting material for carrying out process a) according to the invention is known and can be prepared by known processes (EP-A 242081)

Formula (III) provides a general definition of the acrylic acid halides required to carry out process a) according to the invention as starting materials

In this formula (III), G, R, R ² and Z 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 G, R, R ² and Z has been specified X is halogen, preferably chlorine

Some of the acrylic acid halides of the formula (III) are known (Balsamo, A, Crotti, P, Lapucci, A, Macchia, B, Macchia, F, et al, J Med Chem, 24, 5, 1981, 525-532) and / or can be prepared from the corresponding acrylic acids using methods known per se (compare, for example, Padmanathan, T, Sultanbawa, MUS,

J Chem Soc, 1963, 4210-4218 or Wiley, van der Pias, J Chem Eng Data, 10, 1965, 72) can be prepared by halogenation with conventional halogenating agents, such as, for example, thionyl chloride or oxalyl chloride

New, and also the subject of the present application, are acrylic acid halides of the general formula (IH-a), - f T -

in which

Rl, R ² , R ³ , X and Z have the meanings given above.

The acrylic acid halides of the formula (III-a) are obtained if (process b) acrylic acids of the general formula (IV)

in which

R, R ² , R ³ and Z have the meanings given above,

with a halogenating agent, such as thionyl chloride, phosgene, phosphorus pentachloride or phosphorus oxychloride, optionally in the presence of a diluent, such as 1,2-dichloroethane, at temperatures of 0 to 150 ° C (see also the preparation examples).

Formula (IV) generally defines the acrylic acids required as starting materials for carrying out process b) according to the invention. In this formula (IV), R, R ² , R ³ and Z preferably or in particular have those meanings which have already been in connection with the description of the inventive ß compounds of formula (I) have been indicated as preferred or as particularly preferred for Rl, R ² , R ³ and Z.

The acrylic acids of formula (IV) as new substances are also the subject of the present application. They are obtained if (process c) acrylic acid esters of the formula (V),

in which

R, R ² , R ³ and Z have the meanings given above and

R ^{4 represents} alkyl,

optionally hydrolyzed in the presence of a diluent, for example an alcohol such as methanol or ethanol, optionally in a mixture with water, and optionally in the presence of a base such as sodium hydroxide or potassium hydroxide or an acid such as hydrochloric acid or sulfuric acid.

Formula (V) provides a general definition of the acrylic acid esters required as starting materials for carrying out process c) according to the invention. In this formula (V), R, R ² , R ³ and Z 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, R ² , R ³ and Z were given. R ⁴ represents alkyl, preferably methyl or ethyl. The acrylic acid esters of the formula (V) are also the subject of the present application as new substances. They are obtained if (process d) α-diketone monooximes of the formula (VI),

in which

R, R ³ and Z have the meanings given above,

with an alkoxycarbonylmethanephosphonic acid dialkyl ester of the formula (VII),

in which

R ² and R ^{4 have} the meanings given above and

R ^{5 represents} alkyl,

if appropriate in the presence of a diluent, for example an ether, such as tetrahydrofuran, and if appropriate in the presence of a base, for example potassium t-butoxide or sodium hydride.

Formula (VI) provides a general definition of the α-diketone monooximes required as starting materials for carrying out process d) according to the invention. In of this formula (VI), R, R ³ and Z preferably or in particular have those meanings which have already been given as preferred or as particularly preferred for R, R ³ and Z in connection with the description of the compounds of the formula (I) according to the invention .

The α-diketone monooximes of the formula (VI) are known and / or can be prepared by known methods (compare, for example, Diels; Stern, Chem.Ber., 40 (1907), 1624).

Formula (VII) provides a general definition of the alkoxycarbonylmethanephosphonic acid dialkyl esters further required as starting materials for carrying out process d) according to the invention. In this formula (VII), R ² and R ⁴ preferably or in particular have those meanings which have already been given as preferred or as particularly preferred for R ² and R ⁴ in connection with the description of the compounds of the formula (I) according to the invention. R ^ stands for

Alkyl, preferably for methyl or ethyl.

The alkoxycarbonylmethanephosphonic acid dialkyl esters of the formula (VII) are known synthetic chemicals.

Suitable diluents for carrying out process a) 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; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; Sulfones such as sulfolane; as well as amines, such as pyridine. Process a) according to the invention is optionally carried out in the presence of a suitable acid acceptor. All customary inorganic or organic bases are suitable. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates , such as 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, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecen (DBU)

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

Process a) can be varied over a wide range. In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 0 ° C to 80 ° C.

To carry out process a) according to the invention for the preparation of the compounds of the formula (I), 1 to 15 moles, preferably 1, are generally employed per mole of the methyl 2- (2-hydroxyphenyl) -3-methoxy-acrylic acid of the formula (II) up to 8 moles of the acrylic acid halide of the formula (III)

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 from the reaction products by known processes (see also the preparation 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 control Plasmodiophoromycetes,

Use 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 diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:

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 grarninis;

Sphaerotheca species, such as, for example, Sphaerotheca Fülliginea;

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 fact that the active ingredients 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 used particularly successfully to combat diseases in wine, fruit and vegetable cultivation, such as, for example, against Venturia, Sphaerotheca and Podosphaera species. fought

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

In the protection of materials, the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms. Technical materials in the present context are understood to mean non-living materials which 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 agents - 11- be lubricants and other materials that can be attacked or decomposed by microorganisms. In the context of the materials to be protected, parts of production plants, for example cooling water circuits, are also mentioned which can be impaired by the multiplication of microorganisms. In the context of the present invention, the preferred technical materials are adhesives, glues, papers and cartons,

Leather, wood, paints, cooling lubricants and heat transfer liquids called, particularly preferably wood.

Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can bring about a degradation or a change in the technical materials. The active compounds according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (basidio mycetes) and against slime organisms and algae.

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

Alternaria, 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, very fine Encapsulation in polymeric substances 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 foaming 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, highly 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 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. The following are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and

Tobacco stem. Possible emulsifiers and / or foaming agents are: e.g. nonionic 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. Possible dispersants are: e.g. Lignin liquor and methyl cellulose.

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

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

The formulations generally contain between 0.1 and 95 percent by weight

Active ingredient, 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, anilazine, azaconazole, azoxystrobin,

Benalaxyl, benodanil, benomyl, benzamacril, benzamacrylic isobutyl, bialaphos, binapacrylic, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,

Calcium polysulfide, Capsimyci, Captafol, Captan, Carbendazim, Carboxin, Carvon,

Quinomethionate (quinomethionate), chlobenthiazon, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofüram, Debacarb, dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithorphoxinodonine, dithorphononine

Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,

Famoxadone, fenapanil, fenarimol, fenbuconazole, fenfüram, 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, fucazolecis, furconazoloxis,

Guazatin,

Hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovededione,

Kasugamycin, Kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,

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

Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,

Ofürace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin, Paclobutrazole, Pefürazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin, Polyoxorim, probenazole, Prochloraz, Procymidon, Propamocarb, Propanosine-Sodium, Propiconazole, Propineb, Pyrazophos, Pyrifen, Pyifenox, Pyroyfurilonil

Quinconazole, quintozen (PCNB),

Sulfur and sulfur preparations,

Tebuconazole, tecloftalam, tecnazene, Tetcyclacis, tetraconazole, thiabendazole, Thicyofen, Thifluzamide, thiophanate-methyl, thiram, Tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, Triazbutil, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,

Uniconazole,

Validamycin A, vinclozolin, viniconazole,

Zarilamid, Zineb, Ziram as well

Dagger G,

OK-8705,

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

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, {2-Methyl-l - [[[l- (4-methylphenyl) -ethyl] -ammo] -carbonyl] -propyl} -carbamic acid-l-isopropyl ester

1 - (2,4-dichlorophenyl) -2- (1 H- 1, 2,4-triazol-1-yl) -ethanone-O- (phenylmethyl) -oxime,

1 - (2-methyl-1-naphthalenyl) - 1 H-pyrrole-2, 5-dione, 1 - (3, 5-dichlorophenyl) -3 - (2-propenyl) -2, 5-pyrrolidinedione, l- [ (Diiodomethyl) sulfonyl] -4-methyl-benzene,

1 - [[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1 H-imidazole, l - [[2- (4-chlorophenyl) -3-phenyloxiranyl] - methyl] -IH-l, 2,4-triazole,

1 - [1 - [2 - [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] - 1H-imidazole, 1-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,

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

2,2-dichloro-N- [1 - (4-chloro-henyl) -ethyl] - 1-ethyl-3-methyl-cyclopropanecarboxamide,

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-β-D-glycopyranosyl) -aD-glucopyranosyl] amino] -4-methoxy-1 H-pyrrolo [2,3-d] pyrimidine -5-carbonitrile, 2-aminobutane,

2-bromo-2- (bromomethyl) pentandinitrile,

2-CMor-N- (2,3-dihydro-l, l, 3-trimethyl-lH-inden-4-yl) -3-pyridinecarboxamide,

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

2-phenylphenol (OPP), 3, 4-dichloro-1 - [4- (difluoronethoxy) phenyl] - 1 H-pyrrole-2, 5-dione,

3,5-DicUor-N- [cyan [(1-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-Cuor-2-cyan-N, N-dimethyl-5- (4-methylphenyl) -lH-imidazole-l-sulfonamide, 4-methyl-tetrazolo [1, 5-a] quinazolin-5 (4H) -one ,

8- (1, 1-dimethylethyl) -N-ethyl-N-propyl-1, 4-dioxaspiro [4.5] decane-2-methanamine,

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, ice-1 - (4-chlorophenyl) -2- (1 H- 1, 2, 4-triazol-1 -yl) -cycloheptanol, cis-4- [3- [4- (l, l-dimethylpropyl) phenyl-2-methylpropyl] -2,6-dimethyl-moφholin hydrochloride, ethyl - [( 4-chlorophenyl) azo] cyanoacetate,

Potassium hydrogen carbonate,

Methane tetrathiol sodium salt,

Methyl 1 - (2, 3-dihydro-2,2-dimethyl-1 H-inden-1-yl) - 1 H-imidazole-5-carboxylate,

Methyl N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate, methyl-N- (chloroacetyl) -N- (2, 6-dimethylphenyl) -DL-alaninate,

N- (2,3-dichloro-4-hydroxyphenyl) -1-methylcyclohexane carboxamide.

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) - 1,4,5, 6-tetrahydro-2-pyrinidamine,

N- (4-hexylphenyl) - 1, 4,5,6-tetrahydro-2-pyrimidamine,

N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) acetamide,

N- (6-methoxy) -3-pyridinyl) cyclopropanecarboxamide,

N- [2,2,2-TricWor-l - [(cUoracetyl) aminino] ethyl] benzamide, N- [3-chloro-4,5-bis- (2-propynyloxy) phenyl] -N ' -methoxy-methanimidamide,

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

O, O-diethyl- [2- (dipropylaιrιino) -2-oxoethyl] ethylphosphoramidothioate,

O-methyl-S-phenyl-phenylpropylphosphoramidothioate,

S-methyl-l, 2,3-benzothiadiazole-7-carbothioate, spiro [2H] -l-benzopyran-2, r (3Η) -isobenzofüran] -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, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,

Bacillus thuringiensis, 4-bromo-2- (4-chloro-phenyl) -l- (ethoxymethyl) -5- (trifluoromethyl) - lH-pyrrole-3-carbonitrile, bendiocarb, benfüracarb, bensultap, betacyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin, butocarboxim, butylpyridaben,

Cadusafos, Carbaryl, Carbofüran, Carbophenothion, Carbosulfan, Cartap, Chloethocarb,

Chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, N - [(6-chloro-3-pyridmyl) -methyl] -N'-cyano-N-methyl-etharamidamide, chlorophyros, chloropyrifos M, cis-resmethrin, clocythrin, Clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,

Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos,

Etrimphos,

Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flucycloxuron, Flucythrinat, Flufenproxuron, Flufenproxuron

Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,

Lamda-cyhalothrin, Lufenuron, - 3> o - Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,

Naled, NC 184, Nitenpyram

Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,

Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos, Promecarb,

Propaphos, Propoxur, Prothiophos, Prothoat, Pymetrozin, Pyrachlophos, Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,

Quinalphos,

Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,

Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralathenethrononium, Tralomenhriazonium

Triflumuron, trimethacarb,

Vamidothione, XMC, xylylcarb, zetamethrin.

A mixture with other known active ingredients, such as herbicides or with

Fertilizers and growth regulators are possible.

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 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 Inject active ingredient into the soil yourself. 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 / ha. 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. When treating the floor, the application rates are applied

Active ingredient generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

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

The application concentrations of the active compounds 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

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 effectiveness and the spectrum of activity of the active substances to be used according to the invention in the protection of materials or of the agents, concentrates or very generally formulations which can be produced therefrom can be increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active substances are used to increase the Spectrum of effects or achieving special effects such as added protection against insects. These mixtures can have a broader spectrum of activity than those according to the invention

Links. ~ ll-

Preparation Examples:

Example 1)

Procedure a)

6.9 g (0.03 mol) of 3- (3-trifluoromethyl-phenyl) -but-2-enoic acid are refluxed with 3.9 g (0.033 mol) of thionyl chloride for one hour. Excess thionyl chloride is distilled off under reduced pressure and the residue, the crude 3- (3-trifluoromethylphenyl) but-2-enoyl chloride, is treated with a solution of 5.6 g (0.027 mol) of 2- (2-hydroxyphenyl) -3-methoxy-acrylic acid methyl ester in 30 ml dimethylformamide. After stirring for 15 minutes, 1.08 g (0.027 mol) of 60% sodium hydride suspension are added at 20 ° C. and stirring is continued for 16 hours. Now the reaction mixture is poured onto 200 ml of water, extracted twice with 50 ml of ethyl acetate each time, the organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo. The residue is chromatographed on silica gel using tert-butyl methyl ether / petroleum ether (1: 1). 3.9 g (35% of theory) of 3- (3-trifluoromethylphenyl) but-2-enoic acid 2- (2-methoxy-1-methoxycarbonyl-vinyl) phenyl ester are obtained.

iH-NMR spectrum (CDCI3 / TMS): δ - 2.63 (3H); 3.67 (3H); 3.82 (3H); 6.30-6.31 (1H); 7.22-7.74 (8H); 7.56 (1H) ppm. Production of the starting material:

34 g (0.139 mol) of 3- (3-trifluoromethyl-phenyl) but-2-enoic acid methyl ester are dissolved in 200 ml of methanol, 24.8 g (0.28 mol) of 45% strength aqueous sodium hydroxide solution are added and the mixture is stirred at 20 for 16 hours ° C stirred. The solvent is distilled off in vacuo, the residue is taken up in 100 ml of water, acidified with about 150 ml of 2N hydrochloric acid (pH 1) and extracted twice with 50 ml of ethyl acetate each time. The organic phase is dried over sodium sulfate, the solvent is distilled off in vacuo and the residue is stirred with petroleum ether. 17 g (53% of theory) of 3- (3-trifluoromethyl-phenyl) -but-2-enoic acid are obtained.

iH-NMR spectrum (CDCI3 / TMS): δ = 2.62 (d, 3H); 6.19 (q, 1H); 7.48-7.55 (1H); 7.64-7.73 (3H) ppm.

Preparation of the preliminary stage: W

33.2 g (0.183 mol) of dimethyl methoxycarbonylmethanephosphonate are added dropwise to a solution of 20.5 g (0.183 mol) of potassium tert-butoxide in 200 ml of tetrahydrofuran. 31.2 g (0.16 mol) of 3- (trifluoromethyl) acetophenone are then added dropwise at 20 ° C. and the mixture is then refluxed for three hours. The solvent is distilled off in vacuo, 200 ml of water are added to the residue and the mixture is extracted twice with 100 ml of ethyl acetate each time. The organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo. The product is then distilled at 0.5 torr and 80-90 ° C. 34.6 g (85.4% of theory) of methyl 3- (3-trifluoromethyl-phenyl) -but-2-enate are obtained as a mixture of stereoisomers.

iH-NMR spectrum (CDCI3 / TMS): δ = 2.20 (d, 3H, Z-isomer); 2.59 (d, 3H, E isomer); 3.56 (3H, Z isomer); 3.77 (3H, E isomer); 5.98 (q, 1H, Z isomer); 6, 16 (q, 1H, E isomer); 7.27-8.22 (4H) ppm.

- IX

Example (D

Procedure a)

3.24 g (0.018 mol) of 4-methoxyimino are added dropwise at 20 ° C. to a solution of 3.84 g (0.018 mol) of 2- (2-hydroxyphenyl) -3-methoxy-acrylic acid methyl ester in 20 ml of pyridine -3-methylpent-2-enoic acid chloride. The reaction mixture is left to stand for 30 minutes, 30 ml of toluene are then added and the volatile constituents are distilled off in

Vacuum. The residue is taken up in diethyl ether, washed with 20 ml of 2N aqueous hydrochloric acid and then with saturated aqueous sodium carbonate solution. After the solvent has been distilled off in vacuo, the residue is chromatographed on silica gel using diethyl ether. This gives 2.09 g (32.6% of theory) of 4-methoxyimino-3-methyl-pent-2-enoic acid 2- (2-methoxy-1-methoxycarbonyl-vinyl) phenyl ester as an oil.

iH-NMR spectrum (CDCI3 / TMS): δ = 2.02 (3H); 2.39 / 2.40 (3H, d); 3.66 (3H); 3.80 (3H); 3.99 (3H); 4.02 (3H); 6.21 / 6.21 (1H, q) ppm, 7.18-7.38 (4H); 7.54 (1H) ppm.

- IX

Production of the starting material:

Example (III-a-D

Procedure b)

1.6 g (0.01 mol) of 4-methoxyimino-3-methylpent-2-enoic acid are refluxed with 1.8 g (0.015 mol) of thionyl chloride in 10 ml of dichloroethane for 30 minutes. Volatile constituents are distilled off under reduced pressure and the residue is distilled under high vacuum. 0.8 g (45% of theory) of 4-methoxyimino-3-methylpent-2-enoic acid chloride are obtained as a mixture of stereoisomers.

¹ H NMR Spectrum (CDCI3 / TMS): δ = 2.00 (3H, isomer A + isomer B); 2, 11 / 2.12

(3H, d, isomer B); 2.33 / 2.33 (3H, d, isomer A); 3.92 (3H, isomer B); 4.02 (3H, isomer A); 5.88 (1H, isomer B); 6.36 / 6.37 (1H, q, isomer A) ppm.

- *> -

Production of the preliminary stage:

Example (TV-D:

Procedure c)

35.8 g (0.209 mol) of 4-methoxyimino-3-methylpent-2-enoic acid methyl ester are dissolved in 600 ml of methanol, mixed with 300 ml of 2N sodium hydroxide solution and under for 30 minutes

Reflux cooked. The solvent is distilled off in vacuo, the residue is taken up in 300 ml of water and acidified with about 350 ml of 2N hydrochloric acid (pH <1). The product precipitates and is filtered off. 18.2 g (55.4% of theory) of 4-methoxyimino-3-methylpent-2-enoic acid are obtained as a mixture of stereoisomers.

^Ϊ H NMR Spectrum (CDCI3 / TMS): δ = 2.00 (s, 3H, isomer A); 2.01 (s, 3H, isomer B); 2.06 / 2.07 (d, 3H, isomer B); 2.37 (d, 3H, isomer A); 3.90 (s, 3H, isomer B); 3.99 (s, 3H, isomer A); 5.59 (1H, isomer B); 6.10 (q, 1H, isomer A) ppm.

- ^ 8 -

Production of the preliminary stage:

Example (V-1):

Procedure d)

12.4 g (0.068 mol) of dimethyl methoxycarbonylmethanephosphonate are added dropwise at 0 ° C. to a solution of 7.63 g (0.068 mol) of potassium tert-butoxide in 70 ml of tetrahydrofuran. 0.068 mol) of butane-2,3-dione-mono- (O-methyl-oxime) and then boiled under reflux for 30 minutes. The solvent is distilled off in vacuo, the residue is mixed with 50 ml of water and extracted twice with 50 ml each Diethyl ether The organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo. The product is then distilled at 17 torr. 5.16 g (44% of theory) of methyl 4-methoxyimino-3-methylpent-2-enoate are obtained as a mixture of stereoisomers with a Boiling range from 95 to 105 ° C

¹ H NMR Spectrum (CDCI3 / TMS) δ = 1.98 (s, 3H, isomer A), 2.00 (s, 3H, isomer B), 2.03 (d, 3H, isomer B), 2 , 35 (d, 3H, isomer A), 3.69 (s, 3H, isomer B), 3.74 (s, 3H, isomer A), 3.89 (s, 3H, isomer B), 3.98 (s, 3H, isomer A), 5.83 (q, 1H, isomer

B), 6.08 (q, 1H, isomer A) ppm

Analogously to Examples (1) and (2), and in accordance with the general description of the production process a) according to the invention, the compounds of the formula (Ia) according to the invention listed in Table 1 below are also obtained

Table 1

- o-

Table 1 (continued)

- <1 ι

Examples of use:

Example A

Sphaerotheca test (cucumber) / protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight is mixed

Active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate 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 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 10 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, for example, the following compounds of preparation examples (1) show an efficiency of 97% compared to the untreated control at an exemplary active compound application rate of 100 g / ha. Example B ^" ^ -

Podosphaera test (apple) / protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the 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 the Podosphaera leucotricha apple flour thawing agent. The plants are then placed in the greenhouse at about 23 ° C. and a relative humidity of about 70%.

In this test, for example, the following compound of the preparation examples (1) shows an efficiency of 95% compared to the untreated control with an exemplary active compound application rate of 10 g / ha.

Example C

Venturia test (apple) / protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

To produce a suitable W kstoffl preparation, 1 part by weight of active ingredient 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 conidia suspension of the Venturia inaequalis apple scab pathogen and then remain in an incubation cabin at about 20 ° C. and 100% relative atmospheric humidity for 1 day.

The plants are then placed in the greenhouse at approx. 21 ° C. and a relative humidity of approx. 90%.

Evaluation is carried out 12 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, e.g. the following compound of the preparation examples (1) with an exemplary active ingredient application rate of 10 g / ha an efficiency of 100% compared to the untreated control.

Claims

Claims ~ <i 4

Compounds of the formula (I),

in which

G for a single bond, optionally interrupted by heteroatoms alkanediyl (the carbon atom to which R * is bound is always linked to a carbon atom of the alkanediyl chain)

N, .R ° or a grouping ^l O stands,

wherein

R ^{3 represents} hydrogen or in each case optionally substituted alkyl or cycloalkyl,

R ^{2 represents} hydrogen or in each case optionally substituted alkyl or cycloalkyl,

Z represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heterocyclyl.

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

Rl represents hydrogen, cyano or alkyl optionally substituted by halogen or alkoxy having 1 to 4 carbon atoms and having 1 to 6

R ^{2 represents} hydrogen or alkyl having 1 to 6 carbon atoms optionally substituted by halogen or alkoxy having 1 to 4 carbon atoms or cycloalkyl having 3 to 8 carbon atoms optionally substituted by halogen, alkyl or alkoxy each having 1 to 4 carbon atoms,

for a single bond, optionally interrupted by one or two heteroatoms, alkanediyl with 1 to 5 chain links (but the carbon atom to which R is bound is always linked to a carbon atom of the alkanediyl chain) or a grouping

stands,

wherein

R ^{3 stands} for hydrogen or for alkyl with 1 to 6 carbon atoms optionally substituted by halogen or alkoxy with 1 to 4 carbon atoms or for cycloalkyl with 3 to 8 carbon atoms optionally substituted by halogen, alkyl or alkoxy with 1 to 4 carbon atoms, - 7 for optionally single or multiple, identical or different by halogen, cyano, hydroxy, amino, C j -C4-alkoxy, CJ-C4-alkylthio, C1-C4-alkylsulfinyl or -C-C4-alkylsulfonyl (which in each case optionally by halogen may be substituted) substituted alkyl having 1 to 8 carbon atoms;

or for phenyl, naphthyl, cycloalkyl or cycloalkenyl, each of which is optionally mono- or polysubstituted, the same or different, each having 3 to 8 carbon atoms or for heterocyclyl having 3 to 7 ring members, at least one of which is for oxygen, sulfur or nitrogen and optionally one or two more are nitrogen, where the possible substituents are preferably selected from the list below: halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl;

each straight-chain or branched alkenyl or alkenyl oxy each having 2 to 6 carbon atoms;

each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;

each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 11 identical or different halogen atoms; each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl or alkylsulfonyloxy, each having 1 to 6 carbon atoms in the individual alkyl parts;

each optionally mono- or polysubstituted, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, in each case double-linked

Alkylene or dioxyalkylene each having 1 to 6 carbon atoms;

Cycloalkyl of 3 to 8 carbon atoms;

A ¹ or a grouping _{2 k} ,

wherein

A represents alkyl having 1 to 4 carbon atoms or cycloalkyl having 1 to 6 carbon atoms and

A ^{2 represents} optionally substituted by cyano, alkoxy, alkylthio, alkylamino, dialkylamino or phenyl alkyl having 1 to 4 carbon atoms, alkenyl or alkynyl each having 2 to 4 carbon atoms.

extensions of the formula (I) according to Claim 1, -tf9- in which

R1 represents hydrogen, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, trifluoroethyl, cyclopropyl, cyclobutyl,

G for a single bond, methanediyl, 1,1-ethanediyl, 1,2-ethanediyl 1,1-, 1,2-, 1,3- or 2,2-propanediyl, 1,1-, 1,2-, 1 , 3-, 1,4-, 2,2-, 2,3-butanediyl or 1,1-, 1,2- or l, 3- (2-methyl-propanediyl), -O-CH ₂ - (where Z is connected to the oxygen atom), or a grouping

N, .R ³

° in which R ^{3 represents} hydrogen or optionally substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,

Z for phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, oxazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,4- Oxadiazolyl, 1,3,4-oxadiazolyl, pyridinyl, pyrimidyl, pyridazinyl,

Pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,

3,5-triazinyl or 5,6-di-hydro-l, 4,2-dioxazinyl, the possible substituents preferably being selected from the following list: fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl , Difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, methoxycarbonyl, ethoxycarbonyl, each optionally monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, methyl, trifluoromethyl or ethyl and in each case doubly linked methylenedioxy, ethylenedioxy

A! or a grouping ₂

in which

A ² for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, allyl,

Propargyl, but-2-en-l-yl, 2-methyl-prop-l-en-3-yl, cyanomethyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, methylthioethyl, ethylthioethyl, dimethylaminomethyl, Dimethylaminoethyl,

Methylaminomethyl, methylaminoethyl or benzyl.

4. Compounds of formula (I) according to claim 1,

in which

R ^{2 represents} hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,

Trifluoromethyl, trifluoroethyl, cyclopropyl, cyclobutyl, -S ^" t> - G for a single bond or -O-CH2- (where Z is connected to the oxygen atom) or in particular for a grouping

stands,

woπn

R ³ for hydrogen or optionally mono- to trisubstituted by fluorine, chlorine, bromine, methoxy, ethoxy (which are each optionally substituted by fluorine and / or chlorine) substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,

for each optionally one to six times by fluorine, chlorine, bromine, methoxy, ethoxy, phenyl (which optionally by fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy is substituted), methyl, ethyl, n- or i-propyl substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;

Z is in each case optionally single to triple, identical or different, by chlorine, fluorine, bromine, cyano, hydroxy, amino, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl , Difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl;

for in each case optionally up to three times, identical or different from chlorine, fluorine or bromine, substituted vinyl, allyl or propargyl; or for phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1,2-oxazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1, which are optionally mono- to trisubstituted by identical or different substituents , 2,4-oxadiazolyl, 1,3,4-oxadiazolyl, pyridinyl, pyrimidyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl or 5.6 -Dihydro-l, 4,2-dioxazinyl, the possible substituents preferably being selected from the following list: fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-, i- , s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difoxychlorif Difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, methoxycarbonyl, ethoxycarbonyl,

each optionally monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, methyl, trifluoromethyl or ethyl and in each case double-linked methylendioxy, ethylendioxy

A! or a grouping ₂

in which

A ^ represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl or cyclobutyl and

A ² for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, allyl,

Propargyl, but-2-en-l-yl, 2-methyl-prop-l-en-3-yl, cyanomethyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, methylthioethyl, l-ethylthioethyl, dimethylaminomethyl, dimethylaminoethyl,

Methylaminomethyl, methylaminoethyl or benzyl.

5. Compounds of formula (I) according to claim 1,

in which

R represents methyl or cyclopropyl,

R ^{2 represents} hydrogen,

Z represents 1,2-oxazolyl or in particular phenyl which is optionally monosubstituted to trisubstituted in the same or different ways, the possible substituents preferably being selected from the following list: fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i- Propyl. n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy , Difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, methoxycarbonyl, ethoxycarbonyl,

each optionally mono- to tetrasubstituted, identically or differently, by fluorine, chlorine, methyl, trifluoromethyl or ethyl, in each case double-linked methylenedioxy, ethylendioxy

A ¹ . or a grouping of _{2 N} in which

A ² for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, allyl,

Methylaminomethyl, methylamino ethyl or benzyl.

6. Compounds of formula (I) according to claim 1,

in which

Rl represents methyl or cyclopropyl,

R ^{2 represents} hydrogen,

G for a grouping stands

wherein

R ^{3 represents} methyl,

Z for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, trifluoroethyl, methoxymethyl, methylthiomethyl or methylsulfonylmethyl, vinyl, dichlorovinyl, allyl, propargyl, cyclopropyl, methylcyclopropyl, cyclobutyl, Cyclopentyl, cyclohexyl or is in each case optionally monosubstituted to trisubstituted, identical or differently substituted 1,2-oxazolyl or in particular phenyl, the possible substituents preferably being selected from the list below: fluorine, chlorine, bromine, cyano, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluorochloromethoxy, Trifluoromethylthio, di-fluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, methoxycarbonyl, ethoxycarbonyl,

As _^ CH, or a grouping of _{2 N}

in which

A ² for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, allyl,

Propargyl, but-2-en-l-yl, 2-methyl-prop-l-en-3-yl, cyanomethyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, methylthioethyl,

Ethylthioethyl, dimethylaminomethyl, dimethylaminoethyl, methylaminomethyl, methylaminoethyl or benzyl.

7. pesticides, characterized by a content of at least one compound of the formula (I) according to claim 1.

8. A method for controlling pests, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on pests and / or their habitat.

9. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that (process a) 2- (2-hydroxyphenyl) -3- methoxyacrylic acid methyl ester (II)

with an acrylic acid halide of the general formula (III)

in which

G, R, R ² and Z have the meanings given above and

X represents halogen,

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

10. Connections of (Ill-a),

in which

R, R ² , R ³ , X and Z have the meanings given in claim 1.

11. A process for the preparation of compounds of the formula (III-a) according to claim 10, characterized in that (process b) acrylic acids of the general formula (IV),

in which

Rl, R ² , R ³ and Z have the meanings given in claim 1,

with a halogenating agent, such as thionyl chloride, phosgene, phosphorus pentachloride or phosphorus oxychloride, if appropriate in the presence of a diluent, such as, for example, 1,2-dichloroethane, at temperatures from 0 to 150 ° C. (see also the preparation examples).

12. Compounds of the formula (IV),

in which

R, R ² , R ³ and Z have the meanings given in claim 1.

13. A process for the preparation of compounds of the formula (IV) according to claim 12, characterized in that (process c) acrylic acid esters of the formula (V),

in which

Rl, R ² , R ³ and Z have the meanings given in claim 1 and

R ^{4 represents} alkyl,

14. Compounds of the formula (V),

in which

R, R ² , R ³ and Z have the meanings given in claim 1.

15. A process for the preparation of compounds of the formula (V) according to claim 14, characterized in that (process d) α-diketone monooximes of the formula (VI),

in which

R, R ³ and Z have the meanings given in claim 1,

in which R ² and R ^{4 have} the meanings given above and

R ^{5 represents} alkyl,

optionally in the presence of a diluent, for example one

Ethers, such as tetrahydrofuran, and optionally in the presence of a base, such as potassium t-butoxide or sodium hydride.

16. Use of compounds of formula (I) and agents according to claims 1 to 7 for controlling pests.

17. A process for the preparation of pesticides, characterized in that compounds of the formula (I) according to Claims 1 to 6 are mixed with extenders and / or surface-active agents.