EP0970061A1

EP0970061A1 - Fungicidal alkoximinomethyldioxazine derivatives

Info

Publication number: EP0970061A1
Application number: EP98912428A
Authority: EP
Inventors: Peter Gerdes; Herbert Gayer; Bernd-Wieland Krüger; Ulrich Heinemann; Bernd Gallenkamp; Ralf Tiemann; Stefan Dutzmann; Karl-Heinz Kuck; Klaus Stenzel
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1997-03-13
Filing date: 1998-03-02
Publication date: 2000-01-12
Also published as: WO1998040365A1; DE19710355A1; US6281209B1; AU6727098A; JP2001518082A

Abstract

The invention relates to novel alkoximinomethyldioxazine derivatives of formula (I), a method for the production and the use thereof as fungicides, in addition to novel intermediate products and several methods for the production thereof.

Description

FUNGIZ IDE ALKOXI INOMETHYLDIOXAZINE DERIVATIVES

The invention relates to new alkoximinomethyldioxazine derivatives, a process for their preparation and their use as fungicides, as well as new intermediates and several processes for their production.

It has already become known that certain alkoximinomethyldioxazine derivatives, which are constitutionally similar to those described below, have fungicidal properties (see, for example, WO-A 9504728). The fungicidal activity of these compounds, however, leaves something to be desired, especially at low application rates. The new alkoximinomethyldioxazine derivatives of the general formula (I) have now been found

in which

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

grouping stands in what

R ^ represents optionally substituted alkyl or cycloalkyl,

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

R ^ represents hydrogen or in each case optionally substituted alkyl or cycloalkyl, Z represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heterocyclyl and

E ^, Ε? -, Ε? and E ^ are the same or different and each independently represent hydrogen, alkyl, haloalkyl or hydroxyalkyl, or

El and W- or E * and E ^ or E ^ and E ^ together with the respective carbon atoms to which they are attached form a cycloaliphatic ring and

i, 1? -, L? and i, are the same or different and each independently represent hydrogen, halogen, cyano, nitro, each optionally substituted by halogen substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl.

In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkanediyl, alkenyl or alkynyl, are in each case straight-chain or branched, also in combination with heteroatoms, such as in alkoxy, alkylthio or alkylamino. If an alkyl or alkanediyl chain is interrupted by more than one heteroatom, 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, as well as

Pseudohalogens, such as, for example, cyano, preferably for fluorine, chlorine, bromine or cyano, in particular for fluorine or chlorine.

Aryl stands for aromatic, mono or polycyclic hydrocarbon rings, e.g. 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 is 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. If necessary, the ring-shaped connections form with others carbocyclic or heterocyclic, fused or bridged rings together form a polycychic 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 polycychic ring system with further carbocyclic, fused or bridged rings.

Furthermore, it was found that the new alkoximinomethyldioxazine derivatives of the general formula (I) are obtained if (process a) 3- (l-hydroxyphenyl-l-alkoximinomethyl) dioxazines of the general formula

in which

E, E ^, E ^, E4, L, L ^, l? and have the meanings given above, 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.

Finally, it was found that the new alkoximinomethyldioxazine derivatives of the general formula (I) have a very strong fungicidal activity.

The compounds of the invention can optionally be used as mixtures of various possible isomeric forms, in particular stereoisomers, such as. B. 20

E and Z or optical isomers are present. Both the E and the Z isomers, the individual enantiomers, the racemates and any mixtures of these isomers are claimed.

The present application preferably relates to alkoximinomethyl-dioxazine derivatives of the formula (I) in which

Rl for hydrogen, cyano or optionally with halogen or alkoxy

1 to 4 carbon atoms substituted alkyl with 1 to 6 carbon atoms or for optionally by halogen, alkyl or alkoxy each with 1 to 4

Carbon-substituted cycloalkyl having 3 to 8 carbon atoms,

R ^ 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 (although the carbon atom to which R * is bound always has a carbon atom of

N. .R ^J

Alkanediyl chain is connected) or a group ^' °, in which

R represents hydrogen or alkyl, each optionally substituted by halogen or alkoxy having 1 to 4 carbon atoms, having 1 to 6 Carbon atoms, alkenyl having 2 to 6 carbon atoms or alkynyl having 2 to 6 carbon atoms or for cycloalkyl having 3 to 8 carbon atoms optionally substituted by halogen, alkyl or alkoxy each having 1 to 4 carbon atoms or for arylalkyl having 1 to 4 carbon atoms optionally substituted in the aryl part Alkyl part stands, where the substituents are selected from the following list:

Halogen, cyano, nitro, formyl, carbamoyl, thiocarbamoyl, each straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms, each straight-chain or branched alkenyl, alkenyloxy or alkynyloxy 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 1 1 identical or different halogen atoms, each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroximinoalkyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts, each optionally one or more times, 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 the same or different halogen atoms substituted, in each case doubly linked alkylene or dioxyalkylene, each having 1 to 6 carbon atoms,

for optionally single or multiple, the same or different

Halogen, cyano, hydroxy, amino, Cj-C ^ alkoxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl or C1-C4-alkylsulfonyl (which can in each case optionally be substituted by halogen) 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, haloalkylsulfmyl 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;

straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl or alkylsulfonyloxy, each with

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; t

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 -

or a group in which

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

A ^ is alkyl with 1 to 4 carbon atoms which is optionally substituted by cyano, alkoxy, alkylthio, alkylamino, dialkylamino or phenyl,

Alkenyl or alkynyl each having 2 to 4 carbon atoms and

E, Ε? -, Ε? and Εß are the same or different and independently represent hydrogen, alkyl or hydroxyalkyl each having 1 to 4 carbon atoms or haloalkyl having 1 to 4 carbon atoms and 1 to five identical or different halogen atoms, or

E and E ^ or E * and E- or E ^ and Εß together with the respective carbon atoms to which they are attached form a cycloaliphatic ring with five, six or seven carbon atoms and

let, l2-, l? and are the same or different and each independently represent hydrogen, halogen, cyano, nitro, each optionally substituted by 1 to 5 halogen atoms, alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms.

The present application 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 ^ 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 is connected to the oxygen atom),

Z for each 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, trifluoroethoxy, trifluoroethoxy - methylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl; for phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, oxazolyl, benzofuranmyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,4-oxa which are each mono- to trisubstituted in the same or different ways - diazolyl, 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, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, trifluoromethylthio, Difluorchlor- methylthio, 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

Al represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl or cyclobutyl and 3

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, methylthio-methyl, ethylthiomethyl, methylthioethyl, ethylthioethyl, dimethylamino-methyl, dimethylaminoethyl, methylaminomethyl, methylaminoethyl or

Benzyl stands and

E, E ² , E ^ and E ^ are the same or different and are independently hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, hydroxymethyl, trifluoromethyl or Trifluorethyl stand, or

E and E ² or E * and E- or E ^ and Εß together with the respective carbon atoms to which they are attached form a cycloaliphatic ring with five, six or seven carbon atoms and

L, L ² , L ^ and L ^ are the same or different and are each independently hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, di-fluorochloromethoxy, trifluoromethylthio, difluoromethylthio, difluoromethyl, difluoromethyl, difluoromethyl Trifluoromethylsulfinyl or Trifluormethylsulfonyl stand.

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

R1 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 grouping stands in what lO

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 allyl, crotonyl, 1-methyl-allyl, propargyl or 1-methyl-propargyl which are optionally monosubstituted to trisubstituted by fluorine or chlorine;

for each 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; stands for benzyl, phenyl-1-ethyl or phenyl-2-ethyl which is monosubstituted to trisubstituted in the phenyl part in each case, the possible substituents preferably being selected from the list below:

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

Difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, acetyl, propionyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl, methylsulfonyloxy, ethylsulfonyloxy, hydroximino-methyl, hydroximinoethyl, methoximinomethyl, ethoximinoethyl; ethoximinoethyl;

each optionally mono- or polysubstituted, identically or differently, by fluorine, chlorine, methyl, trifluoromethyl, ethyl, n- or i-propyl, in each case doubly linked trimethylene (propane-1,3-diyl), methylenedioxy or ethylenedioxy, for each optionally single to triple, identical or different, by chlorine, fluorine, bromine, cyano, hydroxyl, amino, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoromethoxy, trifluoromethyl, Trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, substituted 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, benzofüranyl, 1,2,4-thiadiazolyl, 1,3,4-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, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl,

Trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, methoxycarbonyl, ethoxycarbonyl, ethoxy

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, meth- n oxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, methylthioethyl, ethylthioethyl, dimethylaminomethyl, dimethylaminoethyl, methylaminomethyl, methylaminoethyl or benzyl and

El and E ² or E * and E ^ or E- and Ε together with the respective

Carbon atoms to which they are attached form a cycloaliphatic ring with five, six or seven carbon atoms and

L, L ² , L ^ and Ix are the same or different and are each independently hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, di-fluorochloromethoxy, trifluoromethyl, diflifluoromethyl, diflifluoromethyl, diflifluoromethyl, diflifluoromethyl, diflifluoromethyl, difluorifluoromethyl stand.

A particularly preferred group of compounds according to the invention are those compounds of the formula (I) in which

Rl stands for 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 for each optionally single to triple, identical or different, by chlorine, fluorine, bromine, cyano, hydroxyl, amino, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoromethyl, trifluoromethoxy, trifluoromethoxy, , Trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl; or represents 1,2-oxazolyl or benzofüranyl, 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, trifluorethoxy, difluoromethylthio, trifluoromethylthio, trifluoromethyltrifluoromethyloxytrifluoromethyloxytrifluoromethyloxytrifluoromethyloxytrifluoromethyltrifluoromethyltrifluoromethyl or for

each optionally up to four times, the same or different by fluorine,

Chlorine, methyl, trifluoromethyl or ethyl substituted, each linked twice methylenedioxy, ethylenedioxy

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,

El and E ^{2 are the} same or different and are each independently

Are methyl or in particular hydrogen,

E ^ and E ^ stand for hydrogen, Ll and L ^ are the same or different and each independently represent methyl or in particular hydrogen and

L ² and ß stand for hydrogen.

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

Rl stands for cyclopropyl or in particular methyl,

R ^{2 represents} hydrogen.

G stands for a grouping ^N X ° X ^R3 , in which

R ^ in particular represents methyl or benzyl which is monosubstituted to trisubstituted by fluorine, chlorine, bromine, cyano, nitro, methyl or methoxy, optionally in the phenyl part,

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 for 1,2-oxazolyl, benzofüranyl or in particular phenyl which is in each case monosubstituted to trisubstituted by identical or different substituents, 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, trifluorethoxy, difluoromethylthio, trifluoromethylthio, trifluoromethyltrifluoromethyloxytrifluoromethyloxytrifluoromethyloxytrifluoromethyloxytrifluoromethyltrifluoromethyltrifluoromethyl or for each optionally monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, methyl, trifluoromethyl or ethyl and in each case doubly linked methylenedioxy, ethylenedioxy

or a grouping, where

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,

E ^ and E ^{2 are the} same or different and each independently represents methyl or in particular hydrogen,

E ^ and Εß stand for hydrogen,

eats and? are identical or different and each independently represent methyl or in particular hydrogen and

L ² and ß stand for hydrogen.

The general or residual definitions given above or in the preferred ranges 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 radical definitions of the respective other preferred ranges, regardless of the combination specified in each case. Formula (II) provides a general definition of the 3- (l-hydroxyphenyl-l-alkoximinomethyl) dioxazines required as starting materials for carrying out process a) according to the invention. In this formula (II), E *, E ² , E ^, E ^, iß, L ² , L ^ and iß preferably or in particular have those meanings which are already in connection with the description of the compounds of the formula according to the invention

(I) as preferred or as particularly preferred for E ^, E ² , E ^, E ^, iß, L ² , L ^ and iß.

The 3- (l-hydroxyphenyl-l-alkoximinomethyl) dioxazines of the formula (II) are known and can be prepared by known processes (WO 95-04728).

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 have already been mentioned as preferred or as particularly preferred for G, Rl in connection with the description of the compounds of the formula (I) according to the invention , R ² and Z were specified. X represents 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 by known methods from the corresponding acrylic acids (see for example Padmanathan, T .; Sultanbawa, MUS, J.Chem. Soc, 1963, 4210-4218 or Wiley; van der Pias, J.Chem.Eng.Data, 10, 1965, 72) 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),

(Ill-a)

in which '3-

R, R ² , R ^, 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)

(IV)

in which

RR ² , R 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 from 0 to

150 ° C (see also the manufacturing 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 ,? and Z preferably or in particular those meanings which have already been given in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for R, R ² , R ^ 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? and Z have the meanings given above and

R ^{4 represents} alkyl,

optionally 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, hydrolyzed.

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) have Rl, R ² , R? and Z preferably or in particular 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? and Z were specified. 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)

(VI)

in which

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

with an alkoxycarbonylmethanephosphonic acid dialkyl ester of the formula (VII), * 9

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 an ether such as tetrahydrofuran, and optionally in the presence of a base such as

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 this formula (VI), R, R and Z preferably or in particular have those

Meanings which have already been given in connection with the description of the compounds of the formula (I) according to the invention as preferred or as particularly preferred for R, R and Z.

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).

The alkoxycarbonylmethanephosphonic acid dialkyl esters still required as starting materials for carrying out process d) according to the invention are as follows:

Formula (VII) generally defined. 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 ^ is alkyl, preferably methyl or ethyl.

The alkoxycarbonylmethanephosphonic acid dialkyl esters of the formula (VII) are known synthetic chemicals. 2

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 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 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 varied within a substantial range when carrying out process a) according to the invention. 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 mol, preferably 1 to 8 mol, are generally employed per mole of 3- (l-hydroxyphenyl-l-alkoximino-methyl) dioxazine of the formula (II) Mole of an acrylic acid halide of the formula (III). l \

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 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, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and

Use 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; ΎL

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

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; n

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

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

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

The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases 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 Leptosphaeria species, diseases in wine, fruit and vegetable cultivation, for example against Venturia and Plasmopara species, or for rice diseases, for example against Pyricularia species. Other cereal diseases, such as, for example, Septoria, Pyrenophora or Cochliobolus species, are also successfully combated.

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.

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

Cold and warning smoke formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents Means. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol Ή 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 under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and 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 stalks. 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%.

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. 15

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, capsimycin, captafol, captan, carbendazim, carboxin, carvone, quinomethionate (quinomethionate), chlobenthiazon, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyprodinconol, cypodinconol

Debacarb, dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole

M, Dinocap, Diphenylamine, Dipyrithione, Ditalimfos, Dithianon, Dodemorph, Dodine, Drazoxolon,

Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,

Famoxadone, Fenapanil, Fenarimol, Fenbuconazol, Fenfüram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzon, Fluazinam, Flumetover, Fluoromid, Fluquinconazol, Fluφrimidolutin, Flusilimidol, Flusulfimidol, Flusulfimidol, Flusulfimidol, Flusulfimidol, Flusulfimidol, Flusulfilidol, Flusulfinidol, Flusulfilidol, Flusulfinidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusulfilidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusulfilidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusilimidol, Flusulfilidol, Fosetyl sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox,

Guazatin, 2t,

Hexachlorobenzene, hexaconazole, hymexazole,

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

Isovaledione,

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, Mepanipyrirri, 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, pyrifenox, pyrimethanil, pyroquilon, pyroxy for,

Quinconazole, quintozen (PCNB),

Sulfur and sulfur preparations,

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

Triadimefon, Triadimenol, Triazbutil, Triazoxid, Trichlamid, Tricyclazol, Tridemoφh, Triflumizol, Triforin, Triticonazol,

Uniconazole,

Validamycin A, vinclozolin, viniconazole, Zarilamid, Zineb, Ziram as well

Dagger G,

OK-8705,

OK-8801,

α- (1, 1-dimethylethyl) -ß- (2-phenoxyethyl) - IH-1, 2,4-triazole-1-ethanol,

α- (2,4-dichlorophenyl) -ß-fluoro-b-propyl-1 H-1, 2,4-triazole-1-ethanol,

α- (2,4-dichloφhenyl) -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] - IH- 1, 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- (methoxyinτino) -N-methyl-2-phenoxy-phenylacetamide,

{2-Methyl- 1 - [[[1 - (4-methylphenyl) ethyl] amino] carbonyl] propyl} carbamic acid 1-isopropyl ester

1 - (2,4-dichloφhenyl) -2- (IH- 1, 2,4-triazol-1-yl) -ethanone-O- (phenylmethyl) -oxime,

l- (2-methyl-l-naphthalenyl) -lH-pyrrole-2,5-dione,

1 - (3, 5 -dichloφhenyl) -3 - (2-propenyl) -2, 5-pyrrolidinedione,

l - [(diiodomethyl) sulfonyl] -4-methyl-benzene,

1 - [[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] - 1H-imidazole,

1 - [[2- (4-chloro-phenyl) -3-phenyloxiranyl] methyl] - IH-1, 2,4-triazole,

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

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

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

2,6-DicMor-5- (methyltWo) -4-pyrinidinyl-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) pentandinitrile,

2-chloro-N- (2,3-dihydro-1,1,3-trimethyl-1 H-inden-4-yl) -3-pyridinecarboxamide,

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

2-phenylphenol (OPP),

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

3,5-dichloro-N- [cyan [(1-methyl-2-propynyl) oxy] methyl] benzamide,

3 - (1,1-dimethylpropyl-1-oxo-1 H-indene-2-carbonitrile,

3- [2- (4-chloro-phenyl) -5-ethoxy-3-isoxazolidinyl] pyridine, ^" 'S

4-chloro-2-cyan-N, N-dimethyl-5- (4-methylphenyl) -1 H-imidazole-1-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- (1-methylethyl) -3-methyl-4 - [(3 -methylbenzoyl) -oxy] -2, 5 -thiophene dicarboxylate,

ice 1 - (4-chloro-phenyl) -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-chloro-phenyl) -azo] cyanoacetate,

Potassium hydrogen carbonate,

Methane tetrathiol sodium salt,

Methyl 1 - (2,3-dihydro-2,2-dimethyl-1 H-inden-1-yl) - 1H-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-methyl-cyclohexane 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) -l, 4,5,6-tetrahydro-2-pyrimidinamine,

N- (4-hexylphenyl) - 1,4,5,6-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-1 - [(chloroacetyl) amino] 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- (dipropylamino) -2-oxoethyl] ethyl phosphoramidothioate,

O-methyl-S-phenyl-phenylpropylphosphoramidothioate,

S-methyl-1, 2,3-benzothiadiazole-7-carbothioate,

spiro [2H] -1-benzopyran-2, 1 '(3 Η) -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, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,

Bacillus thuringiensis, 4-bromo-2- (4-chloro-phenyl) - 1 - (ethoxymethyl) -5- (trifluoromethyl) - 1H-pyrrole-3-carbonitrile, bendiocarb, benfüracarb, bensultap, betacyfluthrin, bifenthrin,

BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxim, Butylpyridaben, Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N - [(6- Chloro-3-pyridinyl) -methyl] -N-cyano-N-methyl-ethanimidamide, Chloφyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin,

Cyhalothrin, cyhexatin, cypermethrin, cyromazine,

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicüphos, 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, Flufenproxatonophon, Flufenproxaton, Fufenionfonium, Flufenproxofonon, Flufenproxofonon, Furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

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

Lamda-cyhalothrin, Lufenuron,

Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathione, 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, Tralomenhriazon, Tralomenhriazon, Tronomenhrononium,

Vamidothione, XMC, xylylcarb, zetamethrin.

A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also 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 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 process 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 the active compounds according to the invention are used 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 seeds. 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. Manufacturing examples:

example 1

Procedure a)

0.69 g (0.003 mol) of 3- (3-trifluoromethyl-phenyl) -but-2-enoic acid are mixed with 0.39 g

(0.0033 mol) thionyl chloride and 10 ml 1,2-dichloroethane boiled under reflux for one hour. Volatile constituents are distilled off under reduced pressure and the residue, the crude 3- (3-trifluoromethylphenyl) but-2-enoyl chloride, is dissolved in 20 ml of dimethylformamide. This solution is added dropwise to a mixture of 0.62 g (0.0027 mol) (5,6-dihydro- [l, 4,2] dioxazin-3-yl) - (2-hydroxyphenyl) methanone-O methyl oxime and 0.848 g (0.0028 mol) of 80% sodium hydride suspension in 30 ml of dimethylformamide and stirred for a further 16 hours. Now the reaction mixture is poured onto 50 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 ethyl acetate / cyclohexane (1: 1). 0.99 g (82% of theory) of 3- (3-trifluoromethylphenyl) but-2-enoic acid 2 - [(5,6-dihydro- [1,4,2] dioxazin-3-yl ) -methoxyimino-methylj-phenyl ester.

^Ϊ H NMR Spectrum (CDCI3 / TMS): δ = 2.64 (s, 3H); 3.94 (s, 3H); 4.17 (m. 2H); 4.48 (m. 2H); 6.34 (s, IH); 7.26-7.78 (m, 8H) ppm. H

Production of the starting material:

CF,

34 g (0, 139 mol) of methyl 3- (3-trifluoromethyl-phenyl) -but-2-esters 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 for 16 hours stirred at 20 ° C. 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.

^Ϊ H NMR Spectrum (CDCI3 / TMS): δ = 2.62 (d, 3H); 6.19 (q, IH); 7.48-7.55 (IH); 7.64-7.73 (3H) ppm.

Production of the preliminary stage:

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, IH, Z isomer); 6, 16 (q, IH, E isomer); 7.27-8.22 (4H) ppm.

b

Example 2

Procedure a)

To a solution of 1.08 g (0.0046 mol) (5,6-dihydro- [4,2,2] dioxazin-3-yl) - (2-hydroxyphenyl) methanone-O-methyl-oxime 180 mg (0.0045 mol) of 60% sodium hydride suspension are added to 5 ml of dimethylformamide and the mixture is stirred until the evolution of gas has ended. 0.8 g (0.0045 mol) of 4-methoxyimino-3-methylpent-2-enoic acid chloride is added dropwise at 0 ° C. The reaction mixture is left to stand for 10 minutes, poured onto water and extracted with 10 ml of ethyl acetate. The organic phase is dried over sodium sulfate and the volatile constituents are distilled off in vacuo. The residue is stirred with petroleum ether. 2.09 g (32.6% of theory) of 4-methoxyimino-3-methylpent-2-enoic acid 2 - [(5,6-dihydro- [l, 4,2] dioxazin-3-yl) - are obtained methoxyiminomethyl] phenyl ester as an oil.

^Ϊ H NMR Spectrum (CDCI3 / TMS): δ = 2.03 (3H); 2.41 (d, 3H); 3.92 (3H); 4.00 (3H); 4.09-4.17 (2H); 4.45-4.48 (2H); 6.24 (q, IH), 7.25-7.32 (3H); 7.41-7.47 (IH) ppm.

Production of the starting material:

Example (HI-a-1)

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

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

3β

Production of the preliminary stage:

Example (IV-1):

CH ₃ O

^H 3χ, χAlX _OH CH ₃

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.

iH-NMEl 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 (IH, isomer B); 6.10 (q, IH, Isomer A) ppm.

Production of the preliminary stage:

Example (V-l):

Procedure d)

12.4 g (0.068 mol) of dimethyl methoxycarbonylmethanephosphonate are added dropwise to a solution of 7.63 g (0.068 mol) of potassium tert-butoxide in 70 ml of tetrahydrofuran. Then 7.83 g (0.068 mol) of butane-2,3-dione-mono- (O-methyl-oxime) are added dropwise at 20 ° C. and the mixture is then refluxed for 30 minutes. The solvent is distilled off in vacuo, 50 ml of water are added to the residue and the mixture is extracted twice with 50 ml of diethyl ether each time. 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 4-methoxyimino-3-methylpent-2-enoic acid methyl ester are obtained as a mixture of stereoisomers with a boiling range from 95 to 105 ° C.

iH-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, IH, isomer B); 6.08 (q, IH, 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 (I-a) according to the invention listed in Table 1 below are also obtained:

Table 1

Ψ

q2

Examples of use:

Example A

Plasmopara test (vine) / protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

1 part by weight is mixed to produce a suitable preparation of material

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 Plasmopara viticola 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 a greenhouse at about 21 ° C. and about 90% relative atmospheric humidity for 5 days. The plants are then moistened and placed in an incubation cabin for 1 day.

The expansion takes place 6 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), (4), (5), (6), (8) and (9) show an efficiency of up to 100% in the case of an exemplary amount of active ingredient applied of 100 g / ha Comparison to the untreated control. AROUND

Example B

Venturia 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 preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the apple scab pathogen Venturia inaequalis 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 compounds of the preparation examples

(1), (4), (5), (6), (7), (8) and (9) with an exemplary active ingredient application rate of 10 g / ha an efficiency of up to 100% compared to the untreated control. Example C

Leptosphaeria nodorum test (wheat) / protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To 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 sprayed with a spore suspension of Leptosphaeria nodorum. The plants remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 48 hours.

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

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 compound of preparation examples (4) shows an efficacy of 70% compared to the untreated control with an exemplary active compound application rate of 25 g / ha. Ψ

Example D

Pyricularia test (rice) / protective

Solvent: 2.5 parts by weight of acetone

Emulsifier: 0.06 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 amount of solvent and the concentrate is diluted to the desired concentration with water and the stated amount of emulsifier.

To test for protective activity, young rice plants are sprayed with the active substance preparation in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. Then the plants in a greenhouse at 100% relative

Humidity and 25 ° C.

Evaluation is carried out 4 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 (3), (7), (8) and (9) show an efficiency of more than 80% in comparison with an exemplary amount of active ingredient applied of 750 g / ha and an exposure time of one day for untreated control.

y

Example E

Puccinia test (wheat) / protective

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

Emulsifier: 0.06 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 amount of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young planters are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Puccinia recondita. The plants remain at 20 ° C. and 100% relative for 48 hours

Humidity in an incubation cabin.

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

Claims

claims

Compounds of formula (I)

in which

for a single bond, optionally interrupted by heteroatoms alkanediyl (but the carbon atom to which Rl is bound always with a carbon atom of the alkanediyl chain

connected) or a grouping stands in what

R ^ represents 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 and

El, E ² , E ^ and E ^{4 are the} same or different and each independently represent hydrogen, alkyl, haloalkyl or hydroxyalkyl, or L \ C)

El and E ² or El and E- or E ^ and E ⁴ together with the respective carbon atoms to which they are attached form a cycloaliphatic ring and

L, L ² , L ^ and L ⁴ , are the same or different and each independently represent hydrogen, halogen, cyano, nitro, each optionally substituted by halogen substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl.

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

Rl for hydrogen, cyano or for 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,

R ^{2 represents} hydrogen or alkyl having 1 to 6 carbon atoms which is optionally substituted by halogen or alkoxy having 1 to 4 carbon atoms or represents cycloalkyl having 3 to 8 carbon atoms which is 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 Rl is bound is always linked to a carbon atom of the alkanediyl chain) or a grouping

ι ^N ° ^R is what

R ^ for hydrogen or for each optionally by halogen or

Alkoxy with 1 to 4 carbon atoms substituted alkyl with 1 to 6 carbon atoms, alkenyl with 2 to 6 carbon atoms or alkynyl with 2 to 6 carbon atoms or for cycloalkyl with 3 to 8 carbon atoms optionally substituted by halogen, alkyl or alkoxy each with 1 to 4 carbon atoms or for if necessary in SO

Aryl part substituted arylalkyl having 1 to 4 carbon atoms in the alkyl part, the substituents being selected from the following list:

Halogen, cyano, nitro, formyl, carbamoyl, thiocarbamoyl, each straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms, each straight-chain or branched alkenyl, alkenyloxy or alkynyloxy 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, alkylsulfonyloxy, hydroximinoalkyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts, in each case optionally one or more times, 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 with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms substituted, in each case doubly linked alkylene or dioxyalkylene, each with 1 to 6 carbon atoms,

for optionally single or multiple, identical or different, by halogen, cyano, hydroxy, amino, C1-C4-alkoxy, C1-C4-alkylthio, -C-C4-alkylsulfinyl or C1-C4-alkylsulfonyl (which can each be optionally substituted by halogen ) substituted alkyl with 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 by identical or different substituents, 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, the possible substituents preferably being selected from the list below:

Halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl;

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 1 1 identical or different halogen atoms;

in each case straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl or alkylsulfonyloxy, each with 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;

Heterocyclyl or heterocyclyl-methyl each having 3 to 7 ring members, of which 1 to 3 are identical or different heteroatoms

- especially nitrogen, oxygen and / or sulfur - A or a grouping ₂ L., where

A ² ^ ^. NO

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 and

El, E ² , E- and E ^{4 are the} same or different and are independently hydrogen, alkyl or hydroxyalkyl each having 1 to 4 carbon atoms or haloalkyl having 1 to 4 carbon atoms and 1 to five identical or different halogen atoms, or

El and E ² or El and E- * or E- and E ⁴ together with the respective carbon atoms to which they are attached form a cycloaliphatic ring with five, six or seven carbon atoms and

Ll, L ² , iß and L ^{4 are the} same or different and are each independently hydrogen, halogen, cyano, nitro, each optionally substituted by 1 to 5 halogen atoms, alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms Substance atoms stand.

3. Compounds of formula (I) according to claim 1, 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-CH - (where Z is connected to the oxygen atom),

Z is in each case optionally one to three times, the same or different, using chlorine, fluorine, bromine, cyano, hydroxy, amino, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl, , Difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl; for phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, oxazolyl, benzofüranyl, 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- Tri-azinyl 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,

A ¹ or a grouping ₂ ύ _> where

Al 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,

Is ethylthioethyl, dimethylaminomethyl, dimethylaminoethyl, methylaminomethyl, methylaminoethyl or benzyl and

E, E ² , E ^ and E ^{4 are the} same or different and independently of one another for hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-

Butyl, hydroxymethyl, trifluoromethyl or trifluoroethyl are available, or

El and E ² or El and E ^ or E- and E ⁴ together with the respective carbon atoms to which they are attached form a cycloaliphatic ring with five, six or seven carbon atoms and

Ll, L ² , L ^ and L ^{4 are the} same or different and are each independently hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulfinyl,

Ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromifluoromethylsulfonyl.

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

G for a grouping stands in what R ^ for hydrogen or methyl, ethyl, n- or i-propyl, n-, i- , s- or t-butyl,

for each optionally up to six times by fluorine, chlorine, bromine, methoxy, ethoxy, phenyl (which may be 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; for each optionally monosubstituted to trisubstituted in the phenyl part

Is benzyl, phenyl-1-ethyl or phenyl-2-ethyl, the possible substituents preferably being selected from the list below:

Fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n - or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulphinyl, trifluoromethylsulphonyl, acetyl, propionyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl, methylsulfonyloxy,

Ethylsulfonyloxy, hydroximinomethyl, hydroximinoethyl, methoximino-methyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl;

each optionally mono- or polysubstituted, identically or differently, by fluorine, chlorine, methyl, trifluoromethyl, ethyl, n- or i-propyl, in each case doubly linked trimethylene (propane-1,3-diyl), methylenedioxy or ethylenedioxy,

Z for in each case optionally up to three times, identically or differently by chlorine, fluorine, bromine, cyano, hydroxyl, amino, methoxy, ethoxy,

Methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, Trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, substituted 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, benzofüranyl, 1,2,4-thiadiazolyl which are optionally monosubstituted to trisubstituted by identical or different substituents,

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:

A ¹ or a grouping _{2 K} , where

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, X

Dimethylaminoethyl, methylaminomethyl, methylaminoethyl or benzyl and

Butyl, hydroxymethyl, trifluoromethyl or trifluoroethyl are available, or

El and E ² or El and E ^ or E- * and E ⁴ together with the respective carbon atoms to which they are attached form a cycloaliphatic ring with five, six or seven carbon atoms and

Ll, L ² , iß and L ^{4 are the} same or different and are each independently hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulfinyl,

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

Rl represents methyl or cyclopropyl,

R ^{2 represents} hydrogen,

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; represents optionally mono- to trisubstituted, identical or differently substituted phenyl, 1,2-oxazolyl or benzofüranyl, 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,

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

El and E ^{2 are the} same or different and each independently represent hydrogen or methyl,

E ^ and E ^{4 represent} hydrogen,

L and iß are the same or different and each independently represent hydrogen or methyl and ^s 3 iß and L ^{4 represent} hydrogen.

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

Rl represents methyl or cyclopropyl,

R ^{2 represents} hydrogen.

I.

G stands for a grouping ^N v ° x ^R , in which

R ^ represents methyl or benzyl which is monosubstituted to trisubstituted by fluorine, chlorine, bromine, cyano, nitro, methyl or methoxy, optionally in the phenyl part,

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 for each optionally mono- to trisubstituted, identically or differently substituted 1,2-oxazolyl, benzofüranyl or in particular phenyl, the possible substituents preferably being derived from the the following list is selected:

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,

or a grouping, where Al 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, ethylthioethyl, dimethylaminomethyl, dimethylaminoethyl, methylaminomethyl, Methylaminoethyl or benzyl,

E and E ^{2 are the} same or different and each independently represent hydrogen or methyl,

E ^ and E ^{4 represent} hydrogen,

Ll and L- are the same or different and each independently represent hydrogen or methyl and

L ² and L ^{4 represent} hydrogen.

7. pesticide, 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. Use of compounds of formula (I) or agents according to claims 1 to 7, for controlling pests.

10. A process for the preparation of pesticides, characterized in that compounds of the formula (I) or agents according to Claims 1 to 7 are mixed with extenders and / or surface-active agents. 11. A process for the preparation of compounds of formula (I) as defined in claim 1, characterized in that (process a) 3- (l-hydroxyphenyl-l-alkoximinomethyl) dioxazines of the general formula

in which

El, E ² , E ^, E ⁴ , Ll, L ² , L ^ and L ^{4 have} the meanings given in claim 1, with an acrylic acid halide of the general formula (III)

in which

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

X represents halogen,

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

12. Compounds of the formula (III-a),

in which

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

13. A process for the preparation of compounds of the formula (purple) as defined in claim 12, characterized in that (process b) acrylic acids of the general formula (IV)

(iv)

in which

Rl, R ² , R ^ and Z have the meanings given in claim 12,

with a halogenating agent, optionally in the presence of a diluent at temperatures from 0 to 150 ° C.

14. Compounds of formula (IV)

in which b3

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

15. A process for the preparation of compounds of the formula (IV) as defined in claim 14, characterized in that (process c) acrylic acid esters of the formula (V)

in which

Rl, R ² , R ^ and Z have the meanings given in claim 14 and

R ^{4 represents} alkyl,

optionally hydrolyzed in the presence of a diluent, optionally in a mixture with water, and optionally in the presence of a base or an acid.

16. Compounds of the formula (V)

in which

Rl, R ² , R ^ and Z have the meanings given in claim 14 and

R ^{4 represents} alkyl, 17. A process for the preparation of compounds of the formula (V) as defined in claim 16, characterized in that (process d) α-diketone monooximes of the formula (VI)

(VI)

in which

R, R3 and Z have the meanings given in claim 16,

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

in which

R ² and R ^{4 have} the meanings given in claim 16 and

R5 represents alkyl,

if appropriate in the presence of a diluent and if appropriate in the presence of a base.