EP1483248A1

EP1483248A1 - Halobenzyl substituted phenylaceto esters and amides and use thereof for prevention of harmful organisms

Info

Publication number: EP1483248A1
Application number: EP03706519A
Authority: EP
Inventors: Fritz Maurer; Christiane Boie; Herbert Gayer; Ulrich Heinemann; Bernd-Wieland Krüger; Ulrike Wachendorff-Neumann; Astrid Mauler-Machnik; Peter Lösel
Original assignee: Bayer CropScience AG
Current assignee: Bayer CropScience AG
Priority date: 2002-03-01
Filing date: 2003-02-17
Publication date: 2004-12-08
Also published as: DE10209145A1; AU2003208863A1; WO2003074496A8; US20050124498A1; JP2005526746A; WO2003074496A1

Abstract

The invention relates to compounds of formula (I), where R1 = R5-O-#, R5-O-CH2-#, (a), (b), (c), (d) or (e), T= (f), (g), or (h), several methods for production and use thereof for the prevention of harmful organisms and novel intermediate products.

Description

HALOGEN-SUBSTITUTED DERIVATIVES OF PHENYLESSIC ACID ESESTERS AND AMIDES AND THEIR USE FOR COMBATING DANGEROUS ORGANISMS

The invention relates to new halogenobenzenes, several processes for their preparation and their use for controlling harmful organisms, and new ones

Intermediates and processes for their manufacture.

Certain halogen-substituted benzene derivatives, which have a similar substitution pattern to the new compounds described below, and their use as agents for controlling harmful organisms have already been disclosed (compare, for example, WO 95-04728, WO 98-21189, EP 460525, EP 398692, EP 865424, WO 95-18789, EP 253213, EP 382375). However, the action of these previously known compounds is not entirely satisfactory in all areas of application, especially at low application rates and concentrations.

The new halogenobenzenes of the general formula (I) have now been found

in which for one of the groupings

R5-O- # R5-O-CH ₂ - #

stands in what

R ^{5 represents} optionally substituted aryl,

R ^{6 represents} optionally substituted aryl,

R ⁷ , R ⁸ , R ⁹ and R ^{10 are} identical or different and independently of one another represent hydrogen, halogen, optionally substituted alkyl or optionally substituted alkoxy,

R ¹ ! represents optionally substituted alkyl, R ^{12 represents} in each case optionally substituted alkyl, alkoxy or aryl,

R ^{13 represents} in each case optionally substituted alkyl or aryl,

R ^{14 represents} optionally substituted aryl,

R ¹⁵ and R ^{16 are} identical or different and independently of one another represent hydrogen, halogen or alkyl,

X represents hydrogen or halogen

R ² , R ³ and R ^{4 are the} same or different and are independently hydrogen or halogen, but at least one of the radicals R ² , R ³ or R ^{4 is} halogen and

T for a grouping

^Stands -

In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkanediyl, alkenyl or alkynyl, are also each straight-chain or in combination with heteroatoms, such as, for example, in alkoxy, alkylthio or alkylamino branched. Unless otherwise stated, hydrocarbon chains having 1 to 6 carbon atoms are preferred.

Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.

Aryl stands for aromatic, mono- or polycyclic hydrocarbon rings, e.g. Phenyl, naphthyl, anthranyl, phenanthryl, preferably phenyl or naphthyl, especially phenyl.

Furthermore, it was found that the new halopyrimidines of the general formula (I) can be obtained if

a) a hydroxyhalophenyl derivative of the formula (II),

in which

R ² , R ³ , R ⁴ and T have the meanings given above,

with a phenoxypyrimidine of the general formula (III),

in which R ¹ and X have the meanings given above and

Y ^{1 represents} halogen,

or an alkoxypyrimidine of the general formula (IV),

in which

R ¹⁴ , R ¹⁵ and R ^{16 has} the meaning given above and

Y ^{2 represents} alkysulfonyl or arylsulfonyl,

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

4-phenoxypyrimidines of the general formula (V),

in which

R ² , R ³ , R ⁴ , T and X have the meanings given above and Y ^{3 represents} halogen,

with a phenol of the general formula (VI),

R ¹³ -OH (VI) in which

R ^{13 has} the meaning given above,

c) a hydroxyhalophenyl derivative of the formula (II) with a diaryliodonium halide of the general formula (VII),

(Y ⁵ ) ^'

in which

R ^{5 has} the meaning given above and

Y ^{5 represents} halogen,

optionally in the presence of a diluent and optionally in

Presence of an acid acceptor, or if one

d) a 2- (2-halomethylphenyl) -2-methoxyimino derivative of the formula (VIII),

in which

R ² , R ³ , R ⁴ and T have the meanings given above and

Y ^{6 represents} halogen,

with an oxime of the formula (IX),

in which

R ^{6 has} the meaning given above,

or with a benzofuranone oxime of the formula (X),

in which

R ⁷ , R ⁸ , R ⁹ and R ^{10 have} the meanings given above,

or with a bisoxime of the formula (XI), in which

R ¹ 1 and R ^{12 have} the meanings given above,

or with a phenol of the formula (XII),

R5-OH (XII)

in which

R ^{5 has} the meaning given above,

optionally in the presence of a diluent and optionally in

Presence of an acid acceptor, or if one

a halobenzene of the general formula (I-a),

in which

R ¹ , R ² , R ³ and R ^{4 have} the meanings given above, with methylamine, optionally in the presence of a diluent, or if one

f) reacting a halogenobenzene of the general formula (Ia) in a first stage with hydroxylamine or with a salt thereof, optionally in the presence of an acid acceptor and optionally in the presence of a diluent and without isolating the product of the first stage, in a second stage with dibromoethane , if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent.

Finally, it was found that the new halogenobenzenes of the general formula (I) have a strong action against harmful organisms, in particular a very strong fungicidal action.

The compounds of the invention can optionally be used as mixtures of various possible isomeric forms, in particular stereoisomers, such as. B. E- and Z- are present. Both the E and the Z isomers and any mixtures of these isomers are claimed.

The invention preferably relates to compounds of the formula (I) in which

R ¹ for each optionally substituted phenoxy or phenoxymethyl or for one of the groupings

R5-O- # R5-O-CH ₂ - #

stands in what

R ^{5 represents} optionally substituted phenyl,

R ^{6 represents} optionally substituted phenyl,

R ⁷ , R ⁸ , R ⁹ and R ^{10 are} identical or different and independently of one another represent hydrogen, optionally alkyl substituted by halogen or alkoxy optionally substituted by halogen, each having 1 to 4 carbon atoms, fluorine, chlorine, bromine or iodine,

R ^{1 1 represents} alkyl which has 1 to 4 carbon atoms and is optionally substituted by halogen, R ^{12 represents} in each case optionally substituted by halogen alkyl or alkoxy having 1 to 6 carbon atoms or optionally substituted phenyl,

R ^{13 represents} in each case optionally substituted by halogen alkyl having 1 to 6 carbon atoms or optionally substituted phenyl,

R ^{14 represents} alkyl which has 1 to 6 carbon atoms and is optionally substituted by halogen,

R ¹⁵ and R ^{16 are the} same or different and independently of one another represent hydrogen, fluorine, chlorine, bromine or alkyl having 1 to 4 carbon atoms,

X represents hydrogen, fluorine, chlorine, bromine or iodine,

R ² , R ³ and R ^{4 are the} same or different and are independently hydrogen, fluorine, chlorine, bromine or iodine, but at least one of the radicals R ² , R ³ or R ^{4 is} fluorine, chlorine, bromine or iodine and

T for a grouping

stands. The substituents of the aforementioned phenyl, phenoxy or phenoxymethyl radicals are preferably selected from the following list:

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

in each case straight-chain or branched alkyl, hydroxyalkyl, oxoalkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, dialkoxyalkyl, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 8 carbon atoms;

each straight-chain or branched alkenyl or alkenyloxy 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, alkylaminocarbonyl, dialkylaminocarbonyl, arylalkylaminocarbonyl, dialkylaminocarbonyloxy, alkenylcarbonyl or alkynylcarbonyl, with 1 to 6 carbon atoms in the respective hydrocarbon chains;

Cycloalkyl or cycloalkyloxy each having 3 to 6 carbon atoms; each optionally monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, oxo, methyl, trifluoromethyl or ethyl and in each case doubly linked alkylene having 3 or 4 carbon atoms, oxyalkylene having 2 or 3 carbon atoms or dioxyalkylene having 1 or 2 carbon atoms;

A ¹ or a group _M , in which

A ² ^

A ^{1 represents} hydrogen, hydroxy or alkyl having 1 to 4 carbon atoms or cycloalkyl having 1 to 6 carbon atoms and

A ² for hydroxyl, amino, methylamino, phenyl, benzyl or for alkyl or alkoxy with 1 to 4 carbon atoms optionally substituted by cyano, hydroxy, alkoxy, alkylthio, alkylamino, dialkylamino or phenyl, or for alkenyloxy or alkynyloxy each with 2 up to 4 carbon atoms.

The invention relates in particular to compounds of the formula (I) in which

R ⁵ -O- # R5-O-CH ₂ - #

stands in what

R ^{5 represents} optionally substituted phenyl,

R ^{6 represents} optionally substituted phenyl,

R ⁷ , R ⁸ , R ⁹ and R ^{10 are the} same or different and independently of one another represent hydrogen, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoromethoxy, fluorine, chlorine, bromine or iodine,

R ¹ ! represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,

R ^{12 is} methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy or optionally substituted phenyl,

R ^{13 represents} methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, pentyl, hexyl or optionally substituted phenyl,

R ^{14 represents} methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, pentyl, hexyl which is optionally substituted by fluorine or chlorine, R ¹⁵ and R ^{16 are the} same or different and independently of one another represent hydrogen, fluorine, chlorine, bromine, methyl or ethyl,

X represents hydrogen, fluorine, chlorine, bromine or iodine,

R ² , R ³ and R ^{4 are the} same or different and are independently hydrogen, fluorine or chlorine, but at least one of the radicals R ² , R ³ or R ^{4 is} fluorine or chlorine and

T for a grouping

stands.

The substituents of the phenyl radicals mentioned above are preferably selected from the following list:

Fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl

Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, 1-, 2-, 3-, neo-pentyl, 1-, 2-, 3-,

4- (2-methylbutyl), 1-, 2-, 3-hexyl, 1-, 2-, 3-, 4-, 5- (2-methylpentyl), 1-, 2-, 3- (3-methylpentyl ), 2-ethylbutyl, 1-, 3-, 4- (2,2-dimethylbutyl), 1-, 2- (2,3-dimethylbutyl), hydroxymethyl, hydroxyethyl, 3-oxobutyl, methoxymethyl, dimethoxymethyl, Methoxy, ethoxy, n- or i-propoxy, methoxy methyl, ethoxymethyl,

Methylthio, ethylthio, n- or i-propylthio, methylsulfonyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, methylthiomethyl, ethylthiomethyl,

Vinyl, allyl, 2-methylallyl, propen-1-yl, crotonyl, propargyl, vinyloxy, allyloxy, 2-methylallyloxy, propen-1-yloxy, crotonyloxy, propargyloxy;

Trifluoromethyl, trifluoroethyl,

Difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl,

Methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino,

Acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, dimethylaminocarbonyloxy, diethylaminocarbonyloxy, benzylaminocarbonyl, acryloyl, propioloyl,

Cyclopentyl, cyclohexyl,

in each case optionally up to four times, the same or differently substituted by fluorine, chlorine, oxo, methyl or trifluoromethyl, each linked twice

Propanediyl, ethyleneoxy, methylenedioxy, ethylenedioxy

A ¹ or a grouping '', where

A ² "A ^{1 represents} hydrogen, methyl or hydroxy and A ^{2 represents} hydroxy, methoxy, ethoxy, amino, methylamino, phenyl, benzyl or hydroxyethyl.

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

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

Process a) according to the invention can be illustrated by the following reaction equations:

Formula (II) provides a general definition of the hydroxyhalophenyl derivatives required as starting materials for carrying out process a) according to the invention. In this formula (II), R ² , R ³ , R ⁴ and T 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 ² , R ³ , R ⁴ and T were given. The starting materials of formula (II) are new and also the subject of the present application.

They are obtained (process g) if a keto ester of the general formula (XIII),

in which

R ² , R ³ and R ^{4 have} the meanings given above and

R ^{17 represents} alkyl,

R ^{18 represents} hydrogen or alkyl or

R ¹⁷ and R ¹⁸ together with the atoms to which they are attached form a six-membered ring,

or a hydroxyphenylglyoxylic acid ester of the general formula (XIV),

in which

R ² , R ³ and R ^{4 have} the meanings given above,

with methoxyamine hydrochloride, if appropriate in the presence of a diluent,

or if (process h) a hydroxyhalophenyl derivative of the formula (II-a),

in which

R ² , R ³ and R ^{4 have} the meanings given above,

with methylamine, optionally in the presence of a diluent.

Process g) according to the invention can be illustrated by the following reaction equations:

Formula (XIII) provides a general definition of the keto esters required as starting materials for carrying out process g) according to the invention. In this formula (XIII), R ² , R ³ and R ⁴ preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or as particularly preferred for R ² , R ³ and R ^{4 have been} given. R ¹⁷ represents alkyl, preferably methyl or ethyl. R ¹⁸ represents hydrogen or alkyl, preferably hydrogen, methyl or ethyl. R ¹⁷ and R ¹⁸ together with the atoms to which they are attached also represent a six-membered ring, preferably a tetrahydropyran ring.

The keto esters of the formula (XIII) are new and also a subject of the present invention. They are obtained (process i) if a ketal of the general formula (XV),

in which

R ² , R ³ , R ¹⁷ and R ^{18 have} the meanings given above,

with dimethyl oxalate, optionally in the presence of a diluent and optionally in the presence of a strong base.

Process i) according to the invention can be illustrated by the following reaction equation: oxalate

methanol

Formula (XV) provides a general definition of the ketals required as starting materials for carrying out process i) according to the invention. In this formula (XV), R ² , R ³ , R ¹⁷ and R ¹⁸ preferably or in particular have those meanings which are preferred or particularly preferred in connection with the description of the compounds of the formulas (I) and (XIII) according to the invention were preferably given for R ² , R ³ , R ¹⁷ and R ¹⁸ .

The compounds of the formula (XV) are known or can be prepared by known processes (see, for example, J.Amer.Chem.Soc. 119; 6; 1997; 1208-1216).

The dimethyl oxalate further required to carry out process i) according to the invention is a generally known laboratory chemical.

Formula (XIV) provides a general definition of the hydroxyphenylglyoxylic acid esters which are alternatively required as starting materials for carrying out process g) according to the invention. In this formula (XIV), R ² , R ³ and R ⁴ preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or as particularly preferred for R ² , R ³ and R ^{4 have been} given.

The hydroxyphenylglyoxylic acid esters of the formula (XIV) are new and also the subject of the present application. They are obtained (process j) if fluorophenols of the general formula (XVI), in which

R ² , R ³ and R ^{4 have} the meanings given above,

with oxalic acid methyl ester chloride, if appropriate in the presence of a diluent and if appropriate in the presence of a Lewis acid, or if (process k) the ketals of the formula (XV) described above are optionally hydrolyzed in the presence of a diluent and if appropriate in the presence of an acid ,

Process j) according to the invention can be illustrated by the following reaction equation:

Formula (XVI) provides a general definition of the fluorophenols required as starting materials for carrying out process j) according to the invention. In this formula (XVI), R ² , R ³ and R ⁴ preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or as particularly preferred for R ² , R ³ and R ^{4 have been} given. The fluorophenols of the formula (XVI), and also the methyl oxalate chloride required to carry out process j) according to the invention, are commercially available laboratory chemicals.

Process k) according to the invention can be illustrated by the following reaction equation:

The ketals of the formula (XV) required as starting materials for carrying out the process k) according to the invention have already been described above in connection with the description of the process g) according to the invention.

The hydroxylamine and its salts required to carry out process g) according to the invention and their salts are commercially available laboratory chemicals.

Process h) according to the invention can be illustrated by the following reaction equations:

Formula (II-a) generally defines the hydroxyhalophenyl derivatives required as starting materials for carrying out process h) according to the invention. In this formula (II-a), R ² , R ³ and R ⁴ 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 ² , R ³ and R ⁴ .

The hydroxyhalophenyl derivatives of the formula (ITa) are compounds according to the invention and can be prepared by process g).

The methylamine which is furthermore required as starting material for carrying out the process h) according to the invention is a commercially available laboratory chemical.

Formula (III) provides a general definition of the phenoxypyrimidines required as starting materials for carrying out process a) according to the invention. In this formula (III), R ¹³ and X preferably or in particular have the meaning which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred for

R ¹³ and X were given. Y ¹ represents halogen, preferably fluorine or chlorine.

The starting materials of the formula (III) are known and / or can be prepared by known methods (compare, for example, WO 97-27189).

Formula (IV) provides a general definition of the alkoxypyrimidines which can alternatively be used as starting materials for carrying out process a) according to the invention. In this formula (IV), R ¹⁴ , R ¹⁵ and R ¹⁶ preferably or in particular have the meaning which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or particularly preferred for R ¹⁴ , R ¹⁵ and R ^{16 were} specified. Y ² represents alkysulfonyl or arylsulfonyl, preferably methysulfonyl or tolylsulfonyl.

The starting materials of formula (IV) are known and / or can be known

Methods are produced (see, for example, WO 95-24396). Process b) according to the invention can be illustrated by the following reaction equation:

Formula (V) provides a general definition of the 4-phenoxypyrimidines required as starting materials for carrying out process b) according to the invention. In this formula (V), R ² , R ³ , R ⁴ , T and X preferably or in particular have those meanings which have been preferred or particularly preferred in connection with the description of the compounds of the formula (I) according to the invention for R ² , R ³ , R ⁴ , T and X were specified. Y ³ represents halogen, preferably fluorine or chlorine.

The starting materials of formula (V) are new and also the subject of the present application. They are obtained if (process 1) halopyrimidines of the formula (XVII),

in which

Y ³ and X have the meanings given above and

Y7 represents halogen, with a hydroxyhalophenyl derivative of the formula (II)

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

Process 1) according to the invention can be illustrated by the following reaction equation:

Formula (XVII) provides a general definition of the halopyrimidines required as starting materials for carrying out process 1) according to the invention. In this formula (XVII), Y ³ and X preferably or in particular have those meanings which have already been given as preferred or as particularly preferred for Y ³ and X in connection with the description of the compounds of the formula (V) according to the invention. Y7 represents halogen, preferably fluorine or chlorine.

The halopyrimidines of the formula (XVII) are known and can be prepared according to known ones

Processes are prepared (compare, for example, WO 97-27189 or WO 98-41513).

The hydroxyhalophenyl derivatives of the formula (II) which are further required as starting materials for carrying out process 1) according to the invention have already been described above in connection with the description of process a) according to the invention. Formula (VI) provides a general definition of the phenols which are furthermore required as starting materials for carrying out process b) according to the invention. In this formula (VI), R ¹³ preferably or in particular has the meaning which has already been stated as preferred or as particularly preferred for R ¹³ in connection with the description of the compounds of the formula (I) according to the invention.

The phenols of the formula (VI) are generally known synthetic chemicals.

Process c) according to the invention can be illustrated by the following reaction equation:

The hydroxyhalophenyl derivatives of the formula (II) required as starting materials for carrying out process c) according to the invention have already been described above in connection with the description of process a) according to the invention.

Formula (VII) provides a general definition of the diaryliodonium halides required as starting materials for carrying out process c) according to the invention. In this formula (VII), R ⁵ preferably or in particular has the meaning which has already been stated as preferred or as particularly preferred for R ⁵ in connection with the description of the compounds of the formula (I) according to the invention. The diaryliodonium halides of the formula (VII) are known or can be prepared by known methods (compare, for example, Synthesis (1995), (8), 1027-3).

Process d) according to the invention can be illustrated by the following reaction equations:

Formula (VIII) provides a general definition of the 2- (2-halomethylphenyl) -2-methoxyimino derivatives required as starting materials for carrying out process d) according to the invention. In this formula (VIII), R ² , R ³ , R ⁴ and T preferably or in particular have those meanings which have already been preferred in connection with the description of the compounds of the formula (I) according to the invention or as being particularly preferred for R ² , R ³ , R ⁴ and T. Y ⁶ represents halogen, preferably chlorine or bromine.

The compounds of formula (VIII) are new and also the subject of the present application. They are obtained if (process m) a 2- (2-methylphenyl) -2-methoxyimino derivative of the formula (XVIII),

(XVIII)

in which

R ² , R ³ , R ⁴ and T have the meanings given above,

with a halogenating agent, if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst.

Process m) according to the invention can be illustrated by the following reaction equation:

Formula (XVIII) provides a general definition of the 2- (2-methylphenyl) -2-methoxyimino derivatives required as starting materials for carrying out process m) according to the invention. In this formula (XVIII), R ² , R ³ , R ⁴ and T preferably or in particular have those meanings which have already been in connection with the Description of the compounds of formula (I) according to the invention as being preferred or as being particularly preferred for R ² , R ³ , R ⁴ and T.

The 2- (2-methyl-phenyl) -2-methoxyimino derivatives of the formula (XVIII) are new and also the subject of the present application. You will get one

(Process n) O-tolylpyruvic acid ester of the formula (XIX),

in which

R ² , R ³ and R ^{4 have} the meanings given above,

with methoxyamine or one of its salts, optionally in the presence of a diluent, or if (process o) a 2- (2-methylphenyl) -2-methoxyimino derivative of the formula (XVIII-a),

(XVIII-a)

in which

R ² , R ³ and R ^{4 have} the meanings given above,

with methylamine, if appropriate in the presence of a diluent, or if (process q) a 2- (2-methylphenyl) -2-methoxyimino derivative of the formula (XVIII-a) in a first stage with hydroxylamine or with a salt thereof, optionally in the presence of an acid acceptor and optionally in presence of a diluent, reacted and without isolation of the product of the first stage, in a second stage with dibromoethane, optionally in the presence of an acid acceptor and optionally in the presence of a diluent.

Process n) according to the invention can be illustrated by the following reaction equation:

Formula (XIX) provides a general definition of the O-tolylpyruvic acid esters required as starting materials for carrying out process n) according to the invention. In this formula (XIX), R ² , R ³ and R ⁴ preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (XIX) according to the invention, are preferred or particularly preferred for R ² , R ³ and R ^{4 were} given.

The O-tolylpyruvic acid esters of the formula (XIX) are new and also the subject of the present application. They are obtained (process p) if benzoyl cyanides of the formula (XX), in which

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

in the presence of methanol and optionally in the presence of an acid, hydrolyzed and esterified.

Process p) according to the invention can be illustrated by the following reaction equation:

Methanol, hydrogen chloride, acetic anhydride

Formula (XX) provides a general definition of the benzoyl cyanides required as starting materials for carrying out process p) according to the invention. In this formula (XX), R ² , R ³ and R ⁴ preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or as particularly preferred for R ² , R ³ and R ^{4 have been} given.

The benzoyl cyanides of the formula (XX) are new and also the subject of the present application. They are obtained (process r) if benzoic acid derivatives of the formula (XXI),

in which

R ² , R ³ and R ^{4 have} the meanings given above,

in a first stage with a chlorinating agent, if appropriate in the presence of a catalyst and if appropriate in the presence of a diluent, and, if appropriate without isolating the product of the first stage, in a second stage with trimethylsilyl cyanide.

Process r) according to the invention can be illustrated by the following reaction equation:

Formula (XXI) provides a general definition of the benzoic acid derivatives required as starting materials for carrying out process r) according to the invention. In this formula (XXI), R ² , R ³ and R ⁴ preferably or in particular have those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred or as particularly preferred for R ² , R ³ and R ^{4 have been} given. The benzoic acid derivatives of the formula (XXI) are known or can be prepared by known methods (compare, for example, DE 3328494).

The process o) according to the invention can be illustrated by the following reaction equation:

methanol

Formula (XVIII-a) provides a general definition of the 2- (2-methylphenyl) -2-methoxyimino derivative required as starting materials for carrying out process o) according to the invention. In this formula (XVIII-a), R ² , R ³ and R ⁴ 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 ² , R ³ and R ^{4 were} given.

The 2- (2-methyl-phenyl) -2-methoxyimino derivatives of the formula (XVIII-a) are compounds according to the invention and can be prepared by process n).

The methylamine which is furthermore required as starting material for carrying out the process o) according to the invention is a commercially available laboratory chemical.

Process q) according to the invention can be illustrated by the following reaction equation:

The 2- (2-methylphenyl) -2-methoxyimino derivatives required as starting materials for carrying out the process q) according to the invention are generally defined by the formula (XVIII-a) and have already been described in the description of the process n) according to the invention.

The substances hydroxylamine, or its salts and dibromoethane, which are further required as starting materials for carrying out the process q) according to the invention, are commercially available laboratory chemicals.

Suitable halogenating agents for carrying out process m) according to the invention are preferably all customary chlorination, bromination and iodination agents. Examples include: chlorine, bromine, iodine, chlorosuccinimide, bromosuccinimide, 1,3-dibromo-5,5-dimethylhydantoin or iodosuccinimide.

The halogenating agents mentioned are all common laboratory chemicals.

Formula (IX) provides a general definition of the oximes required as starting materials for carrying out process d) according to the invention. In this

Formula (IX) R ⁶ has preferably or in particular has that meaning which preferred as being preferred or particularly in connection with the description of the compounds of formula (I) according to the invention was specified for R. ⁶

The oximes of the formula (IX) are known synthetic chemicals or can be prepared from ketones and hydroxylamine by generally customary methods. Formula (X) provides a general definition of the benzofuranone oximes additionally required as starting materials for carrying out process d) according to the invention. In this formula (X), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ 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 ⁷ , R ⁸ , R ⁹ and R ^{10 were} given.

The benzofuranone oximes of the formula (X) are known or can be prepared by known methods (compare, for example, WO 9621640).

Formula (XI) provides a general definition of the bisoximes additionally required as starting materials for carrying out process d) according to the invention. In this formula (XI), R ^{1 1} and R ¹² 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 ¹ ! and R ^{12 were} given.

The bisoximes of the formula (XI) are known or can be prepared by known methods (compare, for example: WO 97-24317).

Formula (XII) provides a general definition of the phenols which are alternatively required as starting materials for carrying out process d) according to the invention. In this formula (XII), R ⁵ preferably or in particular has the meaning which has already been stated as preferred or as particularly preferred for R ⁵ in connection with the description of the compounds of the formula (I) according to the invention.

The phenols of the formula (XII) are generally known synthetic chemicals.

Process e) according to the invention can be illustrated by the following reaction equation:

Formula (I-a) provides a general definition of the halogenobenzenes required as starting materials for carrying out process e) according to the invention.

The halobenzenes of the formula (I-a) are substances according to the invention and can be prepared by processes a), b), c) or d) according to the invention.

The methylamine which is furthermore required as a starting material for carrying out process e) according to the invention is a commercially available laboratory chemical.

Process f) according to the invention can be illustrated by the following reaction equation:

Formula (Ia) provides a general definition of the halogenobenzenes required as starting materials for carrying out process f) according to the invention. The halobenzenes of the formula (Ia) are substances according to the invention and can be prepared by processes a), b), c) or d) according to the invention.

The substances hydroxylamine, or its salts and dibromoethane, which are further required as starting materials for carrying out the process f) according to the invention, are commercially available laboratory chemicals.

Suitable diluents for carrying out processes a), b) and 1) are all inert organic solvents. These preferably include ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Sulfoxides such as dimethyl sulfoxide; or sulfones, such as sulfolane.

Processes a), b) and 1) according to the invention are optionally carried out in the presence of a suitable acid acceptor. All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, alcoholates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium hydrogen carbonate or sodium hydrogen carbonate ,

The reaction temperatures can be carried out when carrying out the inventive

Processes a), b) and 1) can be varied over a wide range. In general, temperatures from 10 ° C to 80 ° C, preferably at temperatures from 20 ° C to 50 ° C.

To carry out the process a) according to the invention for the preparation of the compounds of the formula (I), per mol of the hydroxyhalophenyl derivative is used Formula (II) generally 1 to 5 moles, preferably 1 to 2 moles of phenoxypyrimidine in the formula (III).

To carry out the process b) according to the invention for the preparation of the compounds of the formula (I), the per

Formula (II) generally 1 to 5 mol, preferably 1 to 2 mol of alkoxypyrimidine of the formula (IV).

To carry out the process 1) according to the invention for the preparation of the compounds of the formula (V), the per

Formula (II) generally 1 to 15 moles, preferably 2 to 8 moles of halopyrimidine in the formula (XVII).

Suitable diluents for carrying out process c) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Ketones such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with Water or pure water. Process c) 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, lithium diisopropylamide, sodium methylate, sodium ethylate, potassium tert. -butylate, sodium hydroxide, potassium hydroxide, sodium 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-dimethyl-benzylamine, pyridine, N- Methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

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

In order to carry out process c) according to the invention for the preparation of the compounds of the formula (I), the per mole of the hydroxyhalophenyl derivative is used

Formula (II) generally 1 to 2 mol, preferably 1 to 1.5 mol of diaryliodonium halide of the formula (VII).

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

Process d) 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, lithium diisopropylamide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide , Sodium 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 diazabicycloundecene (DBU).

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

To carry out process d) according to the invention for the preparation of the compounds of the formula (I), 1 to 5 moles, preferably 1, are generally employed per mole of the 2- (2-halomethylphenyl) -2-methoxyoxy derivative of the formula (VIII) up to 2 mol of oxime of the formula (IX) or benzofuranone oxime of the formula (X) or bisoxime of the formula (XI). Suitable diluents for carrying out processes e), h) and o) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as

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

The reaction temperatures can be varied within a substantial range when carrying out processes e), h) and o) according to the invention. In general, temperatures from 0 ° C to 100 ° C, preferably at temperatures from 0 ° C to 60 ° C.

To carry out process e) according to the invention for the preparation of the compounds of the formula (I), 1 to 100 mol, preferably 1 to 10 mol, of methylamine are generally employed per mol of the halogenobenzene of the formula (I-a).

To carry out the process h) according to the invention for the preparation of the compounds of the formula (II), 1 to 100 mol, preferably 1 to 10 mol, of methylamine are generally employed per mol of the hydroxyhalophenyl derivative of the formula (II-a). To carry out the process o) according to the invention for the preparation of the compounds of the formula (XVIII), 1 to 100 mol are generally employed per mole of the 2- (2-methylphenyl) -2-methoxyimino derivative of the formula (XV-a), preferably 1 to 10 moles of methylamine.

Suitable diluents for carrying out processes f) and q) according to the invention are polar solvents. These preferably include alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propan-l, 2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, their mixtures with water or pure

Water.

The reaction temperatures can be varied within a substantial range when carrying out processes f) and q) 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 f) according to the invention, 1 to 5 mol, preferably 1.0 to 2.5 mol, of hydroxylamine or hydroxylamine hydrogen halide and in general 1 to 10 mol, preferably 1, are generally employed per mole of halogenobenzene of the formula (Ia) , 0 to 5.0 moles of dibromoethane.

To carry out process q) according to the invention, generally 1 to 5 mol, preferably 1.0 to 2.5 mol, of hydroxylamine are used per mole of 2- (2-methylphenyl) -2-methoxyimino derivative of the formula (XVIII-a) or hydroxylamine hydrogen halide and generally 1 to 10 moles, preferably 1.0 to 5.0 moles, of dibromoethane.

Suitable diluents for carrying out processes g) and n) according to the invention are polar solvents. These preferably include alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethane diol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

The reaction temperatures can be carried out when carrying out the inventive

Processes g) and n) 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 the process g) according to the invention for the preparation of the compounds of the formula (II), generally 1 to 15 mol, preferably 1 to 8 mol, of 1 to 8 mol of methoxyamine hydrochloride are employed per mol of the keto ester of the formula (XIII) or of the hydroxyphenylglyoxylic acid ester of the formula (XIV) ,

To carry out process n) according to the invention for the preparation of the compounds of the formula (XVIII), 1 to 15 mol, preferably 1 to 8 mol, of methoxyamine or one of its salts are generally employed per mole of the O-tolylpyruvic acid ester of the formula (XIX) ,

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

Process i) according to the invention is optionally carried out in the presence of a strong base. These preferably include n-, s-, t-butylitium or lithium diisopropyamide. The reaction temperatures can be varied within a substantial range when carrying out process i) according to the invention. In general, temperatures from -150 ° C to 0 ° C, preferably at temperatures from -100 ° C to -40 ° C.

To carry out process i) according to the invention for the preparation of the compounds of the formula (XIII), 1 to 5 mol, preferably 1 to 2 mol, of dimethyl oxalate are generally employed per mol of the ketal of the formula (XV).

Inert organic solvents are suitable as diluents for carrying out process j) according to the invention. These preferably include aliphatic or alicyclic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane or decalin; Halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane.

Process j) according to the invention is optionally carried out in the presence of a Lewis acid. These include, for example, boron trifluoride (also as etherate), boron tribromide, aluminum trichloride, titanium tetrachloride, tetrabutyl orthotitanate, zinc chloride, iron III chloride or antimony pentachloride.

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

To carry out process j) according to the invention for the preparation of the compounds of the formula (XIV), 1 to 5 mol, preferably 1 to 2 mol, of methyl oxalate chloride are generally employed per mol of the fluorophenol of the formula (XVI). Inert organic solvents are suitable as diluents for carrying out process k) according to the invention. These preferably include 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; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol,

Ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

Process k) according to the invention is optionally carried out in the presence of an acid. All inorganic and organic protonic and Lewis acids, as well as all polymeric acids, are suitable as such. These include, for example, hydrogen chloride, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, methanesulphonic acid, trifluoromethanesulphonic acid, toluenesulphonic acid, boron trifluoride (also as etherate), boron tribromide, aluminum trichloride, titanium tetrachloride, tetrabutyl chloride, iron-III-pentahloridotitanate, acidic ion exchangers, acidic clays and acidic silica gel.

The reaction temperatures can be varied within a substantial range when carrying out process k) according to the invention. In general, temperatures from 0 ° C to 120 ° C, preferably at temperatures from 0 ° C to 50 ° C.

Inert organic solvents are suitable as diluents for carrying out process m) according to the invention. These preferably include halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane.

The reaction temperatures can be varied within a substantial range when carrying out process m) according to the invention. Generally works one at temperatures from 0 ° C to 150 ° C, preferably at temperatures from 0 ° C to 100 ° C.

To carry out process m) according to the invention for the preparation of the compounds of the formula (VIII), 1 to 1.5 are generally employed per mole of the 2- (2-methylphenyl) -2-methoxyoxy derivative of the formula (XVIII) Mol, preferably 1 to 1.2 moles of halogenating agent.

Suitable diluents for carrying out process p) 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.

The reaction temperatures can be varied within a substantial range when carrying out process p) according to the invention. In general, temperatures from -20 ° C to 80 ° C, preferably at temperatures from 0 ° C to 50 ° C.

To carry out process p) according to the invention for the preparation of the compounds of the formula (XIX), 1 to 5 mol, preferably 1 to 2 mol, of acetic anhydride are generally employed per mol of the benzoyl cyanide of the formula (XX).

Suitable diluents for carrying out the first step of process r) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclo- hexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane.

As a chlorinating agent for carrying out the first stage of the invention

Process r) are all customary chlorinating agents that can be used for the production of acid chlorides, such as. B. thionyl chloride, phosphorus trichloride or phosphorus pentachloride.

Process r) according to the invention is optionally carried out in the presence of a catalyst, such as, for example, dimethylformamide or dimethylacetamide.

The reaction temperatures can be varied within a substantial range when carrying out both the first and the second stage of process r) according to the invention. In general, the first stage is carried out at temperatures from 20 ° C. to 150 ° C., preferably at temperatures from 20 ° C. to 100 ° C. and for the second stage at 100 to 250 ° C., preferably at 100 to 200 ° C.

To carry out process r) according to the invention for the preparation of the compounds of the formula (XX), one sets per mole of the benzoic acid derivative of the formula

(XXI) generally 1 to 15 mol, preferably 1 to 8 mol of halogenating agent and 1 to 5 mol, preferably 1 to 2 mol of trimethylsilyl cyanide.

All of 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, workup and isolation of the reaction products is carried out using generally customary methods (see also the preparation examples). With good plant tolerance and favorable warm-blood toxicity, the active substances are suitable for combating animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored goods and materials, and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:

From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

From the order of the Diplopoda e.g. Blaniulus guttulatus.

From the order of the Chilopoda e.g. Geophilus carpophagus, Scutigera spp.

From the order of the Symphyla e.g. Scutigerella immaculata.

From the order of the Thysanura e.g. Lepisma saccharina.

From the order of the Collembola e.g. Onychiurus armatus.

From the order of the Orthoptera e.g. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.

From the order of the Blattaria e.g. Blatta orientalis, Periplaneta americana,

Leucophaea maderae, Blattella germanica.

From the order of the Dermaptera e.g. Forficula auricularia.

From the order of the Isoptera, for example Reticulitermes spp. From the order of the Phthiraptera, for example Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp.

From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella accidentalis.

From the order of the Heteroptera e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of the Homoptera e.g. Aleurodes brassicae, Bemisia tabaci,

Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phoropalisumum , Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

From the order of the Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp.,

Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pierilusta s nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana,

Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.

From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni,

Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes sppus, spp., Trog. spp., Trog ., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp.,

Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.

From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp., Liriomyza spp.

From the order of the Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp.

From the class of the Arachnida e.g. Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommodes spp., Ix. Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.,

Hemitarsonemus spp., Brevipalpus spp.

Plant-parasitic nematodes include e.g. Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp.,

Trichodorus spp., Bursaphelenchus spp. They can be used with particularly good success to control insects which damage plants, such as, for example, against the larvae of the green peach aphid (Myzus persicae) and the caterpillars of the green army worm (Spodoptera frugiperda).

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 graminis;

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

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

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

Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea

(Conidial form: Drechslera, Syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus

(Conidial form: Drechslera, Syn: Helminthosporium);

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

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

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

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

Pellicularia species, such as, for example, Pellicularia sasakii;

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

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

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

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

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

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

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

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

The active compounds according to the invention also have a strong strengthening effect in plants. They are therefore suitable for mobilizing the plant's own defenses against attack by unwanted microorganisms.

Among plant-strengthening (resistance-inducing) substances are in the present

To understand the context of such substances that are able to stimulate the immune system of plants so that the treated plants subsequent inocolation with undesirable microorganisms develop extensive resistance to these microorganisms.

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

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

The active compounds according to the invention can be used with particularly good success in combating cereal diseases, such as, for example, against Erysiphe or Leptosphaeria species, and diseases in wine, fruit and vegetable cultivation, such as, for example, against Venturia, Sphaerotheca, Podosphaera- and Phytophtora- Types, use.

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

If appropriate, the active compounds according to the invention can also be used in certain concentrations and application rates as herbicides, for influencing plant growth, and for controlling animal pests. If appropriate, they can also be used as intermediates and precursors for the synthesis of further active compounds. According to the invention, all plants and parts of plants can be treated. Plants are understood here to mean all plants and plant populations, such as desired and unwanted wild plants or crop plants (including naturally occurring crop plants). Cultivated plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which can or cannot be protected by plant breeders' rights. Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

The treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space according to the customary treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, scattering, spreading and, in the case of propagation material, in particular in the case of seeds, furthermore by single- or multi-layer coating.

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

In the present context, technical materials are to be understood as non-living materials that have been prepared for use in technology. For example, technical materials 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 items, coolants and other materials may be those of Microorganisms can be attacked or decomposed. 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, for example, are microorganisms which can cause degradation or a change in the technical materials

Called slime organisms. The active compounds according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.

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

Alternaria, such as Altemaria 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, like 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 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 warm fog formulations.

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

Hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as Dimethylformamide and dimethyl sulfoxide, as well as water. Liquefied gaseous extenders or carriers mean such 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. The following are suitable as solid carriers: for example, natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates. Possible solid carriers for granules are: eg 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 stalks. As emulsifiers and / or foaming agents come in

Question: 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 sulfite liquor and methyl cellulose.

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

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

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

The active compounds according to the invention, as such or in their formulations, can also be mixed with known fungicides, bactericides, acaricides, nematicides or insecticides can be used, for example to spread the spectrum of activity or to prevent the development of resistance. In many cases, synergistic effects are obtained, ie 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, carpropamide, capsimycin, captafol, captan, carbendazim, carboxin, carvone, quinomethionate (quinomethionate), chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymroconililanil

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

Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,

Famoxadone, fenapanil, fenarimol, fenbuconazole, fenfurarn, fenhexamid, fenitropan,

Fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzon, fluazinam, flumetover, fluoromid, fluquinconazole, flurprimidol,

Flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum, fosetyl Sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox,

guazatine,

Hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Iprovalicarb, Irumamycin, 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, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,

Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,

Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin, Paclobutrazol, Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Picoxystrobin, Pimaricin, Piperalin, Polyoxin, Polyoxorim, probenazol, Prochloronine, Propazazoline, Prochlorazinol

Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon, Pyroxyfur,

Quinconazole, quintozen (PCNB), quinoxyfen

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

uniconazole

Validamycin A, vinclozolin, viniconazole,

Zarilamid, Zineb, Ziram as well

Dagger G,

OK 8705,

OK-8801, - (1, 1-dimethylethyl) -ß- (2-phenoxyethyl) - 1 H- 1, 2,4-triazole-1-ethanol, α- (2,4-dichlorophenyl) -ß-fluoro- b-propyl-1 H-1, 2,4-triazole-1-ethanol, - (2,4-dichlorophenyl) -ß-methoxy-a-methyl-1 H-1, 2,4-triazole-1-ethanol , - (5-methyl-l, 3-dioxan-5-yl) -ß - [[4- (trifluoromethyl) phenyl] methylene] -lH-l, 2,4-triazol-1-ethanol, (5RS , 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (lH-l, 2,4-triazol-l-yl) -3-octanone,

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

1 - (2,4-dichloφhenyl) -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, 1 - [(diiodomethyl) sulfonyl] -4-methyl-benzene, l - [[2- (2.4 -Dichlθφhenyl) -l, 3-dioxolan-2-yl] -methyl] -lH-imidazole, l - [[2- (4-Chloφhenyl) -3-phenyloxiranyl] -methyl] -lH-l, 2,4- triazole,

1 - [1 - [2- [(2,4-dichlorothenyl) methoxy] phenyl] ethenyl] -1 H-imidazole, l-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol, 2 ^ 6'-dibromo-2-memyl-4'-tifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide,

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

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

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

2 - [(1-methylethyl) sulfonyl] -5- (trichloromethyl) -1, 3,4-thiadiazole, 2- [[6-deoxy-4-O- (4-O-methyl-β-D-glycopyranosyl ) -aD-glucopyranosyl] -amino] -4- methoxy- 1 H-pyrrolo [2,3-d] pyrimidine-5-carbonitrile,

2-aminobutane,

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

2-chloro-N- (2,3-dihydro-1,3,3-trimethyl-1H-inden-4-yl) -3-pyridinecarboxamide, 2-chloro-N- (2,6-dimethylphenyl) -N - (isothiocyanatomethyl) acetamide,

2-phenylphenol (OPP),

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

3,5-dichloro-N- [cyano [(l-methyl-2-propynyl) -oxy] -methyl] -benzamide,

3 - (1,1-dimethylpropyl-1-oxo-1 H-indene-2-carbonitrile, 3- [2- (4-chloro-phenyl) -5-ethoxy-3-isoxazolidinyl] pyridine,

4-chloro-2-cyano-N, N-dimethyl-5- (4-methylphenyl) -lH-imidazol-l-sulfonamide,

4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one,

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-Chlθφhenyl) -2- (1 H- 1, 2,4-triazol-1-yl) -cycloheptanol, cis-4- [3- [4- (l, 1-dimethylpropyl) -phenyl -2-methylpropyl] -2,6-dimethyl-moφholin hydrochloride,

Ethyl - [(4-chloro-phenyl) -azo] cyanoacetate, potassium hydrogen carbonate,

Methantetrathiol 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- (2,6-dimethylphenyl) -2-memoxy-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-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-pyridyl) 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] ethylphosphoramidothioate, O-methyl-S-phenyl-phenylpropylphosphoramidothioate,

S-methyl-1, 2,3-benzothiadiazole-7-carbothioate, spiro [2H] - 1-benzopyran-2, 1 '(3'H) -isobenzofuran] -3'-one, 4- [3, 4- Dimethoxyphenyl) -3 - (4-fluoφhenyl) acryloyl] moφholin

bactericides:

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

Insecticides / acaricides / nematicides:

Abamectin, Acephate, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb, Alpha-cypermethrin, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azamethiphos, Azinphos A, Azinphos M, Azocyclotin,

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

Butathiofos, butocarboxime, butylpyridaben, Cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, Chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, Chloφyrifos, Chloφyrifos M, Chlovaporthrin, chromafenozide, cis-resmethrin, Cispermethrin, Clocythrin, cloethocarb, clofentezine, Clothianidine,

Cyanophos, Cycloprene, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazine,

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlorvos, Dicofol, Diflubenzuron, Dimethoat, Dimethylvinphos, Diofenolan,

Disulfoton, Docusat-sodium, Dofenapyn,

Eflusilanate, Emamectin, Empenthrin, Endosulfan, Entomopfthora spp., Esfenvalerate, Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos,

Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fipronil, Fluazuron, Flubrocythrinate, Flucycloxuron, Flcythrinate, Fluftoxinhrininate, Fufonoxhrhrininate, Fumetoxinhrininate, Fumetoxin , Furathiocarb,

granulosis

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

Imidacloprid, indoxacarb, isazofos, isofenphos, isoxathion, ivermectin,

nucleopolyhedroviruses

Lambda cyhalothrin, lufenuron Malathion, Mecarbam, Metaldehyde, Methamidophos, Metharhizin anisopliae, Metharhizin flavoviride, Methidathion, Methiocarb, Methoprene, Methomyl, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Milbemycin, Monocrotophos,

Naled, Nitenpyram, Nithiazine, Novaluron

Omethoate, Oxamyl, Oxydemethon M

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

Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propargite, Propoxur, Prothiofos, Prothoat, Pymetrozine, Pyraclofos, Pyresmethrin, Pyrethrum, Pyridroxy, Pyridifenip, Pyridifenip, Pyridfenipion

quinalphos,

ribavirin

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

Tau fluvalinate, Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Temivinphos, Terbufos, Tetrachlorvinphos, Tetradifon Theta- cypermethrin, Thiacloprid, Thiamethoxamoxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxiloxamidone, Thioconoxinoxamate

Triarathenes, triazamates, triazophos, triazuron, trichlophenidines, trichlorfon, triflumuron, trimethacarb,

Vamidothion, Vaniliprole, Verticillium lecanii

YI 5302 Zeta-cypermethrin, zolaprofos

(IR-cis) - [5- (phenylmethyl) -3-furanyl] methyl-3 - [(dihydro-2-oxo-3 (2H) furanylidene) methyl] -2,2-dimethylcyclopropane carboxylate

(3-phenoxyphenyl) methyl 2,2,3,3-tetramethylcyclopropane decarboxylate l - [(2-chloro-5-thiazolyl) methyl] tetrahydro-3,5-dimethyl-N-nitro-l, 3,5-triazine -2 (1H) - imine 2- (2-chloro-6-fluoro-phenyl) -4- [4- (1,1-dimethylethyl) phenyl] -4,5-dihydro-oxazole

2- (acetyloxy) -3-dodecyl-1,4-naphthalenedione

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

2-Chloro-N - [[[4- (2,2-dichloro-1,1-difluoroethoxy) phenyl] amino] carbonyl] benzamide

3-Methylphenyl-propyl carbamate 4- [4- (4-ethoxyphenyl) -4-methylpentyl] -1-fluoro-2-phenoxy-benzene

4-chloro-2- (l, l-dimethylethyl) -5 - [[2- (2,6-dimethyl-4-phenoxyphenoxy) ethyl] thio] -

3 (2H) pyridazinone

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

Bacillus thuringiensis strain EG-2348

Benzoic acid [2-benzoyl-1 - (1, 1-dimethylethyl) hydrazide

Butanoic acid 2,2-dimethyl-3- (2,4-dichloro-phenyl) -2-oxo-l-oxaspiro [4.5] dec-3-en-4-yl ester [3 - [(6-chloro-3-pyridinyl ) methy 1] -2-thiazolidinylidene] cyanamide

Dihydro-2- (nitromethylene) -2H-l, 3-thiazine-3 (4H) -carboxaldehyde

Ethyl [2 - [[l, 6-dihydro-6-oxo-l- (phenylmethyl) -4-pyridazinyl] oxy] ethyl] carbamate

N- (3,4,4-trifluoro-1-oxo-3-butenyl) glycine

N- (4-Chlθφhenyl) -3- [4- (difluoromethoxy) phenyl] -4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide

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

N-methyl-N'-2-propenyl-1, 2-hydrazinedicarbothioamide

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

N-cyanomethyl-4-trifluoromethyl-nicotinamide

3,5-dichloro-l- (3,3-dichloro-2-propenyloxy) -4- [3- (5-trifluoromethylpyridin-2-yloxy) propoxy] benzene.

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

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

Aspergillus niger and Aspergillus fumigatus, Trichophyton species such as Trichophyton mentagrophytes, Microsporon species such as Microsporon canis and audouinii. The list of these mushrooms is in no way a limitation of the detectable mycotic spectrum, but is only of an explanatory nature.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to

Applying active ingredients according to the ultra-low-volume method or injecting the active ingredient preparation or the active ingredient itself into the soil. 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 substantial 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. 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.

When used as insecticides, the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists. Synergists are compounds that increase the effectiveness of the active ingredients without the added synergist itself having to be active.

The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight.

The application takes place in a customary manner adapted to the application forms

Wise.

When used against hygiene pests and pests of stored products, the active ingredient is distinguished by an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.

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

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

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, growing season, nutrition), the treatment according to the invention can also cause superadditive ("synergistic") effects. For example, reduced application rates and / or extensions of the

Spectrum of activity and / or an enhancement of the effect of the substances and agents which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripening, higher crop yields , higher quality and / or higher

Nutritional value of the harvested products, higher shelf life and / or workability of the harvested products possible, which go beyond the effects that are actually to be expected.

The preferred transgenic plants or plant cultivars to be treated according to the invention include all plants which have received genetic material through the genetic engineering modification, which gives these plants particularly advantageous, valuable properties (“traits”). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to water or soil salt content, increased flowering performance, easier harvesting, Acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvest products, higher storability and / or workability of the harvest products. Further and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi,

Bacteria and / or viruses and an increased tolerance of the plants to certain herbicidal active ingredients. Examples of transgenic plants are the important cultivated plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybeans , Potato, cotton and rapeseed are highlighted. The traits are particularly emphasized as the increased defense of the plants against insects by toxins arising in the plants, in particular those which are caused by the genetic material from Bacillus Thuringenisis (eg by the genes CryΙA (a), CryΙA (b ), CryΙA (c), CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF as well as their combinations) in the

Plants are created (hereinafter "Bt plants"). The properties ("traits") also particularly emphasize the increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. The traits are also particularly emphasized by the plants' increased tolerance to certain herbicidal active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example the "PAT" gene). The genes imparting the desired properties (“traits”) can also occur in combinations with one another in the transgenic plants. Examples of "Bt plants" are maize varieties,

Cotton varieties, soy varieties and potato varieties named under the trade names YIELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf ® (potato) are sold. Examples of herbicide-tolerant plants are corn varieties, cotton varieties and soy varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example corn, Cotton, soy), Liberty Link® (tolerance against phosphinotricin, eg rapeseed), IMI® (tolerance against imidazolinones) and STS® (tolerance against sulfonylureas eg maize). The herbicide-resistant plants (conventionally bred to herbicide tolerance) include the varieties sold under the name Clearfield® (for example maize). Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties ("traits").

The plants listed can be particularly advantageous according to the invention with the

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

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

Preparation Examples:

example 1

Procedure a)

A mixture of 1.5 g (6.6 mmol) (2-fluoro-6-hydroxy-phenyl) methoxyiminoacetic acid methyl ester, 1.7 g (6.6 mmol) of 4,5-difluoro-6- ( 2-methyl-3-chlorophenoxy) pyrimidine, 1.4 g (10 mmol) of potassium carbonate and 50 ml of acetonitrile are stirred at room temperature for 18 hours. The reaction mixture is then filtered through Celite and the filtrate is evaporated in vacuo. This gives 2.8 g (91.5% of theory) {2- [6- (3-chloro-2-methylphenoxy) -5-fluoropyrimidin-4-yloxy] -6-fluorophenyl} - methoxyimino-acetic acid methyl ester with the log P (pH 2) = 4.23.

Example 2

Procedure a)

A mixture of 0.7 g (3.1 mmol) of 2- (2-fluoro-6-hydroxy-phenyl) -2-methoxyimino-N-methyl-acetamide, 0.75 g (3.1 mmol) of 4.5 difluoro-6- (2-chloro-phenoxy) -pyrimidine,

0.64 g (4.6 mmol) of potassium carbonate and 50 ml of acetonitrile is added for 18 hours

Room temperature stirred. Then the reaction mixture is filtered through Celite and evaporates the filtrate in vacuo. The residue is triturated with diisopropyl ether and the crystalline product is filtered off with suction. This gives 0.9 g (65% of theory) of 2- {2- [6- (2-chlorophenoxy) -5-fluoropyrimidin-4-yloxy] -6-fluorophenyl} -2-methoxyimino -N-methyl-acetamide with log P (pH 2) = 3.10.

Example 3

Method c) A mixture of 1.8 g (8 mmol) (2-fluoro-6-hydroxy-phenyl) methoxyiminoacetic acid methyl ester, 2.5 g (8 mmol) diphenyliodonium chloride, 1.7 g (12 mmol) Potassium carbonate and 60 ml of acetonitrile are boiled under reflux for 4 hours. The reaction mixture is then filtered through Celite and the filtrate is evaporated in vacuo. The residue is purified by column chromatography (methylene chloride / hexane 5: 1). This gives 2.04 g (84% of theory) of methyl (2-fluoro-6-phenoxy-phenyl) -methoxyimino-acetate with the log P (pH 2) = 3.24.

Example 4

Procedure e)

A mixture of 2.2 g (7.25 mmol) of 2- (2-fluoro-6-phenoxy) -phenyl-2-meth-oximino-acetic acid methyl ester, 6.2 ml of methylamine solution in water (40%) and 80 ml of methanol is stirred overnight at room temperature. Then the solvent is distilled off in vacuo. This gives 1.6 g (73% of theory) of 2- (2-fluoro-6-phenoxyphenyl) -2-methoxyimino-N-methyl-acetamide with the log P (pH 2) = 2.56.

Example 5

Procedure c)

A mixture of 1.14 g (5 mmol) of 2- (4-fluoro-2-hydroxy-phenyl) -2-methoxyimino-N-methyl-acetamide, 1.6 g (5 mmol) of diphenyliodonium chloride, 1.05 g ( 7.5 mmol) of potassium carbonate and 40 ml of acetonitrile is boiled under reflux for 4 hours. The reaction mixture is then filtered through Celite and the filtrate is evaporated in vacuo. The residue is triturated with disopropyl ether and the product is filtered off with suction after crystallization. This gives 1.0 g (66% of theory) of 2- (2-fluoro-6-phenoxy-phenyl) -2-methoxyimino-N-methyl-acetamide with the log P (pH 2) = 2.43. Example 6

Procedure a)

A mixture of 0.7 g (3.1 mmol) of 2- (2-hydroxy-4-fluorophenyl) -2-methoximinoacetic acid methyl ester, 0.8 g (3.1 mmol) of 4,5-difluoro-6 - (2-methyl-3-chlorophenoxy) pyrimidine, 0.64 g (4.64 mmol) of potassium carbonate and 50 ml of acetonitrile is stirred at room temperature for 18 hours. The reaction mixture is then filtered through Celite and the filtrate is evaporated in vacuo. The residue is purified by column chromatography (methylene chloride). This gives 1.2 g (83.5% of theory) {2- [6- (3-chloro-2-methylphenoxy) -5-fluoropyrimidin-4-yloxy] -4-fluorophenyl} - methoxyimino-acetic acid methyl ester with the log P (pH 2) = 4.73.

Example 7

Procedure a)

A mixture of 0.7 g (3.1 mmol) of 2- (2-hydroxy-4-fluoro-phenyl) -2-methoximinoacetic acid-N-methylamide, 0.75 g (3.1 mmol) of 4.5 -Difluoro-6- (2-chlorophenoxy) pyrimidine, 0.64 g (4.6 mmol) of potassium carbonate and 50 ml of acetonitrile is used for 18 hours stirred at room temperature. The reaction mixture is then filtered through Celite and the filtrate is evaporated in vacuo. 1.2 g (87% of theory) of 2- {2- [6- (2-chlorophenoxy) -5-fluoropyrimidin-4-yloxy] -4-fluorophenyl} -2-methoxyimino are thus obtained - N-methyl-acetamide with log P (pH 2) = 3.14.

Example 8

Method d) To a suspension of 0.5 g (0.012 mol) sodium hydride (60% in oil) in 70 ml

Dimethylformamide is added dropwise to 1.12 g (0.01 mol) of o-cresol. The mixture is stirred for 3 hours at room temperature, then a solution of 4.5 g (0.01 mol) of (2-bromomethyl-6-fluorophenyl) methoxyiminoacetic acid methyl ester in 20 ml of dimethylformamide is added and the mixture is stirred Mix overnight at room temperature. Then the reaction mixture is poured into water and extracted twice with

Ethyl acetate. The organic phases are washed with water, dried over sodium sulfate and evaporated in vacuo. The residue is chromatographed on silica gel (methylene chloride / ethyl acetate 2: 1). 1.6 g (48%) (2-fluoro-6-o-tolyloxymethyl-phenyl) -methoxyimino-acetic acid methyl ester with a melting point of 108 ° C. and a logP (pH 2) = 3.65 are obtained.

Example 9

Procedure e)

A mixture of 0.9 g (2.7 mmol) (2-fluoro-6-o-tolyloxymethylphenyl) methoxyimino-acetic acid methyl ester, 3 ml methylamine solution in water (40%) and 30 ml methanol is added overnight Room temperature stirred. Then the solvent is distilled off in vacuo, the residue is triturated with water and diluted

Hydrochloric acid and sucks off the precipitated product. This gives 0.9 g (quant.) 2- (2-fluoro-6-o-tolyloxymethyl-phenyl) -2-methoxyimino-N-methyl-acetamide in the form of colorless crystals with a melting point of 93 ° C. and the log P (pH 2) = 3.03.

Analogous to Examples 1 to 8, and according to the information in the general

Process descriptions of processes a) - f), the compounds of the formula (I) mentioned in Table 1 below are also obtained.

Table 1

The logP values were determined in accordance with EEC Directive 79/831 Annex V. A8 by HPLC (gradient method, acetonitrile / 0.1% aqueous phosphoric acid)

In the compounds listed above, the double bond of the methoxyimino-N-methylacetamide group or the methoxyiminoacetic acid methyl ester group is in the E configuration, if not marked differently.

Manufacture of intermediate products

Compounds of formula (II)

Example (IM)

Procedure g)

A mixture of 47 g (0.282 mol) of [2-fluoro-6- (tetrahydro-pyran-2-yloxy) phenyl] oxo-acetic acid methyl ester, 28.4 g (0.34 mol) of O-methyl-hydroxylamine -Hydrochloride and 250 ml of methanol are boiled under reflux for 18 hours. Then the solvent is evaporated off in vacuo, water is added to the residue and the mixture is extracted with ethyl acetate. The organic phase is dried over sodium sulfate and evaporated in vacuo. The residue is rubbed with a mixture of petroleum ether and diisopropyl ether (approx. 1: 1) and the crystalline product is filtered off with suction. This gives 26.9 g (42% of theory) of methyl (2-fluoro-6-hydroxy-phenyl) methoxyiminoacetate with the logP (pH 2) = 1.67 (content according to HPLC: 96%).

Example (II-2)

Procedure h) A mixture of 11.4 g (0.05 mol) of 2- (2-fluoro-6-hydroxy-phenyl) -2-methoximinoacetate, 43 ml of methylamine solution in water (40%) and 150 ml of methanol is added overnight Room temperature stirred. Then the solvent is distilled off in vacuo, water is added to the residue, the mixture is acidified to pH 4 by adding dilute hydrochloric acid. The precipitated product is suctioned off and washed with water. This gives 10.0 g (88.5% of theory) of 2- (2-fluoro-6-hydroxyphenyl) -2-methoxyimino-N-methyl-acetamide with the log P (pH 2) = 1.18 ,

Example (II-3)

Procedure g)

A mixture of 7.5 g (0.038 mol) (4-fluoro-2-hydroxy-phenyl) -oxoacetic acid methyl ester, 3.8 g (0.045 mol) of O-methyl-hydroxylamine hydrochloride and 70 ml

Methanol is boiled under reflux for 18 hours. Then the solvent is evaporated off in vacuo, water is added to the residue and the mixture is extracted with ethyl acetate. The organic phase is dried over sodium sulfate and evaporated in vacuo. The residue is purified by column chromatography (petroleum ether / acetone = 4: 1). This gives 3.8 g (44% of theory) of methyl (4-fluoro-2-hydroxy-phenyl) methoxyiminoacetate with the logP (pH 2) = 2.62. Example (II-4)

Procedure h)

A mixture of 2.7 g (0.012 mol) of (4-fluoro-2-hydroxy-phenyl) methoxyiminoacetic acid, methyl ester, 12 ml of methylamine solution in water (40%) and 60 ml of methanol is stirred overnight at room temperature. Then the solvent is distilled off in vacuo, the residue is treated with ethyl acetate and the solution is dried with sodium sulfate. Then the solvent is distilled off in vacuo. This gives 2.7 g (quant.) 2- (4-fluoro-2-hydroxyphenyl) -2-methoxyimino-N-methyl-acetamide with the log P (pH 2) = 1.56.

Compounds of the formula (XIII)

Example (XIII-1)

Procedure g)

To a solution of 19.6 g (0.1 mol) of 2- (3-fluorophenoxy) tetrahydropyran (preparation see J.Amer.Chem.Soc. 119; 6; 1997; 1208-1216) in 100 ml Tetrahydrofuran is added dropwise at -75 ° C to 50 ml of a 2.5M solution of butyllithium Hexane (0.12 mol) and the mixture is stirred at -75 ° C. for 1 hour. Then 50 ml of a solution of 13 g (0.11 mol) of dimethyl oxalate in 100 ml of tetrahydrofuran are added dropwise at -75 ° to -85 ° C. and the mixture is stirred at -75 ° C. for 1 hour. The reaction mixture is then allowed to warm up slowly to room temperature and the solvent is then evaporated off at 30 ° C. in vacuo. The residue is mixed with 300 ml of saturated ammonium chloride solution and extracted with ethyl acetate. The organic phase is dried over sodium sulfate and evaporated in vacuo. The residue is triturated with petroleum ether and the crystalline product is filtered off with suction. This gives 14.1 g (50% of theory) of methyl [2-fluoro-6- (tetrahydro-pyran-2-yloxy) phenyl] oxoacetic acid with the logP = (pH 2) 2.78 ( HPLC content: 99%).

Compounds of the formula (XIV)

Example (XIV-1)

Procedure k)

6.6 g are added dropwise at 30 ° C. to a mixture of 21.4 g (0.161 g) of anhydrous aluminum chloride, 6 g (0.0535 mol) of 3-fluorophenol and 100 ml of dichloroethane

(0.0535 mol of oxalic acid methyl ester chloride. The reaction mixture is stirred overnight at room temperature and then poured onto ice water. It is extracted twice with methylene chloride, the organic phase is dried and the solvent is evaporated off in vacuo. 8.9 g of a yellow oil are thus obtained, according to HPLC 77% consists of (4-fluoro-2-hydroxy-phenyl) -oxoacetic acid methyl ester. Log P (pH 2) = 2.10.

Compounds of the formula (NIII)

Example (NIII-1)

Method m) A mixture of 21.6 g (0.096 mol) of (2-fluoro-6-methylphenyl) methoxyiminoacetic acid methyl ester, 13.7 g (0.048 mol) l, 3-dibromo-5.5- Dimethylhydantoin, 1 g of dibenzoyl peroxide and 250 ml of carbon tetrachloride are boiled under reflux for 7 hours. The reaction mixture is then filtered through Celite and the solvent is evaporated off in vacuo. This gives 29.4 g of a product which, according to HPLC analysis, consists of 67% of an E / Z mixture of (2-bromomethyl-6-fluorophenyl) methoxyiminoacetic acid methyl ester (log P (pH 2 ) = 2.58 or 2.87).

Compounds of the formula XVIII)

Example (XVIII-1)

1. Methyl 2- (2-fluoro-6-methyl-phenyl) -2-methoximinoacetate

Procedure n)

A mixture of 19.6 g (0.1 mol) of (2-fluoro-6-methyl-phenyl) -oxoacetic acid methyl ester, 10 g (0.12 mol) of O-methyl-hydroxylamine hydrochloride and 200 ml of methanol is boiled under reflux for 18 hours. Then the solvent is evaporated off in vacuo, water is added to the residue and the mixture is extracted with ethyl acetate. The organic phase is dried over sodium sulfate and evaporated in vacuo. This gives 22.5 g (quant.) (2-fluoro-6-methylphenyl) methoxyiminoacetic acid methyl ester as an E / Z mixture with the logP (pH 2) = 2.43 or 2.74 ,

Compounds of the formula (XIX)

Example (XIX-1)

2. 2-fluoro-6-methyl-phenylglyoxylic acid methyl ester

21.1 g (0.207 mol) of acetic anhydride are added dropwise to a solution of 33.7 g (0.207 mol).) Of 2-fluoro-6-methyl-benzoyl cyanide in 300 ml of methyl tert-butyl ether and the mixture is stirred 10 Minutes at room temperature.

Then it is cooled from -15 ° C. and HCl gas is introduced at this temperature until saturation. The reaction mixture is stirred at room temperature overnight and then 52 ml of methanol are added. The mixture is stirred for a further 18 hours at room temperature and then the solvent is distilled off in vacuo. The residue is mixed with 250 ml of methyl tert-butyl ether and then shaken out twice with 200 ml of water. The organic phase is evaporated in vacuo, the residue is dissolved in 200 ml of methylene chloride and this solution is added dropwise to 42 ml conc. Hydrochloric acid. The mixture is stirred at room temperature overnight and then 100 ml of water are added. The organic phase is separated off, dried over sodium sulfate and the solvent is distilled off in vacuo. This gives 40.7 g (quant.) (2-fluoro-6-methyl-phenyl) -oxoacetic acid methyl ester log P (pH ₂ ) = 2.44 (content according to HPLC: 93.5%).

Compounds of formula (XX)

Example (XX-1)

2-fluoro-6-methyl cyanide

A mixture of 65 g (0.422 mol) of 2-fluoro-6-methylbenzoic acid (preparation see DE 3328494) 60.2 g (0.506 mol) of thionyl chloride, 0.1 ml of dimethylformamide and 250 ml of methylene chloride is boiled under reflux overnight. Then the solvent is distilled off in vacuo. The residue (72 g) is heated to 130 ° C. and 43.5 g (0.438 mol) of trimethylsilyl cyanide are added dropwise. The trimethylchlorosilane formed is distilled off. After the addition has ended, the reaction mixture is heated at 180 ° C. for a further 10 minutes, then this is distilled

Product in a high vacuum. This gives 31.6 g (46.5% of theory) of 2-fluoro-6-methyl-benzoyl cyanide with a boiling point of 80-83 ° C./mbar and a log P (pH ₂ ) = 2.55. applications

Example A

Phytophthora test (tomato) / protective

Solvent: 24.5 parts by weight of acetone

24.5 parts by weight of dimethylacetamide emulsifier: 1.0 part by weight of alkyl aryl polyglycol ether

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

To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Phytophthora infestans. The plants are then placed in an incubation cabin at approx. 20 ° C and 100% relative humidity.

Evaluation is carried out 3 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the examples (2, 7, 9, 12, 14, 15, 31, 33, 45, 46, 47,

48, 50, 51, 56, 57) listed substances according to the invention with an application rate of 100 g / ha an efficiency of 86% or more. Example B

Podosphaera test (apple) / protective

Solvent: 24.5 parts by weight of acetone

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 pod mildew pathogen Podosphaera leucotricha. The plants are then placed in the greenhouse at about 23 ° C. and a relative humidity of about 70%.

Evaluation is carried out 10 days after the inoculation. 0% means a

Efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the substances according to the invention listed in Examples (1, 2, 5, 8, 9, 12, 14, 15, 31, 33, 35, 45, 46, 47, 48, 50, 51, 56, 57) show with an application rate of 100 g / ha, an efficiency of 82% or more. Example C

Sphaerotheca test (cucumber) / protective

Solvent: 24.5 parts by weight of acetone

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 washed with an aqueous spore suspension of

Sphaerotheca fuliginea inoculated. The plants are then placed in the greenhouse at about 23 ° C. and a relative atmospheric humidity of about 70%.

Evaluation is carried out 7 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the substances according to the invention listed in Examples (1, 2, 7, 8, 9, 12, 14, 15, 31, 33, 35, 45, 46, 47, 48, 50, 51, 56, 57) show with an application rate of 100 g / ha, an efficiency of 98% or more. Example D

Venturia test (apple) / protective

Solvent: 24.5 parts by weight of acetone

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 washed with an aqueous conidia suspension

Apple scab pathogen Venturia inaequalis and then remain in an incubation cabin for 1 day at approx. 20 ° C and 100% relative humidity.

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

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, the substances according to the invention listed in Examples (1, 2, 7, 8, 9, 12, 14, 15, 31, 33, 35, 45, 46, 47, 48, 50, 51, 56, 57) show with an application rate of 100 g / ha, an efficiency of 97% or more. Example E

Erysiphe test (barley) / protective

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

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 covered with spores from Erysiphe graminis f.sp. hordei pollinated.

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

In this test, the substances according to the invention listed in Examples (1, 3, 4, 8, 10, 12, 14, 40, 41, 42, 43, 44, 50, 51) show an efficiency at an application rate of 500 g / ha of 98% or more. Example F

Leptosphaeria nodorum test (wheat) / protective

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

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 at 20 ° C and 100% relative for 48 hours

Humidity in an incubation cabin.

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

In this test, the substances according to the invention listed in Examples (2, 16, 22, 31, 45, 46, 47, 48, 57) show an efficiency of 98% or more at an application rate of 500 g / ha. Example G

Myzus test / field beans

Solvent: 31 parts by weight of acetone

Emulsifier: 1 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 stated emulsifier and the concentrate is diluted to the desired concentration with water containing emulsifier.

Seedlings of the field bean (Vicia faba minor), which are infested with the green peach aphid (Myzus persicae), are immersed in an active ingredient preparation of the desired concentration and placed in a plastic can.

After the desired time, the kill is determined in percent. 100% means that all animals have been killed; 0% means that no animals have been killed.

In this test, for example, the compound of preparation example (56) at an exemplary active ingredient concentration of 100 ppm causes a kill of 100% after 6 days.

Example H

Spodoptera frugipereda test / artificial feed

Solvent: 31 parts by weight of acetone

Emulsifier: 1 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 emulsifier and the concentrate is diluted with water containing emulsifier to the desired concentration.

A specified amount of active compound preparation of the desired concentration is pipetted onto a standardized amount of synthetic feed. In 6 repetitions, one larva (L3) of the Herrwurm (Spodoptera frugiperda) is placed on the feed.

After the desired time, the mortality is determined in%. 100% means that all animals have been killed; 0% means that no animals have been killed.

In this test, the substance according to the invention listed in Example (1) shows a degree of destruction of 98% or more at an active substance concentration of 500 ppm.

Claims

claims

Compounds of the general formula (I),

in which

R ¹ for one of the groupings

R5-O- # R ⁵ -O-CH ₂ - #

stands in what

R ^{5 represents} optionally substituted aryl,

R ^{6 represents} optionally substituted aryl,

R ¹ ! represents optionally substituted alkyl,

R ^{12 represents} in each case optionally substituted alkyl, alkoxy or aryl,

R ^{13 represents} in each case optionally substituted alkyl or aryl,

R ^{14 represents} optionally substituted aryl,

X represents hydrogen or halogen

T for a grouping

stands.

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

R5-O- # R ⁵ -O-CH ₂ - #

or

stands in what

R ^{5 represents} optionally substituted phenyl,

R ^{6 represents} optionally substituted phenyl,

R ¹ * represents alkyl which has 1 to 4 carbon atoms and is optionally substituted by halogen,

R ^{12 represents} in each case optionally substituted by halogen alkyl or alkoxy having 1 to 6 carbon atoms or optionally substituted phenyl,

R ¹⁴ for alkyl optionally substituted by halogen with 1 to

6 carbon atoms,

R ¹⁵ and R ^{16 are the} same or different and independently of one another represent hydrogen, fluorine, chlorine, bromine or alkyl having 1 to 4 carbon atoms, X represents hydrogen, fluorine, chlorine, bromine or iodine,

T for a grouping

^Stands

the possible substituents of the aforementioned phenyl, phenoxy or phenoxymethyl radicals are preferably selected from the following list:

each straight-chain or branched alkyl, hydroxyalkyl, oxoalkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, dialkoxyalkyl, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 8 carbon atoms;

each straight-chain or branched alkenyl or alkenyloxy 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 alkylamino, dialkylamino,

Cycloalkyl or cycloalkyloxy each having 3 to 6 carbon atoms;

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

Fluorine, chlorine, oxo, methyl, trifluoromethyl or ethyl substituted, each doubly linked alkylene with 3 or 4 carbon atoms, oxyalkylene with 2 or 3 carbon atoms or dioxyalkylene with 1 or 2 carbon atoms;

A ¹ or a group _M , in which

A ² ^

A ^{1 represents} hydrogen, hydroxy or alkyl having 1 to 4 carbon atoms or cycloalkyl having 1 to 6 carbon atoms and A ² for hydroxyl, amino, methylamino, phenyl, benzyl or for alkyl or alkoxy with 1 to 4 carbon atoms which is optionally substituted by cyano, hydroxy, alkoxy, alkylthio, alkylamino, dialkylamino or phenyl, or for alkenyloxy or alkynyloxy each with 2 to 4 Carbon atoms.

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

R5-O- # R ⁵ -O-CH ₂ - #

stands in what R ^{5 represents} optionally substituted phenyl,

R ^{6 represents} optionally substituted phenyl,

R ¹ ! represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,

R ¹⁴ for optionally substituted by fluorine or chlorine

Is methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, pentyl, hexyl,

R ¹⁵ and R ^{16 are} identical or different and independently of one another represent hydrogen, fluorine, chlorine, bromine, methyl or ethyl,

X represents hydrogen, fluorine, chlorine, bromine or iodine, R ² , R ³ and R ^{4 are the} same or different and are independently hydrogen, fluorine or chlorine, but at least one of the radicals R ² , R ³ or R ^{4 is} fluorine or chlorine and

T for a grouping

the possible substituents of the phenyl radicals mentioned above are preferably selected from the following list:

Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, 1-, 2-, 3-, neo-pentyl, 1-, 2-, 3-, 4- (2nd -Methylbutyl), 1-, 2-, 3-hexyl, 1-, 2-, 3-, 4-, 5- (2-methylpentyl), 1-, 2-, 3- (3-methylpentyl), 2-ethylbutyl, 1-, 3-, 4- (2,2-dimethylbutyl), 1-, 2- (2,3-dimethylbutyl), hydroxymethyl, hydroxyethyl, 3-oxobutyl, methoxymethyl, dimethoxymethyl,

Methoxy, ethoxy, n- or i-propoxy, methoxymethyl, ethoxymethyl,

Methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, methylthiomethyl, ethylthiomethyl, Vinyl, allyl, 2-methylallyl, propen-1-yl, crotonyl, propargyl, vinyloxy, allyloxy, 2-methylallyloxy, propen-1-yloxy, crotonyloxy, propargyloxy;

Trifluoromethyl, trifluoroethyl,

Methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino,

Acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, diefhylaminocarbonyl,

Dimethylaminocarbonyloxy, diethylaminocarbonyloxy, benzylaminocarbonyl, acryloyl, propioloyl,

Cyclopentyl, cyclohexyl,

each optionally optionally up to four times, the same or different, substituted by fluorine, chlorine, oxo, methyl or trifluoromethyl, in each case twice linked propanediyl, ethyleneoxy, methylenedioxy, ethylenedioxy

A ¹ or a grouping '', where

A ² "

A ^{1 represents} hydrogen, methyl or hydroxy and

A ^{2 represents} hydroxy, methoxy, ethoxy, amino, methylamino, phenyl, benzyl or hydroxyethyl. A process for the preparation of compounds of formula (I) as defined in claim 1, characterized in that

a) a hydroxyhalophenyl derivative of the formula (II),

in which

R ² , R ³ , R ⁴ and T have the meanings given in claim 1,

with a phenoxypyrimidine of the general formula (III),

in which

R ¹³ and X have the meanings given in claim 1 and

Y ^{1 represents} halogen,

or an alkoxypyrimidine of the general formula (IV), in which

R ¹⁴ , R ¹⁵ and R ^{16 have} the meaning given in claim 1 and

Y ^{2 represents} alkysulfonyl or arylsulfonyl,

4-phenoxypyrimidines of the general formula (V),

R ² , R ³ , R ⁴ , T and X have the meanings given in claim 1 and

Y ^{3 represents} halogen,

with a phenol of the general formula (VI),

R ¹³ -OH (VI) in which

R ^{13 has} the meaning given in claim 1,

c) a hydroxyhalophenyl derivative of the formula (II) with a diaryl iodonium halide of the general formula (VII),

(Y ⁵ ) ^'

R ^ R = ^(VI1) in which

R ^{5 has} the meaning given in claim 1 and

Y ^{5 represents} halogen,

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

d) a 2- (2-halomethylphenyl) -2-methoxyimino derivative of the formula (VIII),

in which

R ² , R ³ , R ⁴ and T have the meanings given in claim 1 and

Y ^{6 represents} halogen,

with an oxime of the formula (IX),

in which

R ^{6 has} the meaning given in claim 1,

or with a benzofuranone oxime of the formula (X),

in which

R ⁷ , R ⁸ , R ⁹ and R ^{10 have} the meanings given in Claim 1,

or with a bisoxime of the formula (XI), in which

R ^{1 1} and R ^{12 have} the meanings given in claim 1,

or with a phenol of the formula (XII),

R ⁵ -OH (XII)

in which

R ^{5 has} the meaning given in claim 1,

a halobenzene of the general formula (I-a),

in which

R ^ R ² , R ³ and R ^{4 have} the meanings given in claim 1, with methylamine, optionally in the presence of a diluent, or if one

Compounds of the general formula (I-a)

in which

Rl, R ² , R ³ and R ^{4 have} the meanings given in claim 1.

Compounds of the general formula (II),

in which R ² , R ³ , R ⁴ and T have the meanings given in claim 1.

Compounds of the general formula (V),

in which

R ² , R ³ , R ⁴ , T and X have the meanings given in claim 1.

and Y ^{3 represents} halogen.

8. Compounds of the general formula (VIII),

in which

R ² , R ³ , R ⁴ and T have the meanings given in claim 1 and

Y ^{6 represents} halogen.

9. Compounds of the general formula (XIV), in which

R ² , R ³ and R ^{4 have} the meanings given in Claim 1.

10. Compounds of the general formula (XIII),

in which

R ² , R ³ and R ^{4 have} the meanings given in claim 1 and

R ^{17 represents} alkyl,

R ^{18 represents} hydrogen or alkyl or

R ¹⁷ and R ¹⁸ together with the atoms to which they are attached form a six-membered ring.

11. Compounds of the general formula (XVIII), (XVIII)

in which

R ² , R ³ , R ⁴ and T have the meanings given in claim 1.

12. Compounds of the general formula (X Villa)

(XVIIIa)

in which R ² , R ³ and R ^{4 have} the meanings given in Claim 1.

13. Compounds of the general formula (XIX),

in which

R ² , R ³ and R ^{4 have} the meanings given in Claim 1.

14. Compounds of the general formula (XX),

in which

R ² , R ³ and R ^{4 have} the meanings given in Claim 1.

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

16. A method for controlling harmful organisms, characterized in that compounds as defined in claims 1 to 3 or agents as defined in claim 15 are allowed to act on harmful organisms and / or their habitat.

17. Use of compounds as defined in claims 1 to 3 or agents as defined in claim 15 for combating harmful

Organisms.

18. A process for the preparation of agents as defined in claim 15, characterized in that compounds as defined in claims 1 to 3 are used with extenders and / or carriers and / or surface-active agents.