WO1995006033A1 - 2-oximino-2-pyridyl acetic acid derivatives as anti-parasitic agents (fungicides) - Google Patents

Abstract

The application concerns: novel 2-oximino-2-pyridyl acetic acid derivatives of formula (I), wherein R?1, R2, R3¿, Z, Ar and A have the meanings indicated in the description; a number of process for manufacturing the said compounds; and the use of the said compounds as anti-parasitic agents.

Description

2-0XIMINO-2-PYRIDYL ACETIC ACID DERIVATIVES AS A PEST CONTROL (FUNGICIDE)

The invention relates to new 2-oximino-2-pyridyl-acetic acid derivatives, several processes for their preparation and their use as pesticides, in particular as fungicides.

It is known that certain 2-methoxy-acrylic acid esters, such as the compound 3-methoxy-2- (6-phenyl-2-pyridylthio) -acrylic acid methyl ester or the compound 3-methoxy-2- [N - (6-Phenyl-2-pyridyl) -N-methylamino] acrylic acid methyl ester or the compound 3-methoxy-2- [5- (4-chlorophenyl) -3-pyridyloxy] acrylic acid methyl ester fungicidal Have properties (see, for example, EP 383 117).

The effectiveness of these previously known compounds, however, is not entirely satisfactory in all fields of application, in particular when the application rates and concentrations are low.

New 2-oximino-2-pyridyl-acetic acid derivatives of the general formula (I)

in which

Ar represents optionally substituted aryl or heteroaryl, R represents alkyl or haloalkyl,

R ² and R ³ independently of one another each represent hydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkylthio, alkenyl, alkenyloxy, alkynyl, alkynyloxy, haloalkyl, haloalkoxy, haloalkylthio, haloalkenyl, haloalkenyloxy, haloalkynyl, haloalkynyloxy, alkoxycarbonyl,

Hydroximinoalkyl, alkoximinoalkyl or optionally substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy,

A for oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH ₂ -O-, -O-CH ₂ -, -CH ₂ -SO _n -, -SO _n - CH ₂ -, -SO _n -,

-C (R ⁴ ) = NO-, -C (R ⁴ ) = NO-CH ₂ - or -N (R ⁶ ) -, and

Z represents a radical of the formula -OR ⁵ or -NR ⁶ R ⁷ , where

R ^{4 represents} alkyl, haloalkyl, cycloalkyl or cyano,

R ^{5 represents} alkyl or haloalkyl and

R and R ⁷ each independently represent hydrogen, alkyl, haloalkyl, alkoxy or haloalkoxy and

n represents 0, 1 or 2,

found.

Depending on the nature of the substituents, the compounds of the formula (I) can optionally be present as geometric and / or optical isomers or isomer mixtures of different compositions. Both the pure isomers and the isomer mixtures are claimed according to the invention.

in welcherIt has also been found that the new 2-oximino-2-pyridyl-acetic acid derivatives of the general formula (I)

in which

Ar represents optionally substituted aryl or heteroaryl,

R ^{1 represents} alkyl or haloalkyl,

R ² and R ³ independently of one another each represent hydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkylthio, alkenyl, alkenyloxy, alkynyl, alkynyloxy, haloalkyl, haloalkoxy, haloalkylthio, haloalkenyl, haloalkenyloxy, haloalkynyl, haloalkynyloxy, alkoxycarbonyl, Hydroximinoalkyl, alkoximinoalkyl or optionally substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy,

A for oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH ₂ -O-, -O-CH ₂ -, -CH ₂ -SO _n -, -SO _n - CH ₂ -, -SO _n _, -C (R ⁴ ) = N- O-, -C (R ⁴ ) = NO-CH ₂ - or -N (R ⁶ ) -, stands, and

Z represents a radical of the formula -OR ⁵ or -NR ⁶ R ⁷ , where

^{'R 4} represents alkyl, haloalkyl, cycloalkyl or cyano,

R ^{5 represents} alkyl or haloalkyl and

R ⁶ and R ⁷ each independently represent hydrogen, alkyl, halogen alkyl, alkoxy or haloalkoxy and

n stands for 0. 1 or 2 get when one

a) a-oxopyridyl acetic acid derivatives of the formula (Ha),

in which

R ² , R ³ , Ar, A and Z have the meaning given above,

or their ketals of the formula (Ilb),

in which

R ² , R ³ , Ar, A and Z have the meaning given above and

R ^{8 represents} alkyl,

- or mixtures of a-oxopyridyl acetic acid derivatives of the formula (Ila) and their ketals of the formula (Ilb) -

with hydroxylamines of the formula (III),

H ^ -OR ¹ (III)

in which R has the meaning given above,

- or with hydrogen halide adducts of compounds of the formula (III) -

if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary,

or if you

b) 2-oximino-2- (halogenopyridyl) acetic acid derivatives of the formula (IV),

in which

R ¹ , R ² , R ³ and Z have the meaning given above and

X represents halogen,

with nucleophiles of the formula (V),

Ar-A ^ H (V) in which

Ar has the meaning given above and

A ^{1 represents} oxygen, sulfur or a radical of the formula -C (R ⁴ ) = NO-, where

R ^{4 has} the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary,

or if you

c) 2-oximino-2-pyridyl-acetic acid derivatives of the formula (Ia),

in which

R ¹ , R ² , R ³ , R ⁵ , Ar and A have the meaning given above,

with amines of the formula (VI),

R ⁶ HN (VI)

V in which

R ⁶ and R ^{7 have} the meaning given above,

if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary,

or if you

d) 2-pyridyl acetic acid derivatives of the formula (VII)

in which

R ² , R ³ , Ar, A and Z have the meaning given above, with oximation agents and then with alkylating agents of the formula (VIII)

XR ¹ (vπi)

in which

R ^{1 has} the meaning given above and

X represents halogen or the grouping -O-SO ₂ -OR ¹ ,

if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent.

Finally, it was found that the new 2-oximino-2-pyridyl-acetic acid derivatives of the general formula (I) have good activity against organisms which damage plants, in particular against fungal organisms.

Surprisingly, the 2-oximino-2-pyridyl-acetic acid derivatives of the general formula (I) according to the invention show a considerably better activity against microorganisms which damage the plants in comparison to the 2-methoxy-acrylic acid esters known from the prior art, such as, for example, the compound 3- Methyl methoxy-2- (6-phenyl-2-pyridylthio) acrylic acid or the compound 3- methoxy-2- [N- (6-phenyl-2-pyridyl) -N-methylamino] acrylic acid methyl ester or the compound 3- Methyl methoxy-2- [5- (4-chlorophenyl) -3-pyridyloxy] acrylic acid. which are chemically and functionally obvious compounds. The 2-oximino-2-pyridyl-acetic acid derivatives according to the invention are generally defined by the formula (I). Compounds of formula (I) are preferred. in which

Ar for optionally single or multiple, identical or different substituted aryl with 6 to 10 carbon atoms or for optionally single or multiple, identical or different substituted and / or benzo-fused heteroaryl with 2 to 9 carbon atoms and 1 to 5 identical or different heteroatoms stands, with the following being suitable as substituents: halogen, cyano, nitro, hydroxy, amino, formyl, carbamoyl, thiocarbamoyl, in each case straight-chain or branched alkyl, alkoxy, alkylthio,

Alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms, each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms, each straight-chain or branched halogenoalkyl, 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 with 2 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroximinoalkyl or

Alkoximinoalkyl, each having 1 to 6 carbon atoms in the individual alkyl parts, in each case optionally one or more times, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 same or different

Halogen atoms substituted, in each case doubly linked alkylene or dioxyalkylene, each with 1 to 6 carbon atoms, cycloalkyl with 3 to 7 carbon atoms, 3- to 7-membered heterocyclyl with 2 to 6 carbon atoms and 1 to 3 identical or different heteroatoms - especially nitrogen , Oxygen and / or sulfur -, and in each case optionally in the phenyl moiety one or more times, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 same or different halo phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy, with atomic atoms and / or straight-chain or branched alkoxy with 1 to 4 carbon atoms and / or straight-chain or branched haloalkoxy with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms,

R ^{1 represents} straight-chain or branched alkyl having 1 to 8 carbon atoms or straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms,

R ² and R ³ independently of one another each represent hydrogen, halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkylthio

1 to 6 carbon atoms, each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms, each straight-chain or branched alkynyl or alkynyloxy each having 2 to 6 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio 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 13 identical or different halogen atoms, each straight-chain or branched haloalkynyl or haloalkynyloxy each having 2 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, in each case straight-chain or branched alkoxycarbonyl, hydroximinoalkyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts and also for each optionally in the phenyl part simple or m times, identical or different by halogen and / or straight-chain or branched alkyl with

1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and / or straight-chain or branched alkoxy having 1 to 4 carbon atoms and / or straight-chain or branched haloalkoxy having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms are substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy, A represents oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following

Groupings -CH ₂ -O-, -O-CH ₂ -, -CH ₂ -SO _n -, -SO _n -CH ₂ -, -SO _n -, -C (R ⁴ ) = NO-, -C (R ⁴ ) = NO-CH ₂ - or -N (R ⁶ ) -, and

Z represents a radical of the formula -OR ⁵ or -NR ⁶ R ⁷ , where

R ^{4 represents} straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, cycloalkyl having 3 to 8 carbon atoms or cyano,

R ^{5 represents} straight-chain or branched alkyl having 1 to 8 carbon atoms or straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms,

R ⁶ and R ⁷ each independently represent hydrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, or straight-chain or branched alkoxy 1 to 8 carbon atoms stand and

n represents 0, 1 or 2,

those 2-oximino-2-pyridyl-acetic acid derivatives of the formula (I), in which the group Ar-A ¹ - and the oximinoacetic acid residue in the pyridine ring are adjacent, are particularly preferred.

Compounds of the formula (I) in which

Ar for optionally single to five times, identical or differently substituted aryl having 6 or 10 carbon atoms or for optionally single to four times, identical or differently substituted and / or benzo-fused Heteroaryl with 2 to 9 carbon atoms and 1 to 3 identical or different heteroatoms - in particular nitrogen, oxygen and / or sulfur - is available, the following being suitable in each case: halogen, cyano, nitro, hydroxy, amino, formyl, carbamoyl, thiocarbamoyl , in each case straight-chain or branched alkyl, alkoxy, alkylthio,

Alkylsulfinyl or alkylsulfonyl each having 1 to 4 carbon atoms, each straight-chain or branched alkenyl or alkenyloxy each

2 to 4 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 up to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroximinoalkyl or alkoximinoalkyl each having 1 to 4 carbon atoms in the individual alkyl parts , each optionally mono- or polysubstituted, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 3 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms, respectively ils doubly linked alkylene or dioxyalkylene, each with 1 to 4 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, 5- to 7-membered, saturated heterocyclyl with 4 to 6 carbon atoms and 1 or 2 identical or different heteroatoms - in particular nitrogen, oxygen and / or Sulfur, and in each case optionally in the phenyl part, one to three times, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 3 carbon atoms and / or straight-chain or branched haloalkyl having 1 to

3 carbon atoms and 1 to 7 identical or different halogen atoms and / or straight-chain or branched alkoxy with 1 to 3 carbon atoms and / or straight-chain or branched haloalkoxy with 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms substituted phenyl , Phenoxy, benzyl, benzyloxy, phenylethyl or phenyl¬ ethyloxy, R ^{1 represents} straight-chain or branched alkyl having 1 to 6 carbon atoms or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms,

R ² and R ³ independently of one another each represent hydrogen, halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio, each with

1 to 4 carbon atoms, each straight-chain or branched alkenyl or alkenyloxy each having 2 to 4 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight-chain or branched haloalkenyl or

Haloalkenyloxy each having 2 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight-chain or branched alkoxycarbonyl, hydroximinoalkyl or alkoximinoalkyl each having 1 to 4 carbon atoms in the individual alkyl parts and, moreover, in each case optionally in the phenyl part, simply to five times, identical or different from halogen and / or straight-chain or branched alkyl having 1 to 3 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms and / or straight-chain the branched alkoxy having 1 to 3 carbon atoms and / or straight chain or branched

Halogenalkoxy with 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy,

A for oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH ₂ -O-, -O-CH ₂ -, -CH ₂ -SO _n -, -SO _n - CH ₂ -, -SO _n -,

-C (R ⁴ ) = NO-, -C (R ⁴ ) = NO-CH ₂ - or -N (R ⁶ ) - stands and

Z represents a radical of the formula -OR ⁵ or -NR ⁶ R ⁷ , where

R ⁴ for straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, represents cycloalkyl having 3 to 7 carbon atoms or cyano,

R ⁵ for straight-chain or branched alkyl having 1 to 6 carbon atoms or for straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different

Halogen atoms,

R ⁶ and R ⁷ each independently represent hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, or straight-chain or branched alkoxy 1 to 6 carbon atoms are and

n represents 0, 1 or 2,

those 2-oximino-2-pyridyl-acetic acid derivatives of the formula (I), in which the group Ar-A ¹ - and the oximinoacetic acid residue in the pyridine ring are adjacent, are particularly preferred.

Compounds of the formula (I) in which

Ar for phenyl or naphthyl which is optionally monosubstituted to trisubstituted identically or differently or for each optionally monosubstituted to trisubstituted and / or substituted in the same or different ways and / or benzo-annelated

Furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyrazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl or triazinyl, where in each case hydroxyl, chlorine, are suitable: Cyano, nitro, amino, formyl, carbamoyl,

Thiocarbamoyl. Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, Methylthio, ethylthio, methylsulfinyl, methylsulfonyl, allyl, butenyl, allyloxy, butenyloxy, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl, Trifluoromethylsulfonyl, dimethylamino, diethylamino, acetyl, acetoxy, methylsulfonyloxy, ethylsulfonyloxy, methoxycarbonyl, ethoxycarbonyl, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, ethoximinomethyl, ethoximinoethyl, propan-l, 1,4-di-oxy-1, 3-diyl Dioxyethylene, dioxypropylene, difluorodioxymethylene,

Tetrafluorodioxyethylene, cyclopropyl, cyclopentyl, cyclohexyl, 1-pyrrolidinyl, 1-piperidinyl, 1-perhydroazepinyl, 4-morpholinyl or in each case optionally one to three times, identically or differently, by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy-substituted phenyl, phenoxy, benzyl or benzyloxy,

R ^{1 represents} straight-chain or branched alkyl having 1 to 4 carbon atoms or haloalkyl having 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms,

R ² and R ³ independently of one another each represent hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,

Methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, allyl, butenyl, allyloxy, butenyloxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, difluorochloromethylthio, methoxycarbonyl Hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, ethoximinomethyl, ethoximinoethyl or phenyl, phenoxy, benzyl or Benzyloxy stand,

A oxygen, ethene-1,2-diyl, ethyne 1,2-diyl or for one of the following groups -CH ₂ -O-, -O-CH ₂ -, -CH ₂ -SO _n -, -SO _n - CH ₂ -, -SO _n -, -C (R ⁴ ) = NO-, -C (R ⁴ ) = NO-CH ₂ - or -N (R ⁶ ) - stands and

Z represents a radical of the formula -OR ⁵ or -NR ⁶ R ⁷ , where

R ^{4 represents} methyl, ethyl, trifluoromethyl, cyclopropyl or cyano, R represents straight-chain or branched alkyl having 1 to 4 carbon atoms or haloalkyl having 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms and

R ⁶ and R ⁷ each independently represent hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, halogeno alkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms or straight-chain or branched alkoxy have 1 to 4 carbon atoms and

n represents 0, 1 or 2,

those 2-oximino-2-pyridyl-acetic acid derivatives of the formula (I) in which the group Ar-A ¹ - and the oximino-acetic acid residue in the pyridine ring are adjacent are particularly preferred.

A very particularly preferred group of compounds of the formula (I) are the compounds of the formula (IA)

in which

A, Ar, R ¹ , R ² , R ³ and Z are those specified above as being particularly preferred

Have meanings.

The general definitions given above or those specified in preferred ranges apply both to the end products of the formula (I) and correspondingly to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with one another as desired, that is to say also between the specified ranges of preferred compounds.

Particularly preferred groups of compounds of the formula (I) are the compounds of the formulas (IA) to (ID):

in which

A, Ar, R, R 2, _D R3 and Z have the meanings given particularly preferably above. Very particularly preferred groups of compounds of the formula (I) are compounds of the formulas (IA-1) to (IA-17):

Formula; IA-I) = compounds of formula (IA), where A = oxygen;

Formula I; iA-2) = compounds of the formula (IA), where A = sulfur; Formula (iA-3) = compounds of formula (IA), where A = -CH = CH-;

Formula (IA-4) = compounds of the formula (IA), where A = -Q≡C-;

Formula; IA-5) = Compounds of formula (IA), where A = -CH ₂ O-;

Formula: iA-6) = compounds of the formula (IA), where A = -OCH ₂ -;

Formula (IA-7) = compounds of formula (IA), where A = -CH ₂ S-; Formula (IA-8) = compounds of formula (IA), where A = -CH ₂ SO-;

Formula (IA-9) = compounds of formula (IA), where A = -CH ₂ SO ₂ -;

Formula (TA-10) = compounds of the formula (IA), where A = -SCH ₂

Formula (: iA-l l) = compounds of the formula (IA), where A = -SOCH ₂ -;

Formula (; iA-12) = compounds of formula (IA), where A = -SO ₂ CH ₂ Formula (; iA-13) = compounds of formula (IA), where A = -SO-;

Formula (iA-14) = compounds of formula (IA), where A = -SO ₂ -;

Formula (1A-15) = compounds of formula (IA), where A = -C (R ⁴ ) = NO-;

Formula (iA-16) = compounds of formula (IA), where A = -C (R ⁴ ) = NOC

Formula (; IA-Π) = compounds of formula (IA), where A = -NR ⁶ -;

in which

Ar, Rl l ^1, R ^2, R ^3, R ^4, R ⁶ and Z have the meanings given above as being very particularly preferred.

Very particularly preferred groups of compounds of the formula (I) are also compounds of the formulas (IB-1) to (IB-17):

Formula (IB-1) = compounds of formula (IB), where A = oxygen; Formula (IB-2) = compounds of formula (IB), where A = sulfur; Formula (IB-3) = compounds of formula (IB), where A = -CH = CH-; Formula (IB-4) = Compounds of formula (IB), where A = -C≡C-; Formula (IB-5) = compounds of formula (IB), where A = -CH ₂ O-; Formula (IB-6) = compounds of formula (IB), where A = -OCH ₇ -; - 15th

Formula (IB-7) = compounds of formula (IB), wherein A = -CH ₂ S-; Formula (IB-8) = compounds of formula (IB), wherein A = -CH ₂ SO-; Formula (IB-9) = compounds of formula (IB), wherein A = -CH ₂ SO ₂ -; Formula (IB-10) = compounds of formula (IB), where A = -SCH ₂ -; Formula (IB-11) = compounds of formula (IB), where A = -SOCH ₂ -; Formula (IB-12) = compounds of formula (IB), where A = -SO ₂ CH ₂ -; Formula (IB-13) = compounds of formula (IB), where A = -SO-; Formula (IB-14) = compounds of formula (IB), where A = -SO ₂ -; Formula (IB-15) = compounds of formula (IB), where A = -C (R ⁴ ) = NO-; Formula (IB-16) = compounds of formula (IB), where A = -C (R ⁴ ) = NO-CH ₂ -; Formula (IB-17) = compounds of formula (IB), wherein A = -NR ⁶ -;

in which

Ar, R, R, R, R, R and Z have the meanings given above as being particularly preferred.

Very particularly preferred groups of compounds of the formula (I) are furthermore compounds of the formulas (IC-1) to (IC 1-17):

Formula (IC-1) = compounds of formula (IC), where A = oxygen;

Formula (IC-2) = compounds of formula (IC), where A = sulfur;

Formula (IC-3) = compounds of formula (IC), where A = -CH = CH-;

Formula (IC-4) = Compounds of formula (IC), where A = -C≡C-;

Formula (IC-5) = Compounds of formula (IC), wherein A = -CH ₂ O-;

Formula (IC-6) = compounds of formula (IC), where A = -OCH ₂ -;

Formula (IC-7) = Compounds of formula (IC) where A = -CH ₂ S-;

Formula (IC-8) = compounds of formula (IC), where A = -CH ₂ SO-;

Formula (IC-9) = compounds of formula (IC), where A = -CH SO ₂ -;

Formula (IC-10) = compounds of formula (IC), where A = -SCH ₂ ^_ ;

Formula (IC-11) = compounds of formula (IC), where A = -SOCH ₂ -;

Formula (IC-12) = compounds of the formula (IC), where A = -SO ₂ CH ₂ -;

Formula (IC- 13) = compounds of formula (IC), where A = -SO-;

Formula (IC- 14) = compounds of formula (IC), where A = -SO ₂ -;

Formula (IC- 15) = compounds of formula (IC), where A = -C (R ⁴ ) = NO-; Formula (IC- 16) = compounds of formula (IC), where A = -C (R ⁴ ) = NO-CH ₂ -; Formula (IC- 17) = compounds of formula (IC), where A = -NR ⁶ -;

in which

Ar, R ¹ , R ² , R ³ , R ⁴ , R ⁶ and Z have the meanings given above as being particularly preferred.

Very particularly preferred groups of compounds of the formula (I) are also compounds of the formulas (ID-1) to (ID-17):

Formula (ID-1) = compounds of formula (ID), where A = oxygen;

Formula (ID-2) = compounds of formula (ID), where A = sulfur;

Formula (ID-3) = compounds of formula (ID), where A = -CH = CH-;

Formula (ID-4) = compounds of formula (ID), where A = -C≡C-;

Formula (ID-5) = compounds of formula (ID), where A = -CH ₂ O-;

Formula (ID-6) = compounds of formula (ID), where A = -OCH ₂ -;

Formula (ID-7) = compounds of formula (ID), where A = -CH ₂ S-;

Formula (ID-8) = compounds of formula (ID), where A = -CH ₂ SO-;

Formula (ID-9) = compounds of formula (ID), where A = -CH ₂ SO ₂ -;

Formula (ID-10) = compounds of formula (ID), where A = -SCH ₂ -;

Formula (ID-11) = compounds of formula (ID), where A = -SOCH ₂ -;

Formula (ID-12) = compounds of formula (ID), where A = -SO ₂ CH ₂ -;

Formula (ID-13) = compounds of formula (ID), where A = -SO-;

Formula (ID-14) = compounds of formula (ID), where A = -SO ₂ -;

Formula (ID-15) = compounds of formula (ID), where A = -C (R ⁴ ) = NO-;

Formula (ID-16) = Compounds of formula (ID), where A = -C (R ⁴ ) = NO-CH ₂

Formula (ID-17) = compounds of formula (ID), where A = -NR ⁶ -;

in which

Ar, R ¹ , R ² , R ³ , R ⁴ , R ⁶ and Z have the meanings given above as being particularly preferred. Examples of the possible combinations of the compounds of the formulas (IA1) to (ID-17) defined above are listed below, with Z for each of the compounds of the formulas (IA1) to (ID-17) for -OCH ₃ and -NHCH ₃ where R ⁴ and R ⁶ in the examples of formulas (IA, B, C, D-15, 16, 17) is methyl, and R ¹ , R ² , R ³ and Ar are each indicated as follows.

R ¹ RR ^J Ar

CI R ¹ R ² R ³ ar

R¹ R^J Ar

R ¹ R ^J Ar

-CH, H H

-CH, H H

-CH, HH

If, for example, 2- [3- (3-chlorophenoxy-methyl) pyridin-2-yl] -2-oxoacetic acid methyl ester and O-methyl-hydroxylamine hydrochloride are used as starting materials, the course of the reaction can be carried out in accordance with the invention Represent process (a) by the following formula:

If, for example, 2- (2-chloro-pyridin-3-yl) -2-methoximino-acetic acid methyl amide and benzyl mercaptan are used as starting materials, the reaction sequence in process (b) according to the invention can be represented by the following formula:

If, for example, 2- [2- (2-chloropyridin-5-yl-methylamino) -pyridin-3-yl] -2-methoximino-acetic acid methyl ester and methylamine are used as starting materials, the course of the reaction of the process according to the invention ( c) represented by the following formula:

Verwendetmanbeispielsweise2-[4-(2-Furyl)-methoxy-pyridin-3-yl]-essigsäure-ethyl- ester, Methylnitrit und Methyliodid als Ausgangsstoffe, so läßt sich der Reaktions¬ ablauf beim erfindungsgemäßen Verfahren (d) durch das folgende Formelschema dar¬ stellen:

If, for example, ethyl 2- [4- (2-furyl) methoxy-pyridin-3-yl] acetic acid, methyl nitrite and methyl iodide are used as starting materials, the reaction sequence in process (d) according to the invention can be represented by the following formula ¬ make:

The a-oxopyridyl acetic acid derivatives required as starting compounds for carrying out process (a) according to the invention are generally defined by the formula (IIa) and the corresponding ketals by the formula (IIb). In these formulas (Ila) and (Ilb), R ² , R ³ , Ar, A and Z preferably or in particular have those meanings which are preferred or particularly preferred in connection with the description of the compounds of the formula (I) according to the invention were preferably given for R ² , R ³ , Ar, A and Z; R ⁸ preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.

The starting materials of the formulas (Ila) and (Ilb) are not yet known from the literature; as new substances, they are the subject of the present application.

The new compounds of the formulas (Ila) or (Ilb) are obtained if corresponding halogenated oxopyridyl acetic acid derivatives of the general formulas (IXa) or (Kb)

(IXa) (IXb) in which

R ² , R ³ , R ⁸ and Z have the meaning given above and

X represents halogen,

with nucleophiles of the formula (V)

Ar-A ^ H (V)

in which

Ar has the meaning given above and

A ^{1 represents} oxygen, sulfur or a radical of the formula -C (R ⁴ ) = NO-,

in which

R ^{4 has} the meaning given above,

- or with alkali metal salts of compounds of formula (V) -

optionally in the presence of a reaction auxiliary, e.g. Copper (I) chloride, and optionally in the presence of a diluent, e.g. Dioxane, implemented at temperatures between 20 ° C and 150 ° C.

The halogenated oxopyridyl acetic acid derivatives of the general formulas (IXa) and (IXb) are not yet known from the literature; as new substances, they are the subject of the present application.

The new compounds of the formulas (IXa) and ((IXb) are obtained if halogenated pyridine-carboxylic acid cyanides of the formula (X)

in which

R ² and R ^{3 have} the meaning given above and

X represents halogen,

hydrolyzed with aqueous acids, for example with hydrochloric acid at temperatures between 10 ° C and 100 ° C, then by reaction with alcohols, for example with methanol, optionally in the presence of a reaction auxiliary, such as e.g. Sulfuric acid and optionally in the presence of a diluent, e.g. Toluene esterified at temperatures between 20 ° C and 150 ° C, optionally by reaction with orthoesters, for example with trimethyl orthoformate or triethyl ester, at temperatures between 20 ° C and 150 ° C converted into corresponding ketals and / or optionally by reaction with amines, for example with methylamine, at temperatures between 20 ° C and 150 ° C converted into corresponding amides.

The halogenated pyridine-carboxylic acid cyanides of the formula (X) are not yet known from the literature; as new substances, they are the subject of the present application.

The new compounds of the formula (X) are obtained if halogenated pyridinecarboxylic acid chlorides of the formula (XI)

in welcher R², R³ und X die oben angegebene Bedeutung haben,

in which R ² , R ³ and X have the meaning given above,

with metal cyanides, for example with copper (I) cyanide, optionally in the presence of a diluent, such as e.g. Acetonitrile, at temperatures between 10 ° C and 100 ° C.

The halogenated pyridine-carboxylic acid chlorides of the formula (XI) are known and / or can be prepared by processes known per se (cf. DE-OS 2713316, J. Heterocycl. Chem. 25 (1988), 1367-1371).

Formula (III) provides a general definition of the hydroxylamines further required as starting materials in process (a) according to the invention. In formula (III), R ¹ preferably or in particular has the meaning which has already been stated as preferred or as particularly preferred for R ^{1 in} connection with the description of the compounds of the formula (I) according to the invention.

Particularly suitable hydrogen halide adducts are the hydrogen chloride and hydrogen bromide adducts.

The starting materials of formula (III) are known organic synthetic chemicals.

Formula (IV) provides a general definition of the 2-oximino-2- (halogenopyridyl) acetic acid derivatives to be used as starting compounds for carrying out process (b) according to the invention. In the formula (IV), R ¹ , R ² , R ³ and Z preferably or in particular have the meaning which, in connection with the description of the compounds of the formula (I) according to the invention, is preferred or particularly preferred for R ¹ , R ² , R ³ and Z was specified.

The starting materials of the formula (IV) are not yet known from the literature; as new substances, they are the subject of the present application.

The new compounds of the formula (IV) are obtained if corresponding halogenated oxopyridyl acetic acid derivatives of the general formulas (IXa) or (IXb)

in welchen

in which

R ² , R, R and Z have the meaning given above and

X represents halogen,

with hydroxylamines of the formula (III)

H ₂ NOR ^] (III) in which

R ^{1 has} the meaning given above,

- or with hydrogen halide adducts of compounds of the formula (III) -

optionally in the presence of a reaction auxiliary, e.g. Acetic acid, and optionally in the presence of a diluent, e.g. Methanol, at temperatures between 10 ° C. and 100 ° C.

Formula (V) generally defines the nucleophiles to be used further as starting compounds for carrying out process (b) according to the invention. Ar in formula (V) preferably or in particular has the meaning which has already been stated as preferred or as particularly preferred for Ar in connection with the description of the compounds of the formula (I) according to the invention; A ¹ preferably represents oxygen, sulfur or the rest of the formula -O-CH ₂ -, -C (R ⁴ ) = NO- or -C (R ⁴ ) = NO-CH ₂ -, where R ^{4 is} the above preferred or has the meaning given as particularly preferred. The starting materials of formula (V) are known organic synthetic chemicals.

Formula (Ia) provides a general definition of the 2-oximino-2-pyridyl-acetic acid derivatives to be used as starting compounds for carrying out process (c) according to the invention. In formula (Ia), R ¹ , R ² , R ³ , R ⁵ , Ar and A preferably or in particular have the meaning which, in connection with the description of the compounds of the formula (I) according to the invention, is preferred or was given as being particularly preferred for R ¹ , R ² , R ³ , R ⁵ , Ar and A.

The starting materials of the formula (Ia) for process (c) are new compounds according to the invention; they can be prepared by processes (a) and (b) according to the invention.

Formula (VI) provides a general definition of the amines to be used as starting compounds for carrying out process (c) according to the invention. In formula (VI), R ⁶ and R ⁷ preferably or in particular have the meaning which has already been stated as preferred or as particularly preferred for R ⁶ and R ⁷ in connection with the description of the compounds of the formula (I) according to the invention has been.

The starting materials of formula (VI) are known organic synthetic chemicals.

Formula (VII) provides a general definition of the halogenated 2-pyridyl-acetic acid derivatives to be used as starting compounds for carrying out process (d) according to the invention. In formula (VII), R ² , R ³ , Ar, A and Z 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 as particularly preferred for R ² , R ³ , Ar, A and Z was specified. The starting materials of the formula (VII) are known and / or can be prepared by processes known per se (cf. EP-A 243012, EP-A 312243).

Formula (VIII) provides a general definition of the alkylating agents which are further used as starting compounds for carrying out process (d) according to the invention. In formula (VIII), R ¹ preferably or in particular the meaning which has already been given in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for R ¹ ; X preferably represents chlorine, bromine, iodine or the grouping -O-SO ₂ -OR ¹ .

The alkylating agents of formula (VIII) are known organic synthesis chemicals.

Process (a) according to the invention for the preparation of the new 2-oximino-2-pyridylacetic acid derivatives of the formula (I) is preferably carried out using diluents. Inert organic solvents are particularly suitable as diluents for carrying out process (a) according to the invention. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides such as N N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

Process (a) according to the invention is preferably carried out in the presence of a suitable reaction auxiliary. All customary inorganic or organic acids are suitable as such. These preferably include protonic acids, for example hydrochloric acid, sulfuric acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid.

The reaction temperatures can be varied within a substantial range when carrying out process (a) according to the invention. In general, temperatures between 0 ° C and + 150 ° C, preferably at temperatures between 20 ° C and + 120 ° C. Process (a) according to the invention is usually carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

To carry out process (a) according to the invention, 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol, of hydroxylamine are generally employed per mol of a-oxopyridyl acetic acid derivative of the formula (II) Formula (III) or a corresponding hydrogen halide and optionally 1.0 to 6.0 mol, preferably 1.0 to 3.0 mol, of reaction auxiliaries. The reaction is carried out, worked up and isolated by known methods.

Inert organic solvents are particularly suitable as diluents for carrying out process (b) according to the invention. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides such as NJM-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; or sulfoxides such as dimethyl sulfoxide.

If appropriate, the process according to the invention can (b) also be carried out in a two-phase system, such as water / toluene or water / dichloromethane, if appropriate in the presence of a suitable phase transfer catalyst. Examples of such catalysts are: tetrabutylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium chloride, tributyl-methylphosphonium bromide, trimethyl-C ^ / C ^ -alkylammonium chloride, trimethyl-C ^ / C _j s-alkylammonium bromide, dibenzyl-methyl- ₁₂ -dimethyl-ammonium-dimethyl- ₁₄ -methyl-ammonium-ammonium alkylbenzylammonium chloride, dimethyl-C ₁₂ / C ₁₄ -alkyl-benzylammonium bromide, tetrabutylammonium hydroxide, triethylbenzylammonium chloride> ethyltrioctylammonium chloride, trimethylbenzylammonium chloride, 15-crown-5, 18-crown-6 or tris- [2- (2-meth- oxyethoxy) ethyl] amine. Process (b) according to the invention is preferably carried out in the presence of a suitable reaction auxiliary. All customary inorganic or organic bases are suitable as such. These include, for example, alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium ¬ hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N -Dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloun- decene (DBU).

The reaction temperatures can be varied within a substantial range when carrying out process (b) according to the invention. In general, temperatures between 0 ° C and + 150 ° C, preferably at temperatures between 20 ° C and + 120 ° C.

Process (b) according to the invention is usually carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

To carry out process (b) according to the invention, generally 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol, are employed per mole of 2-oximino-2- (halogenopyridyl) acetic acid derivative of the formula (IV) Mol of nucleophile of the formula (V) and, if appropriate, 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol, of reaction auxiliaries. The reaction is carried out, worked up and isolated by known methods.

In addition to water, especially diluents for carrying out process (c) according to the invention are organic solvents. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Alcohols, such as methanol, ethanol, n- or i-propanol; Ether like Diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide or sulfoxides, such as dimethyl sulfoxide.

Process (c) according to the invention is optionally carried out in the presence of a suitable reaction auxiliary. All customary inorganic or organic bases are suitable as such. These include, for example, alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium ¬ hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N -Dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloun- decene (DBU).

It is also possible to use the amine of the formula (III) used as the reactant in a corresponding excess at the same time as a reaction auxiliary.

The reaction temperatures can be varied within a substantial range when carrying out process (c) according to the invention. In general, temperatures between -30 ° C and + 150 ° C, preferably at temperatures between -20 ° C and + 120 ° C.

Process (c) according to the invention is usually carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

To carry out process (c) according to the invention, 2-

Oximino-2-pyridyl-acetic acid derivative of the formula (Ia) in general 1.0 to 3.0 mol, preferably 1.0 to 1.5 mol of amine of the formula (VI) and optionally 0.1 to 3.0 mol, preferably 0.5 to 1.5 mol of base used as reaction auxiliary on. In a special embodiment, it is also possible to prepare the 2-oximino-2-pyridyl-acetic acid derivatives of the formula (Ia) used as starting products in a preceding reaction in the reaction vessel and then without isolation directly in a so-called "one-pot reaction" according to the to further implement method (c) according to the invention. The reaction is carried out, worked up and isolated in each case analogously to known methods (cf. the preparation examples).

Process (d) according to the invention is carried out using an oximation agent. In this context, oximizing agents are the reagents suitable for converting methylene compounds into hydroximino compounds. Examples of suitable oximation agents are: nitrous acid, nitrosyl chloride, alkyl nitrites such as e.g. Methyl, ethyl, n or i propyl, n, i, s and t-butyl nitrite

Inert organic solvents are particularly suitable as diluents for carrying out process (d) according to the invention. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides such as N, N-dimethylformamide, NJNf-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

Process (d) according to the invention is optionally carried out in the presence of a suitable reaction auxiliary. All conventional inorganic or organic bases are suitable as such. These include, for example, alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as sodium hydride, sodium amide, sodium methylate, Sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate. Ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO) , Diazabicyclonones (DBN) or diazabicycloun- decene (DBU).

The reaction temperatures can be varied within a substantial range when carrying out process (d) according to the invention. In general, temperatures between -20 ° C and + 120 ° C, preferably at temperatures between 0 ° C and + 100 ° C.

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

To carry out process (d) according to the invention, 1 to 5 mol, preferably 1.0 to 3.0 mol, of an oximation agent and 1 to 3 mol, preferably 1, are generally employed per mole of 2-pyridyl-acetic acid derivative of the formula (VII) 0 to 1.5 mol of an alkylating agent of the formula (VIII) and optionally 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol, of reaction auxiliaries. The reaction is carried out, worked up and isolated using known methods (cf. the preparation examples).

The active compounds according to the invention have a strong microbicidal action and can be used practically to combat unwanted microorganisms. The active ingredients are suitable for use as crop protection agents, in particular as fungicides.

Fungicidal agents in crop protection are used to combat plasmidiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes. Deuteromycetes. Some pathogens of fungal diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseu¬ doperonospora cubense;

Plasmopara species, such as, for example, Plasmopara viticola;

Peronospora species, such as, for example, Peronospora pisi or Peronospora brassicae;

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The active compounds according to the invention can be used with particularly good success for combating diseases in fruit and vegetable cultivation, such as, for example, against Venturia, Uncinula or Podosphaera species, or for controlling cereal diseases, for example against Erysiphe species. In addition, the active compounds according to the invention have good in vitro activity.

Depending on their respective physical and / or chemical properties, the active compounds can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV Cold and warm mist formulations. These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, under pressure the liquefied gases and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromas, such as xylene, toluene, alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes, or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide or dimethyl sulfoxide, and water; liquefied gaseous extenders or carriers mean those liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; Solid carrier materials are suitable: for example natural flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock flour, such as highly disperse silica, aluminum oxide and silicates; Solid carriers for granules are possible: for example broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene / fatty acid esters, polyoxyethylene fatty alcohol ethers, for example. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; The following may be used as dispersants: for example lignin sulfite waste liquor and methyl cellulose. Adhesives such as carboxymethyl cellulose, natural and synthetic, powdery, granular or latex-shaped polymers can be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils. Dyes such as inorganic pigments can be used. eg iron oxide, titanium oxide, ferrocy 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 can be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and also in mixtures with fertilizers and growth regulators.

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 apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.

In the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range: in general they are between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

In the seed treatment, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

When treating the soil, active ingredient concentrations are from 0.00001 to 0.1% by weight. preferably from 0.0001 to 0.02% by weight required at the site of action. Manufacturing examples:

example 1

3.43 g (1.5 mmol) of methyl 2- (2-chloro-pyridin-3-yl) -2-methoximinoacetate, 1.95 g (1.5 mmol) of sodium 4-cresolate, 0.15 g of copper ( I) chloride and 0.5 g of tris-diaza-heptylamine are suspended in 100 ml of dioxane and heated under reflux for 36 hours. The solvent is removed in a water jet vacuum, the residue is dissolved in 100 ml of ethyl acetate, washed with 10 ml of saturated sodium bicarbonate solution, dried over sodium sulfate and concentrated. The residue is dissolved in ethyl acetate and crystallized by stirring with cyclohexane.

3.15 g of 2- [2- (4-methylphenyl) pyridin-3-yl] -2-methoximinoacetic acid methyl ester of melting point 102 ° C. are obtained.

Example 2

3.0 g (1 mmol) of 2- [2- (4-methylphenyl) pyridin-3-yl] -2-methoximinoacetic acid methyl ester are dissolved in 200 ml of methanol and 1.55 g (5 mmol ) Initiated methylamine. The solution is stirred for a further 18 hours at 20 ° C. and concentrated in a water jet vacuum. The residue is dissolved in dichloromethane and crystallized by stirring with ether.

2.18 g of N-methyl-2- [2- (4-methylphenyl) pyridin-3-yl] -2-methoximinoessi g - acid amide with a melting point of 136 ° C. are obtained.

Example 3

7.29 g (0.03 mol) of methyl 2- (2-phenoxy-pyridin-3-yl) -acetic acid (for the preparation see EP 243 012, page 39) together with 9.3 g (0.09 Mol) of tert-butyl nitrite was added dropwise to a solution of 3.7 g (0.033 mol) of potassium tert-butoxide in 36 ml of tert-butanol. The mixture is stirred at 20 ° C for one hour. Then 4.68 g (0.033 mol) of methyl iodide are added and the mixture is stirred at 20 ° C. for a further hour. Water is added, the mixture is extracted with ethyl acetate, the organic phase is concentrated and the residue is chromatographed on diethyl ether / petroleum ether (low-boiling) in a ratio of 1: 1 on silica gel.

2 g (21% of theory) of 2-methoximino-2- (2-phenoxy-pyridin-3-yl) methyl acetate are obtained as an amorphous product.

1H NMR (CDC1 ₃ , tetraethylsilane): d = 3.864 (3H); 4.103 (3H); 7.05 - 7.38 (6H); 7.74 - 7.77 (1H); 8.19 - 8.22 (1H) ppm.

Example 4

1.0 g (3.5 mmol) of 2-methoximino-2- (2-phenoxy-pyridin-3-yl) -acetic acid methyl ester are added in 10 ml of tetrahydrofuran with 0.2 ml of 40% aqueous methylamine solution and Stirred at 20 ° C for 2 hours. It is poured into water, extracted with ethyl acetate, concentrated and the residue is chromatographed with diethyl ether / petroleum ether (1: 1).

0.9 g (90% of theory) of 2-methoximino-2- (2-phenoxy-pyridin-3-yl) acetic acid-methylamide are obtained as an amorphous product.

1H NMR (CDC1 ₃ , tetramethylsilane): d = 2.911-2.928 (3H); 3.993 (3H); 7.0 - 7.5 (6H); 7.65 - 7.72 (1H); 8.15 - 8.22 (1H) ppm.

Analogously to preparation examples 1 to 4 and in accordance with the general description of the preparation processes according to the invention, the compounds of the formula (I) listed below can also be prepared, for example.

Example 5

2-Methoximino-2- [2- (3-methylphenoxy) pyridin-3-yl] acetic acid methyl ester

1H-NMR (CDC1 ₃ , tetramethylsilane): d = 2.35 (3H); 3.87 (3H); 4.10 (3H); 6.88 7.08 (4H); 7.23 - 7.29 (IH); 7.72 - 7.76 (IH); 8.20 - 8.22 (IH) ppm.

Example 6

2-methoximino-2- [2- (3-methylphenoxy) pyridin-3-yl] acetic acid methyl amide

1H NMR (CDCI ₃ , tetramethylsilane): d = 2.35 (3H); 2.92-2.93 (3H); 4.0 (3H); 6.79 (IH); 6.9 - 7.1 (4H); 7.23 - 7.30 (IH); 7.66 - 7.70 (IH); 8.17 - 8.20 (IH) ppm. Example 7

Methyl 2-methoximino-2- [2- (3-chlorophenoxy) pyridin-3-yl] acetic acid 1H-NMR (CDC1 ₃ , tetramethylsilane): d = 3.87, 4.09 ppm.

Example 8

Methyl 2-methoximino-2- [2- (3-bromo-phenoxy) pyridin-3-yl] acetic acid 1H-NMR (CDCI ₃ , tetramethylsilane): d = 3.87, 4.10 ppm.

Example 9

Methyl 2-methoximino-2- [2- (3-methoxyphenoxy) pyridin-3-yl) acetic acid 1H-NMR (CDC1 ₃ , tetramethylsilane): d = 3.79, 3.86, 4.10 ppm.

Example 10

2-Methoximino-2- [2- (3-chlorophenoxy) pyridin-3-yl] acetic acid methylamide 1H-NMR (CDCI ₃ , tetramethylsilane): d = 2.93, 2.94, 3.99 ppm.

Example 11

2-methoximino-2- [2- (3-bromophenoxy) pyridin-3-yl] acetic acid methylamide 1H-NMR (CDC1 ₃ , tetramethylsilane): d = 2.93. 2.94. 3.99 ppm.

Example 12

Methyl 2-methoximino-2- [2- (4-tert-butylphenoxy) pyridin-3-yl] acetic acid 1H-NMR (CDCI ₃ , tetramethylsilane): d = l, 32, 3.86, 4 , 10 ppm.

Example 13

Methyl 2-methoximino-2- [2- (3,4-dichlorophenoxy) pyridin-3-yl] acetic acid 1H-NMR (CDC13, tetramethylsilane): d = 3.88, 4.10 ppm.

Example 14

2-methoximino-2- [2- (3-trifluoromethylphenoxy) pyridin-3-yl] acetic acid methyl amide

1H-NMR (CDC13. Tetramethylsilane): d = 2.69 (d, J = 4.7 Hz); 3.95 ppm

The following examples are obtained in accordance with Examples 1 to 5 and in accordance with the general description: table

Starting materials of formula (IV):

Example (IV-lϊ

4.0 g (0.02 mol) of methyl 2- (2-chloro-pyridin-3-yl) -glyoxylate are dissolved in 40 ml of methanol, with 16 ml of acetic acid and 5.01 g (0.06 mol) of methoxyamine hydrochloride added and heated under reflux for 18 hours. The solution is evaporated to dryness under reduced pressure, the residue is dissolved in 100 ml of ethyl acetate, washed twice with 10 ml of saturated sodium bicarbonate solution, the aqueous phases are extracted with ethyl acetate, and the combined organic phases are dried over sodium sulfate and concentrated.

3.9 g (85% of theory) of 2- (2-chloro-pyridin-3-yl) -2-methoximino-acetic acid methyl ester are obtained as an amorphous product.

¹ H NMR (CDC1 ₃ , tetramethylsilane): d = 3.9; 4.1 ppm.

Starting materials of the formula ( ^" IXa):

Example (IXa-1)

6.7 g (0.04 mol) of 2- (2-chloro-pyridin-3-yl) glyoxylic acid cyanide is concentrated in 50 ml. Hydrochloric acid dissolved and stirred at 50 ° C for 8 hours. The solution is largely concentrated under reduced pressure, 50 ml of toluene are added and the solvent is removed under reduced pressure. The residue is dissolved in 100 ml of methanol, with 1 ml of conc. Added sulfuric acid and heated under reflux for 24 hours. The solvent is removed under reduced pressure, the residue is dissolved in 100 ml of ethyl acetate, washed with 10 ml of saturated sodium bicarbonate solution, dried over sodium sulfate and concentrated. The crude product thus obtained is distilled over a 20 cm long Vigreux column.

4 g (50% of theory) of methyl 2- (2-chloro-pyridin-3-yl) -glyoxylate with a boiling point of 95-102 ° C. at 0.1 mbar are obtained.

Starting materials of formula (X):

Example (X-l)

A suspension of 0.05 8.8 g 0.05 mol of chloronicotinic acid chloride (for preparation see DE 2713316) and 8.9 g (0.10 mol) of copper (I) cyanide in 100 ml of acetonitrile is at 25 ° for one hour C stirred and then heated under reflux for two hours. The solvent is removed under reduced pressure and the residue is stirred twice with 200 ml of hot toluene and filtered off. Concentration of the solution gives 6.7 g (80% of theory) of 2- (2-chloropyridin-3-yl) glyoxylic acid cyanide.

Examples of use

Example A

Erysiphe test (wheat) / protective

Solvent: 10 parts by weight of N-methyl-pyrrolidone emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

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

To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants are dusted with spores of Erysiphe graminis f.sp.tritici.

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

Evaluation is carried out 7 days after the inoculation.

In this test, for example, the compounds according to Preparation Examples 5, 8, 14 and 18 show an efficiency of 100% at a rate of 400 g / ha.

Example B

PodosphaeraTest (apple) / protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

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

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

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

Evaluation is carried out 10 days after the inoculation.

In this test, for example, the compounds of Preparation Examples 1, 2, 3, 5, 11, 13 and 14 show an efficiency of at least 95% at an active ingredient concentration of 25 ppm.

Example C

Uncinula test (vine) / protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

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

To test for protective effectiveness, young plants are sprayed with the active ingredient preparation to runoff. After the spray coating has dried on, the plants are dusted with conidia of the Uncinula necator fungus.

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

Evaluation is carried out 14 days after the inoculation.

In this test, for example, the compound according to Preparation Example 4 shows an efficiency of at least at an active ingredient concentration of 25 ppm

95%.

Example D

Venturia test (apple) / protective

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

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

To test for protective effectiveness, young plants are sprayed with the active ingredient preparation to runoff. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the apple scab pathogen (Venturia inaequalis) and then remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 1 day.

The plants are then placed in a greenhouse at 20 ° C. and a relative atmospheric humidity of approx. 70%.

Evaluation is carried out 12 days after the inoculation.

In this test, for example, the compounds according to Preparation Examples 2, 3, 4, 5, 6, 7, 8, 10, 11, 12, 13 and 14 show an efficiency of up to 100% at an active ingredient concentration of 10 ppm.

Example E

Pyricularia test (rice) / protective

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

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

To test for protective effectiveness, young rice plants are sprayed with the active ingredient preparation to runoff. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants are then in a greenhouse at 100% rel. Humidity and 25 ° C.

The disease infestation is evaluated 4 days after the inoculation.

In this test, for example, the compounds according to Preparation Examples 8, 9 and 11 show efficiencies of 90 to 100% at an active ingredient concentration of 0.025%.

Example F

Sphaerotheca test (cucumber) / protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

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

To test for protective effectiveness, young plants are sprayed with the preparation of active compound to runoff. After the spray coating has dried on, the plants are dusted with conidia of the fungus Sphaerotheca fuliginea.

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

Evaluation is carried out 10 days after the inoculation.

In this test e.g. the compounds of preparation examples 8, 14, 17 and 18 have an efficacy of up to 100% at an active ingredient concentration of 10 ppm.

Claims

claims 1. 2-oximino-2-pyridyl-acetic acid derivatives of the general formula (I),

in which Ar represents optionally substituted aryl or heteroaryl, R ^{1 represents} alkyl or haloalkyl, R ² and R ³ independently of one another each represent hydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkylthio, alkenyl, alkenyloxy, alkynyl, alkynyloxy, haloalkyl, haloalkoxy, haloalkylthio, halogenalkenyl, haloalkenyloxy, haloalkynyl, haloalkynyloxy, Alkoxycarbonyl, hydroximinoalkyl, alkoximinoalkyl or represent in each case optionally substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy, A for oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH ₂ -O-, -O-CH ₂ -, -CH ₂ -SO _n -, -SO _n -CH ₂ -, -SO _n -, -C (R ⁴ ) = NO-, -C (R ⁴ ) = NO-CH ₂ - or -N (R ⁶ ) -, and Z represents a radical of the formula -OR ⁵ or -NR ⁶ R ⁷ , where R ^{4 represents} alkyl, haloalkyl, cycloalkyl or cyano, R ^{5 represents} alkyl or haloalkyl and R ⁶ and R ⁷ each independently represent hydrogen, alkyl, haloalkyl, alkoxy or haloalkoxy and n stands for 0, 1 or 2. 2. Compounds of formula (I) according to claim 1, in which Ar for optionally single or multiple, identically or differently substituted aryl with 6 to 10 carbon atoms or for optionally single or multiple, identical or differently substituted and / or benzo-fused heteroaiyl with 2 to 9 carbon atoms and 1 to 5 identical or different heteroatoms stands, whereby the following are possible as substituents: Halogen, cyano, nitro, hydroxy, amino, formyl, carbamoyl, thiocarbamoyl, each straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms, each straight-chain or branched alkenyl 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 carbons Substance atoms and 1 to 13 identical or different halogen atoms, in each case straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroximinoalkyl or alkoximinoalkyl, each having 1 to 6 carbon atoms in the individual alkyl parts, in each case, if appropriate, simply ode r multiply, identically or differently, in each case doubly linked alkylene or substituted by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms Dioxyalkylene, each with 1 to 6 carbon atoms, cycloalkyl with 3 to 7 carbon atoms, 3- to 7-membered heterocyclyl with 2 to 6 carbon atoms and 1 to 3 identical or different heteroatoms - in particular nitrogen, oxygen and / or sulfur - and in each case optionally in the phenyl moiety one or more times, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and / or straight-chain or branched alkoxy having 1 to 4 carbon atoms and / or straight-chain or branched halogenoalkoxy having ^'l atoms up to 4 carbon atoms and 1 to 9 identical or different halogen atoms substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy, R ¹ for straight-chain or branched alkyl having 1 to 8 carbon atoms or for straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different Halogen atoms, R ² and R ³ independently of one another each represent hydrogen, halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio each having 1 to 6 carbon atoms, each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms , each straight-chain or branched alkynyl or alkynyloxy each having 2 to 6 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched halo genalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched haloalkynyl or haloalkynyloxy each having 2 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched alkoxycarbonyl, Hydroximinoalk yl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts and also for each optionally in the Phenyl part single or multiple, identical or different by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and / or straight-chain or branched Alkoxy with 1 to 4 carbon atoms and / or straight-chain or branched haloalkoxy with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms are substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy, A for oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH ₂ -O-, -O-CH ₂ -, -CH ₂ -SO _n -, -SO _n -CH ₂ -, -SO _n -, -C (R ⁴ ) = NO-, -C (R ⁴ ) = NO-CH ₂ - or -N (R ⁶ ) -, and Z represents a radical of the formula -OR ⁵ or -NR ⁶ R ⁷ , where R ⁴ for straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched haloalkyl 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, represents cycloalkyl having 3 to 8 carbon atoms or cyano, R ^{5 represents} straight-chain or branched alkyl having 1 to 8 carbon atoms or straight-chain or branched halogeno alkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, R ⁶ and R ⁷ independently of one another each represent hydrogen, for straight-chain or branched alkyl having 1 to 8 carbon atoms, for straight-chain or branched haloalkyl having 1 to 6 Carbon atoms and 1 to 13 identical or different halogen atoms or stand for straight-chain or branched alkoxy with 1 to 8 carbon atoms and n stands for 0, 1 or 2. 3. Compounds of formula (I) according to claim 1, in which Ar for optionally single to five times, identical or differently substituted aryl having 6 or 10 carbon atoms or for optionally single to four times, identical or differently substituted and / or benzo-fused heteroaryl with 2 to 9 carbon atoms and 1 to 3 identical or various heteroatoms - in particular nitrogen, oxygen and / or sulfur -, the following being suitable in each case: halogen, cyano, nitro, hydroxyl, amino, formyl, carbamoyl, thiocarbamoyl, in each case straight-chain or branched alkyl, alkoxy, Alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 4 carbon atoms, each straight-chain or branched alkenyl or alkenyloxy each having 2 to 4 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight-chain or branched haloalkenyl or haloalkenyloxy each with 2 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, Alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroximinoalkyl or alkoximinoalkyl each having 1 to 4 carbon atoms in the individual alkyl parts, in each case optionally one or more times, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 3 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms substituted, in each case doubly linked alkylene or dioxyalkylene, each having 1 to 4 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, 5- to 7-membered, saturated heterocyclyl with 4 to 6 carbon atoms and 1 or 2 identical or different heteroatoms - in particular nitrogen, oxygen and / or sulfur - as well as in each case in the phenyl part in one to three times, identical or different by halogen and / or straight-chain or branched Alkyl with 1 to 3 carbon atoms and / or straight-chain or branched haloalkyl with 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms and / or straight-chain or branched alkoxy with 1 to 3 carbon atoms and / or straight-chain or branched haloalkoxy with 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy, R ¹ for straight-chain or branched alkyl having 1 to 6 carbon atoms or for straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, R ² and R ³ independently of one another each represent hydrogen, halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio, each with 1 to 4 carbon atoms, each straight-chain or branched alkenyl or alkenyloxy, each with 2 to 4 carbons ¬ atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, each with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight-chain or branched haloalkenyl or haloalkenyloxy, each with 2 to 4 carbon atoms and 1 to 9 the same or different halogen atoms, in each case straight-chain or branched alkoxycarbonyl, hydroximinoalkyl or alkoximinoalkyl, each having 1 to 4 carbon atoms in the individual alkyl parts and, moreover, in each case in the phenyl part, in each case optionally up to five times, identically or differently by halogen and / or straight-chain or branched alkyl with 1 to 3 Ko Hydrogen atoms and / or straight-chain or branched haloalkyl having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms and / or straight-chain or branched alkoxy having 1 to 3 Carbon atoms and / or straight-chain or branched haloalkoxy having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms are substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy, A for oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH ₂ -O-, -O-CH ₂ -, -CH ₂ -SO _n -, -SO _n -CH ₂ -, -SO _n -, -C (R ⁴ ) = NO-, -C (R ⁴ ) = NO-CH ₂ - or -N (R ⁶ ) - stands and Z represents a radical of the formula -OR ⁵ or -NR ⁶ R ⁷ , where R ⁴ for straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched haloalkyl with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, for cycloalkyl with 3 to 7 Represents carbon atoms or cyano, R ^{5 represents} straight-chain or branched alkyl having 1 to 6 carbon atoms or straight-chain or branched halogenalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, R ⁶ and R ⁷ independently of one another each represent hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, or straight-chain or branched Alkoxy with 1 to 6 carbon atoms and n represents 0, 1 or 2, those 2-oximino-2-pyridyl-acetic acid derivatives of the formula (I), in which the group Ar-A ¹ - and the oximinoacetic acid residue in the pyridine ring are adjacent, are particularly preferred. 4. Compounds of formula (I) according to claim 1, in which Ar for phenyl or naphthyl which is optionally monosubstituted to trisubstituted identically or differently or for each optionally monosubstituted to trisubstituted, identically or differently, and / or benzo-fused furanyl, thienyl, pyrrolyl, Oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyrazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl or triazinyl, the substituents in each case being: fluorine, chlorine, bromine, hydroxyl, aminocro, nitro Formyl, Carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t- Butoxy, methylthio, ethylthio, methylsulfinyl, methylsulfonyl, allyl, butenyl, allyloxy, butenyloxy, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, Dimethylamino, diethylamino, acetyl, acetoxy, methylsulfonyloxy, ethylsulfonyloxy, methoxycarbonyl, ethoxycarbonyl, hydroximino¬ methyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, ethoximinomethyl, ethoximinoethyl, propane-l, 3-diyl, butane-1,4-methylene, dioxy, dioxy Dioxypropylene, difluorodioxymethylene, Tetrafluorodioxyethylene, cyclopropyl, cyclopentyl, cyclohexyl, 1-pyrrolidinyl, 1-piperidinyl, 1-perhydroazepinyl, 4-morpholinyl or in each case optionally one to three times, identically or differently, by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy substituted phenyl, phenoxy, benzyl or Benzyloxy, R ^{1 represents} straight-chain or branched alkyl having 1 to 4 carbon atoms or haloalkyl having 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms, R ² and R ³ are each independently of one another hydrogen, fluorine, chlorine, Bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, Methylthio, ethylthio, allyl, butenyl, allyloxy, butenyloxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, difluorochloromethylthio, methoxycarbonyl, ethoxycarbonyl, hydroximinoethyl, hydroximinoethyl, methoximinomethyl, ethoximinoethyl, ethoximinoethyl, ethoximinoethyl triple, identical or different from fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy are phenyl, phenoxy, benzyl or benzyloxy, A is oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or for one of the following groups -CH ₂ -O-, -O-CH ₂ -, -CH ₂ -SO _n -, -SO _n -CH ₂ -, -SO _n -, -C (R ⁴ ) = NO-, -C (R ⁴ ) = NO-CH ₂ - or -N (R ⁶ ) - stands and Z represents a radical of the formula -OR ⁵ or -NR ⁶ R ⁷ , where R ^{4 represents} methyl, ethyl, trifluoromethyl, cyclopropyl or cyano, R ^{5 stands} for straight-chain or branched alkyl with 1 to 4 carbon atoms or for haloalkyl with 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms and R ⁶ and R ⁷ each independently represent hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms or straight-chain or branched alkoxy having 1 to 4 Carbon atoms stand and n represents 0, 1 or 2, those 2-oximino-2-pyridyl-acetic acid derivatives of the formula (I), in which the group Ar-A ¹ - and the oximinoacetic acid residue in the pyridine ring are adjacent, are particularly preferred. 5. pesticides, characterized by a content of at least one compound of the formula (I) according to Claim 1. 6. A method for controlling pests, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on pests and / or their habitat. 7. Process for the preparation of compounds of formula (I)

in which Ar, A, R ¹ , R ² , R ³ and Z have the meaning given in Claim 1, characterized in that one a) a-oxopyridyl acetic acid derivatives of the formula (Ila),

in which R ² , R ³ , Ar, A and Z have the meaning given above, or their ketals of the formula (Ilb),

in which 5 R ² , R ³ , Ar, A and Z have the meaning given above and R ^{8 represents} alkyl, - or mixtures of a-oxopyridyl acetic acid derivatives of the formula (Ila) and their ketals of the formula (ü) - with hydroxylamines of the formula (HI), 10 H ^ -OR ¹ (HI) in which R ^{1 has} the meaning given above, - or with hydrogen halide adducts of compounds of the formula (in) - 15 if appropriate in the presence of a diluent and, if appropriate, in the presence of a reaction auxiliary, or b) 2-oximino-2- (halogenopyridyl) acetic acid derivatives of the formula (IV),

in which R, R, R and Z have the meaning given above and X represents halogen, with nucleophiles of the formula (V), Ar-A ^ H (V) in which Ar has the meaning given above and A ¹ for oxygen, sulfur or for a radical of the formula 10 -C (R ⁴ ) = NO-, where R ^{4 has} the meaning given above, if appropriate in the presence of a diluent and, if appropriate, in the presence of a reaction auxiliary, or 15 c) 2-oximino-2-pyridyl-acetic acid derivatives of the formula (Ia),

in which R ¹ , R ² , R ³ , R ⁵ , Ar and A have the meaning given above, with amines of the formula (VI),

in which R ⁶ and R ^{7 have} the meaning given above, if appropriate in the presence of a diluent and, if appropriate, in the presence of a reaction auxiliary, 10 or d) 2-pyridyl acetic acid derivatives of the formula (VII)

in which R ² , R ³ , Ar, A and Z have the meaning given above, with oximation agents and then with alkylating agents of the formula (VIII) XR ¹ (VIII) in which R ^{1 has} the meaning given above and X represents halogen or the Gmppiemng -O-SO ^ OR ¹ , if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent. 8. Use of compounds of formula (I) according to claims 1 to 4 for controlling pests. 9. A process for the preparation of pesticides, characterized in that compounds of the formula (I) according to Claims 1 to 4 are mixed with extenders and / or surface-active agents. 10. Compounds of formula (Ila) according to Anspmch 7. 11. Compounds of the formula (IIb) according to Claim 7. 12. Compounds of the formula (IV) according to Claim 7. 13. A process for the preparation of the compounds of the formulas (Ila) and (Ilb) according to Claims 10 and 11, characterized in that corresponding halogenated oxo-pyridyl-acetic acid derivatives of the general formulas (IXa) and (IXb)

in which R ² , R ³ , R ⁸ and Z have the meaning given above and X represents halogen, with nucleophiles of the formula (V) Ar-A ^ H (V) in which Ar has the meaning given above and A ^{1 represents} oxygen, sulfur or a radical of the formula -C (R ⁴ ) = NO-, in which R ^{4 has} the meaning given above, - or with alkali metal salts of compounds of formula (V) - optionally in the presence of a reaction auxiliary, e.g. Copper (I) chloride, and optionally in the presence of a diluent, e.g. Dioxane, at temperatures between 20 ° C and 150 ° C. 14. Compounds of the formulas (IXa) and (IXb) according to claim 13. 15. A process for the preparation of compounds of the formulas (IXa) and (IXb) according to Anspmch 14, characterized in that halogenated pyridine-carboxylic acid cyanides of the formula (X)

in which R ² and R ^{3 have} the meaning given above and X represents halogen, hydrolyzed with aqueous acids, for example with hydrochloric acid at temperatures between 10 ° C. and 100 ° C., then by reaction with alcohols, for example with methanol, optionally in the presence of a reaction auxiliary, such as, for example, Sulfuric acid and optionally in the presence of a diluent, e.g. Toluene esterified at temperatures between 20 ° C and 150 ° C, optionally by reaction with ortho esters, for example with trimethyl ortho formate or triethyl ester, at temperatures between 20 ° C and 150 ° C converted into corresponding ketals and / or optionally by reaction with amines, for example with methylamine, at temperatures between 20 ° C and 150 ° C converted into corresponding amides. 16. Compounds of the formula (X) according to Claim 15.