DE4328385A1 - 2-oximino-2-pyridyl acetic acid derivatives - Google Patents

Description

The invention relates to new 2-oximino-2-pyridyl-acetic acid derivatives, several processes their manufacture and their use as pesticides, especially as fungicides.

It is known that certain 2-methoxy-acrylic acid esters, such as Ver bond 3-methoxy-2- (6-phenyl-2-pyridylthio) acrylic acid methyl ester or the Ver Binding 3-methoxy-2- [N- (6-phenyl-2-pyridyl) -N-methylamino] acrylic acid methyl-1 ester or the compound 3-methoxy-2- [5- (4-chlorophenyl) -3-pyridyloxy] acrylic acid methyl ester have fungicidal properties (see, for example, EP 383117).

However, the effectiveness of these previously known compounds is particularly low application rates and concentrations not completely in all areas of application satisfactory.

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

in which
Ar represents optionally substituted aryl or heteroaryl,
R¹ represents alkyl or haloalkyl,
R² and R³ are each independently of one another hydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkylthio, alkenyl, alkenyloxy, alkynyl, alkynyloxy, haloalkyl, haloalkoxy, haloalkylthio, haloalkenyl, haloalkenyloxy, haloalkynyl, haloalkynyloxy, alkoxycarbonyl, hydroximinoalkyl, alkoximinoalkyl or each represent 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 -CH₂-O-, -O-CH₂-, -CH₂-SO _n -, -SO _n -CH₂-, -SO _n -, -C (R⁴) = NO-, -C (R⁴) = NO-CH₂- or -N (R⁶) -, and
Z represents a radical of the formula -O-R⁵ or -NR⁶R⁷, wherein
R⁴ represents alkyl, haloalkyl, cycloalkyl or cyano,
R⁵ represents alkyl or haloalkyl and
R⁶ and R⁷ each independently represent hydrogen, alkyl, haloalkyl, alkoxy or haloalkoxy and
n represents 0, 1 or 2,
found.

The compounds of formula (I) may optionally, depending on the type of the substituents as geometric and / or optical isomers or isomer mixtures different composition. Both the pure isomers as the isomer mixtures are also claimed according to the invention.

Furthermore, it was found that the new 2-oxime-2-pyridyl-acetic acid derivatives of the general formula (I),

in which
Ar represents optionally substituted aryl or heteroaryl,
R¹ represents alkyl or haloalkyl,
R² and R³ 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 each represent 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 -CH₂-O-, -O-CH₂-, CH₂-SO _n -, -SO _n -CH₂-, - SO _n -, -C (R⁴) = NO-, -C (R⁴) = NO-CH₂- or -N (R⁶) -, stands, and
Z represents a radical of the formula -O-R⁵ or -NR⁶R⁷, wherein
R⁴ represents alkyl, haloalkyl, cycloalkyl or cyano,
R⁵ represents alkyl or haloalkyl and
R⁶ and R⁷ each independently represent hydrogen alkyl, haloalkyl, alkoxy or haloalkoxy and
n stands for 0, 1 or 2
get when one

• a) a-oxopyridyl acetic acid derivatives of the formula (IIa), in which
  R², R³, Ar, A and Z have the meaning given above, or their ketals of the formula (IIb), in which
  R², R³, Ar, A and Z have the meaning given above and R⁸ represents alkyl,
  - or mixtures of a-oxopyridyl acetic acid derivatives of the formula (IIa) and their ketals of the formula (IIb) -
  with hydroxylamines of the formula (III), H₂N-O-R¹ (III) in which
  R¹ 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
  R¹, R², R³ and Z have the meaning given above and
  X represents halogen,
  with nucleophiles of the formula (V), Ar-A¹-H (V) in which
  Ar has the meaning given above and
  A¹ is oxygen or sulfur or a radical of the formula -C (R⁴) = NO-, wherein
  R⁴ 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
  R¹, R², R³, R⁵, Ar and A have the meaning given above,
  with amines of the formula (VI), in which
  R⁶ and R⁷ 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
  R², R³, Ar, A and Z have the meaning given above,
  with oximation agents and then with alkylating agents of the formula (VIII) X-R¹ (VIII) in which
  R1 has the meaning given above and
  X represents halogen or the grouping -O-SO₂-O-R¹,
  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 the general formula (I) good activity against harmful plants Organisms, especially against fungal organisms.

Surprisingly, the 2-oximino-2-pyridyl-acetic acid according to the invention show Derivatives of the general formula (I) compared to a significantly better activity plant-damaging microorganisms compared to those from the prior art Technically known 2-methoxy-acrylic acid esters, such as 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, - 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 stands for optionally single or multiple, identically or differently substituted aryl with 6 to 10 carbon atoms or for optionally single or multiple, identically or differently substituted and / or benzo-fused heteroaryl with 2 to 9 carbon atoms and 1 to 5 identical or different heteroatoms, where as Substituents come into question in each case:
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 carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched alkylamino, dialkylamino, alkyl carbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroximino alkyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts, each optionally one or more times, the same ch or different, in each case doubly linked alkylene or dioxyalkylene, each having 1 to 6, 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 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 in the phenyl part, once or several times, the same or different from 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 having 1 to 4 carbon atoms and / or straight chain or ver branched haloalkoxy having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy,
R¹ 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,
R² and R³ independently of one another each represent hydrogen, halogen, cyano, nitro, each 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 because 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 halogen alkenyl 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, hydroximinoalkyl or alkoxy minoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts and also for each optionally in the phenyl part, 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 with 1 up 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 substituted phenyl, phenoxy, benzyl, Are benzyloxy, phenylethyl or phenylethyloxy,
A for oxygen ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH₂-O-, -O-CH₂-, -CH₂-SO _n -, -SO _n -CH₂-, - SO _n -, -C (R⁴) = NO-, -C (R⁴) = NO-CH₂- or -N (R⁶) -, and
Z represents a radical of the formula -O-R⁵ or -NR⁶R⁷, wherein
R⁴ 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,
R⁵ 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,
R⁶ and R⁷ independently of one another each 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 having 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) are particularly preferred in which the group Ar-A 1 and the oximino acetic acid residue in the pyridine ring are adjacent.

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 hetero aryl with 2 to 9 carbon atoms and 1 to 3 identical or different heteroatoms - in particular Nitrogen is oxygen and / or sulfur - where the following are suitable 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 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 having 2 to 4 carbon atoms and 1 to 9 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 4 carbon atoms in the individual alkyl parts, in each case optionally one or more times, identical to o which is differently substituted 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, in each case double-linked alkylene or dioxyalkylene, each having 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 the phenyl part in each case simply to three fold, identical or different 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 having 1 up to 3 carbon atoms and / or straight active or branched haloalkoxy having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy,
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,
R² and R³ are each independently of one another hydrogen, halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkylthio, 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 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 also for each optionally in the phenyl part simple to five times, the same or different by halogen and / or straight-chain or branched alkyl having 1 to 3 carbon atoms and nd / 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 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 -CH₂-O-, -O-CH₂-, -CH₂-SO _n -, -SO _n -CH₂-, - SO _n -, -C (R⁴) = NO-, -C (R⁴) = NO-CH₂- or -N (R⁶) - is and
Z represents a radical of the formula -O-R⁵ or -NR⁶R⁷, wherein
R⁴ represents 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, cycloalkyl having 3 to 7 carbon atoms or cyano,
R⁵ 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,
R⁶ and R⁷ 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 having 1 to 6 carbon atoms stand and
n represents 0.1 or 2,
those 2-oximino-2-pyridyl-acetic acid derivatives of the formula (I) are particularly preferred in which the group Ar-A 1 and the oximino acetic acid residue are adjacent in the pyridine ring.

Compounds of the formula (I) in which
Ar for phenyl or naphthyl which is optionally monosubstituted to trisubstituted identically or differently or for furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyrazolyl, imidazolyl and is optionally monosubstituted to trisubstituted, identically or differently , Oxadiazolyl, thiadiazolyl, triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl or triazinyl, the substituents in each case being:
Fluorine, chlorine, bromine, hydroxy, 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, trifluoromethylmethylsulfonyl, diethyl , Acetoxy, methylsulfonyloxy, ethylsulfonyloxy, methoxycarbonyl, ethoxycarbonyl, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximino ethyl, ethoximinomethyl, ethoximinoethyl, propane-1,3-diyl, butane-1,4-diyl, dioxymethylene, dioxyethylene, dioxodioxyethylene, dioxoxylene, difluorodioxylyl, 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 he trifluoromethoxy-substituted phenyl, phenoxy, benzyl or benzyloxy,
R¹ 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,
R² and R³ are each independently hydrogen for 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, hydroximinoethyliminoethylimethylethyliminoethyliminoethylimethyl Are methoximinoethyl, ethoximinomethyl, ethoximinoethyl or phenyl, phenoxy, benzyl or benzyloxy which are each mono- to triple, identical or different, substituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy,
A oxygen ethene-1,2-diyl, ethyne-1,2-diyl or for one of the groupings below
-CH₂-O-, -O-CH₂-, -CH₂-SO _n -, -SO _n -CH₂-, -SO _n -, -C (R⁴) = NO-, -C (R⁴) = NO-CH₂- or -N (R⁶) - stands and
Z represents a radical of the formula -O-R⁵ or -NR⁶R⁷, wherein
R⁴ represents methyl, ethyl, trifluoromethyl, cyclopropyl or cyano,
R⁵ 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
R⁶ and R⁷ each independently represent hydrogen for straight-chain or branched alkyl having 1 to 4 carbon atoms, for haloalkyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, or for straight-chain or branched alkoxy with 1 to 4 carbon atoms and
n represents 0, 1 or 2,
in particular those 2-oximino-2-pyridyl-acetic acid derivatives of the formula (I) are very particularly preferred in which the group Ar-A 1 and the oximino acetic acid residue in the pyridine ring are adjacent.

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

in which
A, Ar, R¹, R², R³ and Z have the meanings given above as being particularly preferred.

The radicals listed above or specified in preferred ranges definitions apply both to the end products of the formula (I) and correspondingly for the raw materials or intermediate products required for the production.

These residual definitions can be among themselves, that is, between the specified Areas of preferred connections, can be combined as desired.

Examples of the possible combinations of the groups A defined above, Ar, R¹, R², R³ and Z are listed below:

If, for example, 2- [3- (3-chlorophenoxymethyl) pyridin-2-yl] -2-oxo- methyl acetate and O-methyl-hydroxylamine hydrochloride as starting materials, the course of the reaction in process (a) according to the invention can be carried out by represent the following formula:

For example, if 2- (2-chloro-pyridin-3yl) -2-methoximino-acetic acid is used methyl amide and benzyl mercaptan as starting materials, so the reaction can in process (b) according to the invention by the following formula:

If, for example, 2- [2- (2-chloro-pyridin-5-yl-methyl-amino) -pyridin-3- yl] -2-methoximino-acetic acid methyl ester and methylamine as starting materials, so lets the course of the reaction of process (c) according to the invention is as follows Represent formula scheme:

For example, 2- [4-2-furyl) methoxy-pyridin-3-yl] -acetic acid ethyl is used esters, methyl nitrite and methyl iodide as starting materials, so the reaction sequence in process (d) according to the invention by the following formula put:

The to carry out the method (a) according to the invention as a starting ver a-Oxo-pyridyl-acetic acid derivatives required by bonds are represented by the formula (IIa), the corresponding ketals are generally defined by the formula (IIb). In these Formulas (IIa) and (IIb) have R², R³, Ar, A and Z preferably or in particular those meanings that are already related to the description of the Compounds of formula (I) according to the invention as preferred or as special were preferably given for R², R³, Ar, A and Z; R⁸ preferably stands for Alkyl with 1 to 4 carbon atoms, especially for methyl or ethyl.

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

The new compounds of the formulas (IIa) and (IIb) are obtained if one ent speaking halogenated oxo-pyridyl-acetic acid derivatives of the general formulas (IXa) or (IXb)

in which
R², R³, R⁸ and Z have the meaning given above and
X represents halogen,
with nucleophiles of the formula (V)

Ar-A¹-H (V)

in which
Ar has the meaning given above and
A¹ represents oxygen, sulfur or a radical of the formula -C (R⁴) = NO-,
in which
R⁴ has the meaning given above,
- or with alkali metal salts of compounds of formula (V) -
optionally in the presence of a reaction auxiliary, such as. B. copper (I) chloride, and optionally in the presence of a diluent, such as. B. dioxane, at temperatures between 20 ° C and 150 ° C.

The halogenated oxo-pyridyl-acetic acid derivatives of the general formulas (IXa) and (IXb) are not yet known from the literature; they are the subject of new substances 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
R² and R³ 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. B. sulfuric acid and optionally in the presence of a diluent, such as. B. 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 in appropriate ketals and / or optionally by reaction with amines , for example with methylamine, at temperatures between 20 ° C and 150 ° C converts into corresponding amides.

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

The new compounds of formula (X) are obtained when halogenated pyridine carboxylic acid chloride of the formula (XI)

in which
R², R³ 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. B. 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 produced by processes known per se (cf. DE-OS 27 13 316, J. Heterocycl. Chem. 25 (1988), 1367-1371).

Those further required as starting materials in process (a) according to the invention Hydroxylamines are generally defined by the formula (III). In formula (III) R¹ preferably or in particular that meaning that already together hang with the description of the compounds of formula (I) as was preferred or indicated as being particularly preferred for R 1.

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

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

The starting compounds for carrying out process (b) according to the invention gene to be used 2-oximino-2- (halogenopyridyl) acetic acid derivatives are by the formula (IV) is generally defined. In formula (IV), R¹, R², R³ and Z preferably or in particular that meaning that is already related with the description of the compounds of formula (I) according to the invention as before added or was specified as particularly preferred for R¹, R², R³ and Z.

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

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

in which
R², R³, R⁸ and Z have the meaning given above and
X represents halogen,
with hydroxylamines of the formula (III)

H₂N-O-R¹ (III)

in which
R1 has the meaning given above,
- Or with hydrogen halide adducts of compounds of formula (III) - optionally in the presence of a reaction auxiliary, such as. B. acetic acid, and if necessary ge in the presence of a diluent, such as. B. methanol, at temperatures between 10 ° C and 100 ° C.

The to carry out the method (b) according to the invention as starting Compounds to be used nucleophiles are generally de by the formula (V) finishes. In formula (V), Ar preferably or in particular has that Meaning already in connection with the description of the Invention compounds of the formula (I) as preferred or as particularly preferred was specified for Ar; A¹ preferably represents oxygen or sulfur Rest of the formula -O-CH₂-, -C (R⁴) = N-O- or -C (R⁴) = N-O-CH₂-, where R⁴ is the has the meaning given above as preferred or as particularly preferred.  

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

The to carry out the method (c) according to the invention as a starting ver 2-Oximino-2-pyridyl-acetic acid derivatives to be used are by the Formula (Ia) generally defined. In formula (Ia), R¹, R², R³, R⁵, Ar and A have preferably or in particular that meaning that is already related with the description of the compounds of formula (I) according to the invention as before adds or specified as particularly preferred for R¹, R², R³, R⁵, Ar and A. has been.

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

The to carry out the method (c) according to the invention as a starting ver Amines to be used are generally defined by the formula (VI). In of the formula (VI) R⁶ and R⁷ preferably or in particular that Meaning already in connection with the description of the Invention compounds of the formula (I) as preferred or as particularly preferred was specified for R⁷ and R⁷.

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

The to carry out the method (d) according to the invention as a starting ver halogenated 2-pyridyl-acetic acid derivatives to be used are by the Formula (VII) generally defined. In formula (VII), R², R³, Ar, A and Z have preferably or in particular the meaning already in connection with the description of the compounds of formula (I) according to the invention as preferred or was specified as particularly preferred for R², R³, Ar, A and Z.

The starting materials of formula (VII) are known and / or can be per se known processes can be produced (cf. EP-A 243012, EP-A 312243).

Those used to carry out process (d) according to the invention as starting Compounds alkylating agents to be used are represented by the formula (VIII)  generally defined. In formula (VIII), R 1 preferably or in particular the meaning already in connection with the description of the Compounds of formula (I) according to the invention as preferred or as special was given preferably for R¹; X preferably represents chlorine, bromine, iodine or the grouping -O-SO₂-O-R¹.

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-pyridyl Acetic acid derivatives of formula (I) is preferably using Ver carried out fertilizers. As a diluent to carry out the he Process (a) according to the invention mainly involves inert organic solvents into consideration. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as gasoline, benzene, Toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, Dichloromethane, chloroform, carbon tetrachloride ether, 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 th reaction aid performed. As such come all the usual inorganic or organic acids. These preferably include protons acids, for example hydrochloric acid, sulfuric acid, methanesulfonic acid, benzenesulfone acid and p-toluenesulfonic acid.

The reaction temperatures can be carried out when carrying out the process according to the invention Process (a) can be varied over a wide range. Generally works  one at 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 leads. However, it is also possible to work under increased or reduced pressure ten.

To carry out process (a) according to the invention, Oxo-pyridyl-acetic acid derivative of the formula (II) in general 1.0 to 3.0 mol preferably 1.0 to 2.0 mol of hydroxylamine of the formula (III) or one the hydrogen halide and optionally 1.0 to 6.0 mol, preferably 1.0 to 3.0 Mole of reaction auxiliary. The implementation of the reaction, workup and Iso lation of the reaction products is carried out according to known methods.

As a diluent for carrying out process (b) according to the invention inert organic solvents are particularly suitable. This includes in particular aliphatic, alicyclic or aromatic, optionally halogenated Hydrocarbons, such as gasoline, benzene, toluene, xylene, chlorobenzene, Dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetra chlorinated carbon; 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, N, N-dimethylacetamide, N-methylformanilide, N-Me thylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate esters or ethyl acetate; or sulfoxides such as dimethyl sulfoxide.

The process according to the invention can (b) optionally also in a two phase system, such as water / toluene or water / dichloromethane, if necessary in the presence of a suitable phase transfer catalyst. When Examples of such catalysts may be mentioned: tetrabutylammonium iodide, tetrabu tylammonium bromide, tetrabutylammonium chloride, tributyl-methylphosphoniumbro mid, trimethyl-C₁₃ / C₁₅-alkylammonium chloride, trimethyl-C₁₃ / C₁₅-alkylammoni umbromide, dibenzyl-dimethyl-ammonium methyl sulfate, dimethyl-C₁₂ / C₁₄-alkyl-ben zylammonium chloride, dimethyl-C₁₂ / C₁₄-alkyl-benzylammonium bromide, tetrabutyl  ammonium hydroxide, triethylbenzylammonium chloride, methyltrioctylammoniumchlo rid, trimethylbenzylammonium chloride, 15-crown-5, 18-crown-6 or tris- [2- (2- methoxyethoxy) ethyl] amine.

Process (b) according to the invention is preferably carried out in the presence of a th reaction aid performed. As such come all the usual inorganic or organic bases in question. These include, for example, alkaline earth or Alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hyd roe 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, tributyl amine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, Diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can be carried out when carrying out the process according to the invention Process (b) can be varied over a wide range. Generally works one at 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 leads. However, it is also possible to work under increased or reduced pressure ten.

To carry out process (b) according to the invention, 2-ox are employed per mole imino-2- (halogenopyridyl) acetic acid derivative of formula (IV) generally 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol of nucleophile of the formula (V) and ge optionally 1.0 to 3.0 moles, preferably 1.0 to 2.0 moles, of reaction auxiliary a. Carrying out the reaction, working up and isolating the reaction products takes place according to known methods.

As a diluent for carrying out process (c) according to the invention In addition to water, organic solvents are particularly suitable. This includes  in particular aliphatic, alicyclic or aromatic, optionally halogenated Hydrocarbons, such as gasoline, benzene, toluene, xylene, chlorobenzene, Dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetra chlorinated carbon; 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 like N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methyl pyrrolidone or hexamethylphosphoric triamide or sulfoxides such as dimethyl sulfate oxide.

If appropriate, process (c) according to the invention is suitable in the presence of a Neten reaction auxiliary carried out. As such come all the usual inorganic or organic bases in question. These include, for example, alkaline earth or Alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hyd roe 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, tributyl amine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, Diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

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

The reaction temperatures can be carried out when carrying out the process according to the invention Process (c) can be varied over a wide range. Generally works one at 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 leads. However, it is also possible to work under increased or reduced pressure ten.  

To carry out process (c) according to the invention, 2-ox are employed per mole imino-2-pyridyl-acetic acid derivative of the formula (Ia) generally 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 a reaction auxiliary. It is also possible in a special implementation form, which as Aus products used 2-oximino-2-pyridyl-acetic acid derivatives of the formula (Ia) in an upstream reaction in the reaction vessel and then without isolation directly in a so-called "one-pot reaction" according to the inventions to implement method (c) further. The implementation of the reaction, Aufar Processing and isolation of the reaction products is done in analogy methods (see the manufacturing 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 B. methyl, ethyl, n- or i-propyl, n-, i-, s- and t-butyl nitrite.

As a diluent for carrying out process (d) according to the invention inert organic solvents are particularly suitable. This includes in particular aliphatic, alicyclic or aromatic, optionally halogenated Hydrocarbons, such as gasoline, benzene, toluene, xylene, chlorobenzene, Dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetra chlorinated carbon; 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, N, N-dimethylacetamide, N-methylformanilide, N-Me thylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate esters or ethyl acetate, sulfoxides such as dimethyl sulfoxide, alcohols such as Methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol colmonoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.  

If appropriate, process (d) according to the invention is suitable in the presence of a Neten reaction auxiliary carried out. As such come all the usual inorganic or organic bases in question. These include, for example, alkaline earth or Alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hyd roe 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, tributyl amine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, Diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can be carried out when carrying out the process according to the invention Process (d) can be varied over a wide range. Generally works one at 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 leads. However, it is also possible to work under increased or reduced pressure ten.

To carry out process (d) according to the invention, 2- pyridyl acetic acid derivative of the formula (VII) in general 1 to 5 mol, preferably 1.0 to 3.0 moles of an oximation agent and 1 to 3 moles, preferably 1.0 to 1.5 Mol of an alkylating agent of formula (VIII) and optionally 1.0 to 3.0 Mol, preferably 1.0 to 2.0 mol of reaction auxiliary. The reaction The reaction products are carried out, worked up and isolated according to be Known methods (see the manufacturing examples).

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

Fungicides in crop protection are used to combat plasmo diophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basi diomycetes, 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 good plant tolerance of the active ingredients in the control of plants Concentrations necessary for diseases allow treatment above ground Parts of plants, of seedlings and soil.

The active compounds according to the invention can be used with particularly good success fighting diseases in fruit and vegetable growing, such as against Venturia, Uncinula or Podosphaera species, or to control cereals diseases such as against Erysiphe species. Next to it be the active compounds according to the invention have good in vitro activity.

The active ingredients can depend on their respective physical and / or chemical properties are converted into conventional formulations, such as solutions genes, emulsions, suspensions, powders, foams, pastes, granules, aerosols, Fine encapsulation in polymeric substances and in coating compositions for seeds, as well ULV cold and warm fog formulations.  

These formulations are prepared in a known manner, e.g. B. by mixing of the active ingredients are under pressure with extenders, i.e. liquid solvents the liquefied gases and / or solid carriers, if necessary with use of surface-active agents, i.e. emulsifiers and / or dispersants agents and / or foaming agents. In case of using water as Extenders can e.g. B. also ver organic solvents as auxiliary solvents be applied. The following are essentially suitable as liquid solvents: aroma ten such as xylene, toluene, alkylnaphthalenes, chlorinated aromatics or chlorinated aliphati cal hydrocarbons, such as chlorobenzenes, chlorethylenes, or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fraction NEN, 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 solvents, such as dimethylformamide or dimethyl sulfoxide, and water; with ver liquid gaseous extenders or carriers are such liquids means which are gaseous at normal temperature and pressure, e.g. B. Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers come into question: B. natural rock flours such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as finely divided silica, Alumina and silicates; as solid carriers for granules are: e.g. B. broken and fractionated natural rocks such as calcite, marble, pumice, Sepiolite, dolomite and synthetic granules from inorganic and organic Flours and granules made of organic material such as sawdust, coconut shells, Corn cobs and tobacco stalks; as emulsifying and / or foam-generating agents come into question: z. B. non-ionic and anionic emulsifiers, such as polyoxyethy len fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, Alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a disperser middle come into question: z. B. Ligninsulfitablaugen and methyl cellulose.

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

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferrocy blue and organic dyes such as alizarin, azo and metal phthalocyanine substances 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 Active ingredient preferably between 0.5 and 90%.

The active compounds according to the invention can be mixed with in the formulations other known active ingredients are present, such as fungicides, insecticides, acaricides and Herbicides and in mixtures with fertilizers and growth regulators.

The active substances can be used as such, in the form of their formulations or in the form thereof rode application forms, such as ready-made solutions, suspensions, spray powders, pastes, soluble powders, dusts and granules can be used. The Application happens in the usual way, e.g. B. by pouring, spraying, spraying, Scattering, dusting, foaming, brushing, etc. It is also possible to use the Apply active ingredients according to the ultra-low-volume process or the active ingredient preparation or inject the active substance yourself into the soil. It can also do that Seeds of the plants are treated.

In the treatment of parts of plants, the drug concentrations in the Application forms can be varied in a larger area: They are generally mean between 1 and 0.0001% by weight, preferably between 0.5 and 0.001 % By weight.

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

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, is 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) sodium 4-cresolate, 0.15 g copper (I) chloride and 0.5 g tris-diaza heptylamine are suspended in 100 ml of dioxane and refluxed for 36 hours heated. The solvent is removed in a water jet vacuum, the residue in 100 ml of ethyl acetate dissolved, with 10 ml of saturated sodium bicarbonate washed solution, dried over sodium sulfate and concentrated. The backlog will dissolved in ethyl acetate and by stirring with cyclohexane for crystallization brought.

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

Example 2

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

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

Example 3

7.29 g (0.03 mol) of methyl 2- (2-phenoxy-pyridin-3-yl) -acetate (for the preparation see. EP 243 012, page 39) are added together with 9.3 g (0.09 mol) of tert-butyl nitrite a solution of 3.7 g (0.033 mol) of potassium tert-butoxide in 36 ml of tert-butanol dripped. The mixture is stirred at 20 ° C for one hour. Then you give 4.68 g (0.033 mol) of methyl iodide and stir for a further hour at 20 ° C. You move with water, extracted with ethyl acetate, the organic phase is concentrated and chromatograph the residue with diethyl ether / petroleum ether (low-boiling) in 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.
1 H-NMR (CDCl₃, tetramethylsilane): 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 methyl 2-methoximino-2- (2-phenoxy-pyridin-3-yl) -acetate are in 10 ml of tetrahydrofuran with 0.2 ml of 40% aqueous methylamine solution added and stirred at 20 ° C for 2 hours. Pour on water, extract with vinegar acid ethyl ester, concentrated and chromatographed the residue 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.
1 H-NMR (CDCl₃, 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.

Analogous to the preparation examples 1 to 4 and in accordance with the general Description of the manufacturing method according to the invention can for example the compounds of the formula (I) listed below can also be prepared.  

Example 5 2-Methoximino-2- [2- (3-methylphenoxy) pyridin-3-yl] acetic acid methyl ester

1 H-NMR (CDCl₃, tetramethylsilane): d = 2.35 (3H); 3.87 (3H); 4.10 (3H); 6.88 - 7.08 (4H); 7.23-7.29 (1H); 7.72-7.76 (1H); 8.20-8.22 (1H) ppm.

Example 6 2-methoximino-2- [2- (3-methylphenoxy) pyridin-3-yl] acetic acid methyl amide

1 H-NMR (CDCl₃, tetramethylsilane): d = 2.35 (3H); 2.92-2.93 (3H); 4.0 (3H); 6.79 (1H); 6.9-7.1 (4H); 7.23 - 7.30 (1H); 7.66-7.70 (1H); 8.17-8.20 (1H) ppm.  

Example 7 2-Methoximino-2- [2- (3-chlorophenoxy) pyridin-3-yl] acetic acid methyl ester

1 H-NMR (CDCl₃, tetramethylsilane): d = 3.87, 4.09 ppm.

Example 8 2-methoximino-2- [2- (3-bromo-phenoxy) pyridin-3-yl] acetic acid methyl ester

1 H-NMR (CDCl₃, tetramethylsilane): d = 3.87, 4.10 ppm.  

Example 9 2-Methoximino-2- [2- (3-methoxyphenoxy) pyridin-3-yl) acetic acid methyl ester

1 H-NMR (CDCl₃, tetramethylsilane): d = 3.79, 3.86, 4.10 ppm.

Example 10 2-methoximino-2- [2- (3-chlorophenoxy) pyridin-3-yl] acetic acid methyl amide

1 H-NMR (CDCl₃, tetramethylsilane): d = 2.93, 2.94, 3.99 ppm.  

Example 11 2-Methoximino-2- [2- (3-bromophenoxy) pyridin-3-yl] acetic acid methyl mid

1 H-NMR (CDCl₃, tetramethylsilane): d = 2.93. 2.94. 3.99 ppm.

Example 12 2-Methoximino-2- [2- (4-tert-butylphenoxy) pyridin-3-yl] acetic acid m-ethyl ester

1 H-NMR (CDCl₃, tetramethylsilane): d = 1.32, 3.86, 4.10 ppm.  

Example 13 2-Methoximino-2- [2- (3,4-dichlorophenoxy) pyridin-3-yl] methyl acetate

1 H-NMR (CDCl₃, tetramethylsilane): d = 3.88, 4.10 ppm.

Example 14 2-methoximino-2- [2- (3-trifluoromethylphenoxy) pyridin-3-yl] acetic acid re-methyl amide

1 H-NMR (CDCl₃, tetramethylsilane): d = 2.69 (d, J = 4.7 Hz); 3.95 ppm.  

Starting materials of formula (IV) Example (IV-1)

4.0 g (0.02 mol) of methyl 2- (2-chloro-pyridin-3-yl) glyoxylate are dissolved in 40 ml Dissolved methanol, with 16 ml acetic acid and 5.01 g (0.06 mol) methoxyamine added hydrochloride and heated under reflux for 18 hours. The solution is at concentrated to dryness under reduced pressure, the residue in 100 ml of acetic acid dissolved ethyl ester, twice with 10 ml of saturated sodium bicarbonate solution washed, the aqueous phases extracted with ethyl acetate, the combined organic phases 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 (CDCl₃, 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 reduced The pressure was largely concentrated, 50 ml of toluene were added and the solvent was added reduced pressure removed. The residue is dissolved in 100 ml of methanol, with 1 ml conc. Added sulfuric acid and heated under reflux for 24 hours. The Solvent is removed under reduced pressure, the residue in 100 ml Dissolved ethyl acetate, with 10 ml of saturated sodium bicarbonate solution washed, dried over sodium sulfate and concentrated. The raw so obtained product is distilled over a 20 cm long Vigreux column.

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

Starting materials of formula (X) Example (X-1)

A suspension of 0.05 8.8 g of 0.05 mol of chloronicotinic acid chloride (for preparation see. DE 27 13 316) and 8.9 g (0.10 mol) of copper (I) cyanide in 100 ml of acetonitrile Stirred at 25 ° C for one hour and then heated under reflux for two hours. The Solvent is removed under reduced pressure and the residue twice with 200 ml of hot toluene are stirred and filtered off. Concentration of the solution gives 6.7 g (80% of theory) 2- (2-chloro-pyridin-3-yl) glyoxylic acid cyanide.  

Examples of use Example A

Erysiphe test (barley) / 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, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the Active ingredient preparation dewy. After the spray coating has dried on, the Plants dusted with spores from Erysiphe graminis f.sp.tritici.

The plants are grown in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80% set up to the development of Favor mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, for example, the compound according to Preparation Example 5 showed an application rate of 400 g / ha an efficiency of 100%.  

Example B

Podosphaera test (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, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

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

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

Evaluation is carried out 10 days after the inoculation.

In this test, for example, the compounds from Preparation Examples 3 were shown and 6 at an active ingredient concentration of 25 ppm an efficiency of at least 95%.  

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, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

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

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

Evaluation is carried out 14 days after the inoculation.

In this test, for example, showed the compound according to Preparation Example 4 an active ingredient concentration of 25 ppm an efficiency of at least 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, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

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

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

Evaluation is carried out 12 days after the inoculation.

In this test, for example, the compounds according to the Production Examples 2, 3, 4, 5 and 6 at an active ingredient concentration of 0.025 ppm an efficiency of 100%.

Claims (16)

1. 2-oximino-2-pyridyl-acetic acid derivatives of the general formula (I), in which
Ar represents optionally substituted aryl or heteroalkyl,
R¹ represents alkyl or haloalkyl,
R² and R³ are each independently hydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkylthio, alkenyl, alkenyloxy, alkynyl, alkynyloxy, haloalkyl, haloalkoxy, haloalkylthio, haloalkenyl, haloalkenyloxy, haloalkynyl, haloalkynyloxy, alkoxycarbonyl, hydroximinoalkyl, alkoximinoalkyl or for each 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 -CH₂-O-, -O-CH₂-, -CH₂-SO _n -, -SO _n -CH₂-, -SO _n -, -C (R⁴) = NO-, -C (R⁴) = NO-CH₂- or -N (R⁶) -, and
Z represents a radical of the formula -O-R⁵ or -NR⁶R⁷, wherein
R⁴ represents alkyl, haloalkyl, cycloalkyl or cyano,
R⁵ represents alkyl or haloalkyl and
R⁶ and R⁷ 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 stands for optionally single or multiple, identically or differently substituted aryl with 6 to 10 carbon atoms or for optionally single or multiple, identically or differently substituted and / or benzo-fused heteroaryl with 2 to 9 carbon atoms and 1 to 5 identical or different heteroatoms, where as Substituents come into question:
Halogen, cyano, nitro, hydroxy, amino, formyl, carbamoyl, thio carbamoyl, 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, halo genalkylsulfinyl 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 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 optionally one or more times, The same or different 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, each having a double bond, alkylene or dioxyalkylene each having 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 hetero atoms - in particular nitrogen, oxygen and / or sulfur - and in each case optionally in the phenyl part once or more, 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 having 1 to 4 carbon atoms and / or straight chain or he branched haloalkoxy having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy,
R¹ 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,
R² and R³ independently of one another each represent hydrogen, halogen, cyano, nitro, each 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 haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 13 identical or different NEN halogen atoms, each straight-chain or branched halogen alkynyl or haloalkynyloxy each having 2 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched alkoxycarbonyl, hydroximinoalkyl or alk ox are iminoalkyl 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 halogen alkoxy with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms substituted phenyl, phenoxy, Are benzyl, benzyloxy, phenylethyl or phenylethyloxy,
A for oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH₂-O-, -O-CH₂-, -CH₂-SO _n -, - SO _n -CH₂-, -SO _n -, -C (R⁴) = NO-, -C (R⁴) = NO-CH₂- or -N (R⁶) -, and
Z represents a radical of the formula -O-R⁵ or -NR⁶R⁷, wherein
R⁴ 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,
R⁵ 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,
R⁶ and R⁷ each independently 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 for straight-chain or branched alkoxy having 1 to 8 carbon atoms are 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 different heteroatoms - in particular nitrogen , Oxygen and / or sulfur - is available, the following being suitable as substituents:
Halogen, cyano, nitro, hydroxy, amino, formyl, catamoyl, thio carbamoyl, each 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 having 2 to 4 carbon atoms and 1 to 9 of the same or ver 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, gle I or differently, each substituted 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, each having two bonds, alkylene or dioxyalkylene each having 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 simply to triple, identical or different by halogen and / or straight-chain or branched alkyl having 1 to 3 carbon atoms and / or straight-chain or ver 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 with 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy,
R¹ 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,
R² and R³ independently of one another each represent hydrogen, halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkylthio, each having 1 to 4 carbon atoms, each straight-chain or ver 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, up to five times, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 3 carbon atoms n 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 the same 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 -CH₂-O-, -O-CH₂-, CH₂-SO _n -, -SO _n -CH₂-, - SO _n -, -C (R⁴) = NO-, -C (R⁴) = NO-CH₂- or -N (R⁶) - is and
Z represents a radical of the formula -O-R⁵ or -NR⁶R⁷, wherein
R⁴ represents 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, cycloalkyl having 3 to 7 carbon atoms or cyano,
R⁵ 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,
R⁶ and R⁷ independently of one another each represent hydrogen for straight-chain or branched alkyl having 1 to 6 carbon atoms, for straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms or for straight-chain or branched alkoxy having 1 to 6 Carbon atoms stand and
n represents 0, 1 or 2,
those 2-oximino-2-pyridyl-acetic acid derivatives of the formula (I) are particularly preferred in which the group Ar-A 1 and the oximino acetic acid residue in the pyridine ring are adjacent. 4. Compounds of formula (I) according to claim 1, in which
Ar for phenyl or naphthyl which is optionally monosubstituted to trisubstituted in the same or different ways or for furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyrazolyl, imidazolyl, oxadiazolyl and in each case monosubstituted to trisubstituted, identically or differently and / or benzo-fused , Thiadiazolyl, triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl or triazinyl, where the following are suitable as substituents:
Fluorine, chlorine, bromine, hydroxy, 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, methylsulphinyl, methylsulphonyl, allyl, butenyl, allyloxy, butenyloxy, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulphinyl, trifluoromethylmethylsulphonyl, dimiflmethylamulphonyl , Acetoxy, Methylsulfonyloxy, Ethylsulfonyloxy, Methoxycarbonyl, Ethoxycarbonyl, Hydroximinomethyl, Hydroximinoethyl, Meth oximinomethyl, Methoximinoethyl, Ethoximinomethyl, Ethoximinoethyl, Propane-1,3-diyl, Butane-1,4-diyl, Dioxymethylene, Dioxyethylene, Dioxfluorodioxy, Difluorethylene Cyclopropyl, cyclopentyl, cyclohexyl, 1-pyrrolidinyl, 1-piperidinyl, 1-perhy droazepinyl, 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,
R¹ 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,
R² and R³ are each independently hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, allyl, butenyl, allyloxy, butenyloxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, difluorochloromethylthio, methoxycarbonyl, ethoxyethylimino, hydroxymethyl, hydroxymethyl, hydroxym Methoximinomethyl, methoximinoethyl, ethoximino methyl, ethoximinoethyl or phenyl, phenoxy, benzyl or benzyloxy which are optionally mono- to triple, the same or different, fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy,
A oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or for one of the following groups -CH₂-O-, -O-CH₂-, -CH₂-SO _n -, -SO _n -CH₂-, -SO _n -, -C (R⁴) = NO-, -C (R⁴) = NO-CH₂- or -N (R⁶) - is and
Z represents a radical of the formula -O-R⁵ or -NR⁶R⁷, wherein
R⁴ represents methyl, ethyl, trifluoromethyl, cyclopropyl or cyano,
R⁵ 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
R⁶ and R⁷ independently of one another each 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 and
n represents 0, 1 or 2,
those 2-oximino-2-pyridyl-acetic acid derivatives of the formula (I) are particularly preferred in which the group Ar-A 1 and the oximino acetic acid residue in the pyridine ring are adjacent. 5. pesticide, characterized by a content of at least one compound of formula (I) according to claim 1. 6. A method for controlling pests, characterized in that Compounds of formula (I) according to claim 1 on pests and / or their Living space.   7. Process for the preparation of compounds of formula (I) in which
Ar, A, R¹, R², R³ and Z have the meaning given in claim 1, characterized in that

• a) a-oxopyridyl acetic acid derivatives of the formula (IIa), in which
  R², R³, Ar, A and Z have the meaning given above, or their ketals of the formula (IIb), in which
  R², R³, Ar, A and Z have the meaning given above and
  R⁸ represents alkyl,
  - or mixtures of a-oxopyridyl acetic acid derivatives of the formula (IIa) and their ketals of the formula (IIb) -
  with hydroxylamines of the formula (III), H₂N-O-R¹ (III) in which
  R¹ 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
• b) 2-oximino-2- (halogenopyridyl) acetic acid derivatives of the formula (IV), in which
  R¹, R², R³ and Z have the meaning given above and
  X represents halogen,
  with nucleophiles of the formula (V), Ar-A¹-H (V) in which
  Ar has the meaning given above and
  A¹ is oxygen, sulfur or a radical of the formula -C (R⁴) = NO-, where
  R⁴ has the meaning given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary,
  or
• c) 2-oximino-2-pyridyl-acetic acid derivatives of the formula (Ia), in which
  R¹, R², R³, R⁵, Ar and A have the meaning given above,
  with amines of the formula (VI), in which
  R⁶ and R⁷ have the meaning given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary,
  or
• d) 2-pyridyl acetic acid derivatives of the formula (VII) in which
  R², R³, Ar, A and Z have the meaning given above,
  with oximation agents and then with alkylating agents of the formula (VIII) X-R¹ (VIII) in which
  R1 has the meaning given above and
  X represents halogen or the grouping -O-SO₂-O-R¹,
  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 Pest control. 9. Process for the preparation of pesticides, characterized characterized in that compounds of formula (I) according to claims 1 to 4 with Extenders and / or surfactants mixed. 10. Compounds of formula (IIa) according to claim 7. 11. Compounds of formula (IIb) according to claim 7.   12. Compounds of formula (IV) according to claim 7. 13. A process for the preparation of the compounds of the formulas (IIa) and (IIb) 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
R², R³, R⁸ and Z have the meaning given above and
X represents halogen,
with nucleophiles of the formula (V) Ar-A¹-H (V) in which
Ar has the meaning given above and
A¹ represents oxygen, sulfur or a radical of the formula -C (R⁴) = NO-,
in which
R⁴ has the meaning given above,
- Or with alkali metal salts of compounds of formula (V) - optionally in the presence of a reaction auxiliary, such as. B. copper (I) chloride, and optionally in the presence of a diluent, such as. B. 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 claim 14, characterized in that halogenated pyridine carboxylic acid cyanides of the formula (X) in which
R² and R³ 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. B. sulfuric acid and optionally in the presence of a diluent, such as. B. toluene esterified at temperatures between 20 ° C and 150 ° C, optionally by reaction with orthoesters, for example with ortho formic acid trimethyl or triethyl ester, converted at temperatures between 20 ° C and 150 ° C into corresponding ketals and / or optionally by reaction with Amines, for example with methylamine, converted into corresponding amides at temperatures between 20 ° C and 150 ° C. 16. Compounds of formula (X) according to claim 15.