DE4405428A1 - 2-oximino-2-thienyl acetic acid derivatives - Google Patents

Description

The invention relates to new 2-oximino-2-thienyl-acetic acid derivatives, several Process for their preparation and their use as pest control medium.

It is known that certain 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 acids ethyl ester or the compound 3-methoxy-2- [5- (4-chlorophenyl) -3-pyridyloxy] acrylic Acid methyl ester have fungicidal properties (see, for example, EP 383 117).

The effectiveness of these previously known compounds is, however, in particular low application rates and concentrations not in all application areas completely satisfactory.

There were new 2-oximino-2-thienyl-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, hydroxyminoalkyl, Alkoximinoalkyl or optionally substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy,
A represents oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH₂-O-; -O-CH₂-, -CH₂-S (O) _n -, -S (O) _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 hydrogen, alkyl haloalkyl, cycloalkyl or cyano,
R⁵ represents alkyl or haloalkyl and
R⁶ and R⁷ each independently represent hydrogen, alkyl, haloalkyl or alkoxy, and
n represents 0, 1 or 2,
found.

The compounds of formula (I) may optionally, depending on the Type of substituents as geometric and / or optical isomers or isomers Mixtures of different compositions are present. Both the pure Isomers as well as the isomer mixtures are claimed according to the invention.  

Furthermore, it was found that the new 2-oximino-2-thienyl-acetic acid derivatives vate of the general formula (I),

in which
Ar represents optionally substituted aryl or heteroaryl,
R¹ represents alkyl or haloalkyl,
R² and R³ each independently 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 represents oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH₂-O-; -O-CH₂-, -CH₂-S (O) _n -, S (O) _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 hydrogen, alkyl, haloalkyl, cycloalkyl or cyano,
R⁵ represents alkyl or haloalkyl and
R⁶ and R⁷ each independently represent hydrogen, alkyl, haloalkyl or alkoxy, and
n represents 0, 1 or 2,
get when one

• a) a-oxothienyl 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-oxothienyl-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 their hydrogen halide adducts, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary or if
• b) 2-oximino-2- (halogenomethyl-2-thienyl) 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
  A and Ar have the meaning given above and
  if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary or if one
• c) 2-oximino-2-thienyl-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.

The compounds according to the invention can optionally be in the form of mixtures various possible isomeric forms, in particular E and Z isomers, available. There are both the E and the Z isomers as well as any Mixtures of these isomers claimed.

Finally, it was found that the new 2-oximino-2-thienyl-acetic acid derivatives of the general formula (I) have good activity against pests.

Surprisingly, the 2-oximino-2-thienyl acetic acid according to the invention rederivate of the general formula (I) a significantly better effectiveness against plant-damaging microorganisms compared to those from the State of the art 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 acids ethyl ester or the compound 3-methoxy-2- [5- (4-chlorophenyl) -3-pyridyloxy] acrylic acid methyl ester, which is the chemically and / or functionally obvious verb are.  

The 2-oximino-2-thienyl-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:
Halogen, cyano, nitro, hydroxy, amino, formyl, carbamoyl, thio carbamoyl, each straight-chain or branched alkyl, alkoxy, alkyl thio, 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 various halogen atoms, in each case straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroxyiminoalkyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts, in each case optionally one or more times, 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 / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms substituted alkylene or dioxyalkylene, each of which is linked twice, 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 part singly or multiply, identically or differently by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and / or straight active 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, benzyloxy, phenylethyl or phenylethoxy,
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 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 alkoxi are minoalkyl 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 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 benzyloxy, phenylethyl or phenylethyloxy,
A represents oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH₂-O-; -O-CH₂-, -CH₂-S (O) _n -, -S (O) _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 hydrogen, 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 and
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, as well
n represents 0, 1 or 2,
those 2-oximino-2-thienyl-acetic acid derivatives of the formula (I) in which the group Ar-A and the oximinoacetic acid residue in the thiophene ring are adjacent are particularly preferred.

Compounds of the formula (I) in which
Ar for optionally monosubstituted to pentasubstituted, identically or differently substituted aryl having 6 or 10 carbon atoms or for optionally monosubstituted to quadruple, identically or differently substituted and / or benzo-fused heteroaryl with 2 to 9 carbon atoms and 1 to 3 identical or different heteroatoms - especially nitrogen Oxygen and / or sulfur - is available, the following being suitable 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 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 same 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, eq Calibrated 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 carbons and 1 to 7 identical or different halogen atoms, each doubly linked alkylene or dioxyalkylene, each with 1 up 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 single 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 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 having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy and
R¹ represents straight-chain or branched alkyl having i 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 branched alkenyl or alkenyloxy each having 2 to 4 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkyl thio 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 have 1 to 4 carbon atoms in the individual alkyl parts and also for each optionally in the phenyl part from one to five times, identically or differently by halogen and / or ge rad-chain or branched alkyl having 1 to 3 carbon atoms en 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 ge straight-chain 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,
A represents oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH₂-O-; -O-CH₂-, -CH₂-S (O) _n -, S (O) _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 hydrogen, 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 and
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, as well
n represents 0, 1 or 2,
those 2-oximino-2-thienyl-acetic acid derivatives of the formula (I) in which the group Ar-A and the oximinoacetic acid residue in the thiophene ring are adjacent are particularly preferred.

Compounds of the formula (I) 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, methylsulfinyl, methylsulfonyl, allyl, butenyl, allyloxy, butenyloxy, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylethylsulfonyl, diethylamethyl, sulfonyl , Acetoxy, methylsulfonyloxy, ethylsulfonyloxy, methoxycarbonyl, ethoxycarbonyl, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, ethoximinomethyl, ethoximinoethyl, propane-1,3-diyl, butane-1,4-diyl, dioxymethylene, dioxyethylene, dioxodioxy dioxy, dioxoxioxy, 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 un d / or trifluoromethoxy substituted phenyl, phenoxy, benzyl or benzyloxy and
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 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, ethoxyethyloxymethyl, hydroxymethyl, hydroxymethyl, hydroxymethyl , Methoximinoethyl, Ethoximinomethyl, Ethoximino ethyl or each optionally mono- to triple, identical or different to the phenyl, phenoxy, benzyl or benzyloxy substituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy ,
A represents oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH₂-O-; -O-CH₂-, -CH₂-S (O) _n -, -S (O) _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 hydrogen, methyl, ethyl, trifluoromethyl or cyano,
R⁵ for straight-chain or branched alkyl having 1 to 4 carbon atoms such as methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or for haloalkyl with 1 to 2 carbon atoms and 1 to 5 identical or ver different halogen atoms and
R⁶ and R⁷ are each independently of one another hydrogen, for straight-chain or branched alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, for haloalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms or stand for straight-chain or branched alkoxy with 1 to 4 carbon atoms, and
n represents 0, 1 or 2,
those 2-oximino-2-thienyl-acetic acid derivatives of the formula (I) in which the group Ar-A and the oximino acetic acid residue in the thiophene ring are adjacent are particularly preferred.

The radicals listed above or specified in preferred ranges definitions apply to both the end products of the formula (I) and ent speaking for the respective starting materials or Intermediates.

These residual definitions can be among each other, that is, between the specified areas of preferred connections, can be combined as desired.

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

For example, 2- [3- (2-methylphenoxy-methyl) -2-thienyl] -2-oxo is used methyl acetate and O-methylhydroxylamine hydrochloride as starting substances, the course of the reaction of process (a) according to the invention can be represented by the following formula:

For example, 2- (3-chloromethyl-2-thienyl) -2-methoximino-vinegar is used acid methyl ester and thiophenol as starting materials, so the reaction can run of the method (b) according to the following formula put:

For example, 2- [3- (2-methylphenoxy-methyl) -2-thienyl] -2-meth is used oximino-acetic acid methyl ester and methylamine as starting materials, so can the course of the reaction of the method (c) according to the invention by the following Represent formula scheme:

To carry out the method according to the invention as Aus a-Oxo-thienyl-acetic acid derivatives are required by the Formula (IIa) generally defined. In this formula (IIa) R², R³, Ar, A and Z are preferably for those residues that are already related to the Description of the compounds of formula (I) according to the invention as preferred for these substituents.

α-Oxothienyl acetic acid derivatives of the formula (IIa) are known in some cases or available in analogy to known methods (cf., for example, EP 243 014), for example by using halomethyl-thiophenecarboxylic acid esters of the formula (VII),

in which
R² and R³ have the meaning given above,
X represents halogen and
R⁹ represents alkyl,
initially in a first stage in analogy to carrying out process (b) according to the invention 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 represents alkyl, haloalkyl, cycloalkyl or cyano,
optionally in the presence of a diluent such as acetonitrile and optionally in the presence of a reaction auxiliary such as sodium hydride at temperatures between 0 ° C. and 100 ° C. and then the thiophenecarboxylic acid esters of the formula (VIII) obtainable in this way,

in which
R², R³, R⁹, Ar and A¹ have the meaning given above,
in a subsequent second stage with water in the presence of a basic reaction auxiliary at temperatures between 20 ° C. and 70 ° C. and then the thiophenecarboxylic acids of the formula (IX) obtainable in this way,

in which
R², R³, Ar and A¹ have the meaning given above,
in a subsequent third stage with conventional acid halide formers such as thionyl chloride, if appropriate in the presence of a diluent such as dichloroethane, at temperatures between 20 ° C. and 120 ° C. and then the thiophenecarboxylic acid halides of the formula (X) thus obtainable,

in which
R², R³, Ar and A¹ have the meaning given above and
Hal represents halogen, in particular chlorine or bromine,
in a subsequent 4th stage with sodium cyanide, if appropriate in the presence of a diluent such as dichloroethane / water and if appropriate in the presence of a reaction auxiliary such as tetrabutylammonium bromide at temperatures between 0 ° C and 50 ° C and then the 2-oxo-2 thus obtainable thienylacetonitriles of the formula (XI),

in which
R², R³, Ar and A¹ have the meaning given above,
in a subsequent 5th stage with acid such as hydrochloric acid and alcohols of the formula (XII),

R⁵-OH (XII)

in which
R⁵ has the meaning given above,
if appropriate in the presence of a diluent such as, for example, t-butyl methyl ether and, if appropriate, in the presence of a reaction auxiliary such as, for example, acetic anhydride at temperatures between 20.degree. C. and 150.degree. C. and if appropriate subsequently the a-oxothienyl-acetic acid derivatives of the formula (IIa -1),

in which
R², R³, R⁵, Ar and A¹ have the meaning given above,
or their ketals of the formula (IIb-1),

in which
R², R³, R⁵, Ar and A¹ have the meaning given above,
or mixtures of -oxothienyl-acetic acid esters of the formula (IIa-1) and their ketals of the formula (IIb-1) in a subsequent 6th stage in analogy to carrying out process (c) according to the invention 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 reactant.

a-oxothienyl acetic acid ester of the formula (IIa-1),

in which
R², R³, R⁵, Ar and A¹ have the meaning given above,
can alternatively also be obtained if 2-oxo-2- (3-methyl-2-thienyl) acetic acid ester of the formula (XIII)

in which
R², R³ and R⁵ have the meaning given above,
initially in a 1st stage with formic acid orthoesters of the formula (XIV),

H-C (OR⁸) ₃ (XIV)

in which
R⁸ represents alkyl, in particular methyl or ethyl,
if appropriate in the presence of a diluent such as methanol or ethanol and if appropriate in the presence of a reaction auxiliary such as sulfuric acid at temperatures between 0 ° C. and 120 ° C. and then the ketals of the formula (XV) obtainable in this way,

in which
R², R³, R⁵ and R⁸ have the meaning given above,
in a subsequent second stage with a halogenating agent, such as N-bromosuccinimide, if appropriate in the presence of a diluent such as carbon tetrachloride and optionally in the presence of a reaction auxiliary such as azodiisobutyrodinitrile (AIBN) at temperatures between 20 ° C and 150 ° C and then the halomethyl ketals of the formula (XVI) thus obtainable,

in which
R², R³, R⁵ and R⁸ have the meaning given above and
Hal represents halogen, in particular chlorine or bromine,
in a subsequent third stage in analogy to carrying out process (b) according to the invention using 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 represents alkyl, haloalkyl, cycloalkyl or cyano,
optionally in the presence of a diluent such as acetonitrile and optionally in the presence of a reaction auxiliary such as sodium hydride at temperatures between 0 ° C. and 100 ° C., then the ketals of the formula (XVII) obtainable in this way,

in which
R², R³, R⁵, R⁸, Ar and A¹ have the meaning given above
in a subsequent 4th stage with aqueous acid, such as hydrochloric acid, if appropriate in the presence of a diluent such as dichloromethane, at temperatures between 20 ° C. and 120 ° C.

Halomethyl-thiophenecarboxylic acid esters of the formula (VII) are known or available in analogy to known processes (cf., for example, J. Org. Chem. 51, 235 [1986]).

2-oxo-2- (3-methyl-2-thienyl) acetic acid esters of the formula (XIII) are known or available in analogy to known processes (cf. e.g. Org. Prep. Proced. 2, 249-251 [1970]; BE 896054; US 3,622,569 and the manufacturing examples) for example by reacting the generally known methylthiophene carboxylic acids with thionyl chloride to the corresponding acid chlorides; these are in turn reacted with sodium cyanide in a subsequent reaction corresponding a-oxonitriles in a third stage in the usual way are saponified with acids in the presence of an alcohol and esterified at the same time.

Alcohols of the formula (XII) and formic acid orthoesters of the formula (XIV) are all Commonly known compounds of organic chemistry.

Not yet known and also the subject of the invention are the following Intermediates: thiophene carboxylic acid ester of formula (VIII), thiophene carbon acids of the formula (IX), thiophene carboxylic acid halides of the formula (X), 2-oxo-2- thienylacetonitrile of the formula (XI), ketals of the formula (XV), halomethyl ketals  of the formula (XVI), ketals of the formula (XVII) and a-oxothienyl-acetic acid derivatives of formula (IIa) and their ketals of formula (IIb) with the exception of the compound 2-Oxo-2- (3-phenoxymethyl-2-thienyl) acetic acid methyl ester.

The to carry out the method (a) according to the invention as out Required hydroxylamines are generally defi by the formula (III) kidney. In this formula (III), R1 preferably represents those radicals which already exist in connection with the description of the compounds according to the invention of formula (I) have been mentioned as preferred for these substituents.

The hydroxylamines of the formula (III) are, like their hydrohalide salts, such as, for example, their hydrochlorides or hydrobromides organic chemistry bonds.

Those used to carry out process (b) according to the invention as starting materials required 2-oximino-2- (3-halogenomethyl-2-thienyl) acetic acid derivatives are by the formula (IV) is generally defined. In this formula (IV) R¹, R², R³ and Z are preferably for those residues that are already related to the Description of the compounds of formula (I) according to the invention as preferred for these substituents. X preferably represents halogen, especially for chlorine or bromine.

The 2-oximino-2- (3-halomethyl-2-thienyl) acetic acid derivatives of the formula (IV) are not yet known and are also the subject of the invention. You get them if one can obtain those obtainable with the aid of processes (a) or (c) 2-oximino-2-thienyl-acetic acid derivatives of the formula (Ib),

in which
R¹, R², R³, Ar and Z have the meaning given above,
with hydrogen halides, such as hydrogen chloride or hydrogen bromide, if appropriate in the presence of a diluent such as methanol at temperatures between 0 ° C and 80 ° C.

The compounds of formula (IV) can also by reacting Compounds of the formula (XIII) - above - with hydroxylamines of the formula (III) - above - (analogous to process (a)) and then with halogenating agents, such as e.g. B. N-chloro or N-bromo-succinimide, can be obtained by conventional methods (see the manufacturing examples).

Those for carrying out process (b) according to the invention and for synthesizing the Intermediates of formula (II) nucleophiles still required as starting materials are generally defined by the formula (V). In this formula (V) is Ar preferably for those residues that are already in connection with the Description of the compounds of formula (I) according to the invention as preferred for these substituents. A¹ preferably represents oxygen, Sulfur or for a radical of the formula -C (R⁴) = N-O-, where R⁴ is preferably for those residues that are already related to the description of the Compounds of formula (I) according to the invention as preferred for this Substituents were called.

The nucleophiles of the formula (V) are generally known compounds of the organic chemistry.

Those used to carry out process (c) according to the invention as starting materials required 2-oximino-2-thienyl-acetic acid derivatives are represented by the formula (Ia) generally defined. In this formula (Ia) R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and A preferably for those residues that are already associated with the Description of the compounds of formula (I) according to the invention as preferred for these substituents.  

The 2-oximino-2-thienyl-acetic acid derivatives of the formula (Ia) are according to the invention Compounds and obtainable with the aid of processes (a) and (b).

The to carry out the method (c) according to the invention as out Formula (VI) generally defines amines required for starting materials. In of this formula (VI) R¹⁰ and R¹¹ are preferably those radicals which already in connection with the description of the invention Compounds of formula (I) mentioned as preferred for these substituents were.

The amines of the formula (VI) are generally known compounds of organic chemistry.

As a diluent for carrying out process (a) according to the invention inert organic solvents are suitable. These include in particular ali phatic, alicyclic or aromatic, optionally halogenated coal water substances such as gasoline, benzene, toluene, xylene, chlorobenzene, dichlor benzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachlor carbon; 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 hexamethyl phosphoric triamide; Alcohols, such as methanol, ethanol, n- or i-propanol, ethyl lenglycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol mono methyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

Process (a) according to the invention is preferably used in the presence of a Neten reaction auxiliary carried out. As such come all the usual anorga African or organic bases in question. These include, for example, alkaline earth or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or -hydrogen carbonates, such as sodium hydride, sodium amide, sodium me ethylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, Ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium ace  tat, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and tertiary amines, such as trimethylamine, tri ethylamine tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-di methylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or Diazabicycloundecene (DBU).

The reaction temperatures can be carried out when carrying out the process according to the invention Process (a) can be varied over a wide range. 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 guided. However, it is also possible to increase or decrease the pressure work.

To carry out process (a) according to the invention, Oxothienyl 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 corresponding hydrohalide and optionally 1.0 to 6.0 mol, preferably 1.0 to 3.0 moles of reaction auxiliary. The reaction The reaction products are carried out, worked up and isolated according to be knew procedures.

As a diluent for carrying out process (b) according to the invention inert organic solvents are suitable. These include in particular ali phatic, alicyclic or aromatic, optionally halogenated coal water substances such as gasoline, benzene, toluene, xylene, chlorobenzene, dichlor benzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachlor 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; Ami de, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N- Methylpyrrolidone or hexamethylphosphoric triamide; Esters such as acetic acid ethyl ester or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethyl  lenglycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono ethyl ether, their mixtures with water or pure water.

The process according to the invention can (b) optionally also in a two-pha system such as water / toluene or water / dichloromethane if necessary in the presence of a suitable phase transfer catalyst become. Examples of such catalysts are: tetrabutylammoni umiodide, tetrabutylammonium bromide, tetrabutylammonium chloride, tributyl-me thylphosphonium bromide, trimethyl-C₁₃ / C₁₅-alkylammonium chloride, trimethyl- C₁₃ / C₁₅-alkylammonium bromide, dibenzyl-dimethyl-ammonium methyl sulfate, dime thyl-C₁₂ / C₁₄-alkyl-benzylammonium chloride, dimethyl-C₁₂ / C₁₄-alkyl-benzylammo nium bromide, tetrabutylammonium hydroxide, triethylbenzylammonium chloride, Me thyltrioctylammonium chloride, trimethylbenzylammonium chloride, 15-crown-5, 18-crown-6 or tris [2- (2-methoxyethoxy) ethyl] amine.

Process (b) according to the invention is preferably used in the presence of a Neten reaction auxiliary carried out. As such come all the usual anorga African or organic bases in question. These include, for example, alkaline earth or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or -hydrogen carbonates, such as sodium hydride, sodium amide, sodium me ethylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, Ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium ace tat, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and tertiary amines, such as trimethylamine, tri ethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-di methylaminopyridine, 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 guided. However, it is also possible to increase or decrease the pressure work.

To carry out process (b) according to the invention, 2- Oximino-2- (3-halomethyl-2-thienyl) acetic acid derivative of the formula (IV) in general mean 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol of nucleophile of the formula (V) and optionally 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol of reacti on aids. Carrying out the reaction, working up and isolating the Reaction products are carried out according to known methods.

As a diluent for carrying out process (c) according to the invention inert organic solvents are suitable. These include in particular ali phatic, alicyclic or aromatic, optionally halogenated coal water substances such as gasoline, benzene, toluene, xylene, chlorobenzene, dichlor benzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachlor carbon; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Nitriles such as acetonitrile, Pro pionitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethyl acetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphorus acid triamide or sulfoxides, such as dimethyl sulfoxide.

Process (c) according to the invention is preferably used in the presence of a Neten reaction auxiliary carried out. As such come all the usual anorga African or organic bases in question. These include, for example, alkaline earth or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or -hydrogen carbonates, such as sodium hydride, sodium amide, sodium me ethylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, Ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium ace tat, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and tertiary amines, such as trimethylamine, tri ethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-di methylaminopyridine, 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 temperature between -20 ° C and + 120 ° C.

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

To carry out process (c) according to the invention, 2- Oximino-2-thienyl-acetic acid derivative of the formula (Ia) generally 1.0 to 3.0 Mol, preferably 1.0 to 1.5 mol of amine of formula (VI) and optionally 0.1 to 3.0 mol, preferably 0.5 to 1.5 mol of as a reaction aid base used. It is also in a special implementation form possible, the 2-oximino-2-thienyl-acetic acid used as starting products derivatives of the formula (Ia) in an upstream reaction in the reaction vessel produce and then directly in a so-called "One-pot reaction" according to process (c) according to the invention to implement. Carrying out the reaction, working up and isolating the reactants onproducts are carried out in analogy to known processes (cf. for example EP 398 692 and the production examples).

The end products of the formula (I) are purified with the aid of customary ones Processes, for example by column chromatography or by Recrystallize.

The characterization takes place with the help of the melting point or not crystallizing compounds using the refractive index or the proton Nuclear magnetic resonance spectroscopy (1 H-NMR).

The active compounds according to the invention have a strong microbicidal action and can be useful to combat unwanted microorganisms  be used. The active ingredients are for use as pesticides, particularly suitable as fungicides.

Fungicides in crop protection are used to combat plas modiophoromycetes, 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 Pseudoperonospora 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: Drechslera, 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 herpotrichoi des.

The good plant tolerance of the active ingredients in the control of the plant Concentrations necessary for diseases allow treatment from above parts of plants, planting and seeds and the soil.

The active compounds according to the invention can be used with particularly good success Combating diseases in fruit and vegetable growing, such as against the pathogen of apple scab (Venturia inaequalis) or for combating of cereal diseases such as against the pathogen of the real  Powdery mildew (Erysiphe graminis) or against the pathogen of the Net spot disease of barley (Pyrenophora teres) or against the pathogen of the Brown fur of the wheat (Leptosphaeria nodorum) or against the pathogen brown spot disease of barley or wheat (Cochliobolus sativus) or against Fusarium species or to fight rice diseases like with for example against the causative agent of rice stain disease (Pyricularia oryzae) be set. In addition, the active compounds according to the invention have a good in vitro effectiveness.

The active ingredients can depend on their respective physical and / or chemical properties converted into customary formulations such as solutions, emulsions, suspensions, powders, foams, pastes, Granules, aerosols, very fine encapsulations in polymeric substances and in Envelopes for seeds, as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, e.g. B. by Mixing the active ingredients with extenders, i.e. liquid solvents, under Pressurized liquefied gases and / or solid carriers, if necessary using surface-active agents, ie emulsifiers and / or Dispersing agents and / or foaming agents. In case of use of water as an extender can e.g. B. also organic solvents Auxiliary solvents can be used. As liquid solvents come in essential in question: aromatics, such as xylene, toluene, alkylnaphthalenes, chlorinated Aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene, or methylene chloride, aliphatic hydrocarbons, such as Cyclohexane or paraffins, e.g. B. 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 dime thylformamide or dimethyl sulfoxide, and water; with liquefied gaseous Extenders or carriers are those liquids which mean normal temperature and under normal pressure are gaseous, e.g. B. Aerosol Propellants, such as halogenated hydrocarbons and 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 pebbles  acid, alumina and silicates; come as solid carriers for granules in question: 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 Foaming agents are possible: B. non-ionic and anionic Emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and Protein hydrolyzates; as dispersants come into question: z. B. Lignin sulfite liquor and methyl cellulose.

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic, powdery, granular or latex-shaped polymers are used, 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, e.g. B. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, Copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 Weight percent active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be formulated as such also in a mixture with known fungicides, bactericides, acaricides, Nematicides or insecticides can be used, e.g. B. the effect to broaden the spectrum or to prevent the development of resistance. In many Cases have synergistic effects.

The following are preferably suitable for the mixtures:
Fungicides:
2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ′, 6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thizole-5-carboxanide; 2,6-di chloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- (2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl-3-methoxyacrylate; methyl- (E) methoximino- [alpha- (o-tolyloxy) -o -tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampro pylfos, anilazine, azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate, calcium polazulfimide, cap , Carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram, dichlorophen, diclobutrazole, diclofluanid, diclomezin, dicloranifenetholol, dicllorophenolimidolol, dicllorometholidolol, diazloridirol, diazolol, dicllorometholol, dimlolidometholol, diclorometholol, dimloconidolol, diclloridometholonol, dicllorometholidol, dicllorometholidol, diclodimetholol, dicloflidolinol, diclofirolone, aminocarbyl , Ditalimfos, Dithianon, Dodin, Drazoxolon, Edifenphos, Epoxyconazole, Ethirimol, Etridiazol, Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fen propimorph, Fentinacetate, Fentinhydroxyd, Fluide, Fluoride, Fidamonazole, Ferbamazolezone, Ferbamazole, Ferbamazole, Ferbamazole, Ferbamazole, Ferbamazole , Flusul famide, FIutolanil, Flu triafol, Folpet, Fosetyl-Aluminum, Fthalide, Fuberidazol, Furalaxyl, Furmecyclox, Guazatine, Hexachlorobenzol, Hexaconazol, Hymexazol, Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprofiol, Iprofiol
Kasugamycin, copper preparations, such as. Copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxin-copper and Bordeaux mix, Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobamatolitholyl, nickel carbamate methyl nitrate, nickel carbamate methyl nitrate, nickel carbamate methyl nitrate, nickel carbamate methyl nitrate, nickel carbamate methyl nitrate, nickel carbamate methyl nitrate, nickel carbamate methyl nitrate , Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin, Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin, Probenazol, Prochloraz, Procymidon, Propamocarb, Propiconazole, Propineb, Pyrazophos, PCifenil, Pyronox, Quinoxilon, Pyronox, Pyrimoxon, Pyrimoxil, Pyrimethil, Pyrimoxon, Pyrimethil, Pyrimoxonil sulfur preparations, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, tri adimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, validamycin A, vinclozolin , Zineb, ziram
Bactericides:
Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, Kasugamy cin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.
Insecticides / acaricides / nematicides:
Abamectin, Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin, Bacillus thuringiensis, Bendiocyl, Betulin Bifin, Carburin, Benfuracarbens , Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, ButyIpyridaben, Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chloretoxyfos, Chlorfluazosifone, Chlorfluorosurpone, Chlorfluorosurpone, Chlorfluorosurpone, Chlorfenazosphonophone, Chlorfenazosphonophone, Chlorfenazosphonophone, Chlorofazosphonophone, Chlorofenzosphonophone, Chlorofenzosphonophone, Chlorfenazosphonophone, Chlorofenzosphonophone, Chlorofenzosphonophone, Chlorofenzosphonophone, Chlorofenzosphonophone, Chlorofungosphonophone, Chlorofungosphonophone, Chlorofenzosphonophone, Chlorofungosphonophone, Chlorofenzosphonophosphorus Cis-resmethrin, Clo cythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexa tin, Cypermethrin, Cyromazin, Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazi non, dichloflos, Dichl , Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton, Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etho prophos, Etofenprox, E trimphos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, Fipro nil, fluazinam, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathiocarb , HCH, Heptenophos, Hexaflumuron, Hexythiazox, Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin, Lamda-cyhalothrin, Lufenuron, Malathion Mecarbam, Mervinphos, Mesulfenphos, Metaldidomidolomethomyl, Methaldidyl Carbomethion, Methaldidyl Carbomethionate, Methaldidyl Carbomethionate, Methaldidyl Carbomethane Milbemectin, Monocrotophos, Moxidectin, Naled, NC 184, NI 25, Nitenpyram Omethoat, Oxamyl, Oxydemethon M, Oxydeprofos, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamdon, Phoximos, Piriphos Miphimos, Phimimos A, Profenofos, Profenophos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothiophos, Prothoat, Pymetrozin, Pyrachlophos, Pyraclofos, Pyracloph os, Pyradaphenthion, Pyresme thrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos, RH 5992, Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos, Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzufos, Teflachoxin, Teflachoxin, Teflachoxin, Teflachoxin, Teflachoxin Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron, Trichlorfon, Triflumuron, Trimethacarb, Vamidothion, XMC, Xylylcarb, YI 5301/5302, Zetamethrin.

A mixture with other known active ingredients, such as herbicides or with Fertilizers and growth regulators are possible.

The active substances can be used as such, in the form of their formulations or in the form thereof prepared application forms, such as ready-to-use solutions, suspensions, Spray powder, pastes, soluble powders, dusts and granules are used become. The application is done in the usual way, e.g. B. by pouring, Spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to use the active ingredients according to the ultra-low-volume method apply or the drug preparation or the drug itself in the Inject soil. The seeds of the plants can also be treated.

When treating parts of plants, the active substance concentrations can be in the application forms can be varied in a larger area:  generally 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 at the site of action required.

Manufacturing examples example 1

(Method a)

5.23 g (0.018 mol) of 2-oxo-2- [3- (2-methylphenoxymethyl) -2-thienyl] acetic acid ethyl ester and 1.5 g (0.018 mol) of O-methylhydroxylamine hydrochloride in 27 ml Methanol are heated to reflux temperature for 4 hours, then in Concentrated vacuum and the residue was partitioned between chloroform and water. The chloroform phase is separated off, concentrated and the residue is evaporated through Chromatography on silica gel (eluent: dichloromethane) cleaned.

1.7 g (30% of theory) of (Z) -2- [3- (2-methylphenoxymethyl) -2- thienyl] -2-methoximino-acetic acid methyl ester as an oil.

1 H-NMR (CDCl₃ / tetramethylsilane): d = 2.274 (3H); 3,841 (3H); 4.006 (3H); 5.148 (2H); 6.78-6.90 (2H); 7.1-7.17 (2H); 7.238-7.255 (1H); 7.350-7.367 (1H) ppm
and 2.5 g (44% of theory) of (E) -2- [3- (2-methylphenoxymethyl) -2-thienyl] -2-methoximino-acetic acid methyl ester, melting point 78-81 ° C.

Preparation of the starting compounds Example IIa-1

To 7.2 g (0.028 mol) of 2- [3- (2-methylphenoxymethyl) -2-thienyl] -2-oxo-acetonitrile in 30 ml of t-butyl methyl ether are added at room temperature with stirring, 2.9 g (0.028 mol) acetic anhydride and then passes between at a temperature -10 ° C and 0 ° C dry hydrogen chloride gas until saturation. Subsequently is stirred for 24 hours at room temperature, then 40 ml of methanol and heated to reflux temperature for 10 hours. For processing the Cooled reaction mixture, filtered off the precipitated solid, in 150 ml Dichloromethane taken up, filtered, the filtrate washed with water and in Vacuum concentrated.

4.7 g (58% of theory) of 2-oxo-2- [3- (2-methylphenoxymethyl) -2- methyl thienyl] acetic acid, melting point 94-96 ° C.  

Example XI-1

To 8.5 g (0.032 mol) of 3- (2-methylphenoxymethyl) thiophene-2-carboxylic acid chloride 100 mg of tetrabutylammo are added to 28.8 ml of dichloroethane at room temperature nium bromide and then dropwise a solution of 1.7 g with stirring (0.035 mol) sodium cyanide in 20 ml water, the temperature of the Reaction mixture is kept below 25 ° C by external cooling. To when the addition is complete, the mixture is stirred at room temperature for a further 60 minutes and then separated the phases, extracted the aqueous phase with dichloroethane and washes then the combined organic phases three times with 10 ml each Water. The organic phase is dried and concentrated in vacuo.

7.2 g (88% of theory) of 2- [3- (2-methylphenoxymethyl) -2-thienyl] - are obtained 2-oxo-acetonitrile as an oil.

1 H-NMR (CDCl₃ / tetrmethylsilane): d = 2.315 (3H); 5.414 (2H); 6.83-6.94 (2H); 7.14-7.20 (2H); 7.564-7.581 (1H); 7.945-7.961 (1H) ppm.  

Example X-1

To 8.4 g (0.034 mol) of 3- (2-methylphenoxymethyl) thiophene-2-carboxylic acid in 40 ml Dichloromethane is added at room temperature to 10.1 g (0.085 mol) of thionyl chloride and then heated to reflux temperature for 2 hours. To work up the volatiles are removed in vacuo.

8.5 g (94% of theory) of 3- (2-methylphenoxymethyl) thiophene-2- are obtained. carboxylic acid chloride as an oil.

1 H-NMR (CDCl₃ / tetramethylsilane): d = 2.315 (3H); 5.346 (2H); 6.82-6.93 (2H); 7.13-7.19 (2H); 7.254-7.466 (1H); 7.741-7.758 (1H) ppm.  

Example IX-1

To 13.8 g (0.0526 mol) of 3- (2-methylphenoxymethyl) thiophene-2-carboxylic acid methyl esters in 50 ml of methanol are added 9.4 g (0.106 mol) of 45- percent aqueous sodium hydroxide solution and then stirred for one hour at 60 ° C. For Working up is concentrated in vacuo, the residue with 2N hydrochloric acid acidified, the precipitate filtered off and dried.

8.4 g (64% of theory) of 3- (2-methylphenoxymethyl) thiophene-2- are obtained. carboxylic acid.

1 H-NMR (DMSO-d₆ / tetramethylsilane): d = 2.216 (3H); 5.420 (2H); 6.83- 6.92 (2H); 7.12-7.18 (2H); 7.275-7.292 (1H); 7.833-7.850 (1H) ppm.  

Example VIII-1

Add to 7.0 g (0.065 mol) of 2-methylphenol in 65 ml of dimethylformamide Stirring and cooling in portions 1.94 g (0.065 mol) of 80 percent sodium hy drid and stir until the end of gas evolution. Then 15.2 g (0.065 Mol) of 3-bromomethylthiophene-2-carboxylic acid methyl ester (see, for example, J. Org. Chem 51, 235 [1986]) and then stirred for 30 minutes at room temperature. For Working up is concentrated in vacuo, the residue between dichloromethane and distributed water, the dichloromethane phase separated, dried and in Vacuum concentrated.

13.8 g (81% of theory) of 3- (2-methylphenoxymethyl) thiophene-2- are obtained. carboxylic acid methyl ester as an oil.

1 H-NMR (CDCl₃ / tetramethylsilane): d = 2.31 (3H); 3.89 (3H); 5.47 (3H); 6.8- 7.0 (2H); 7.0-7.2 (2H); 7.34-7.35 (1H); 7.47-7.49 (1H) ppm.  

Example IV-1

25.0 g (0.078 mol) of 2- [3- (2-methylphenoxymethyl) -2-thienyl] -2-methoximino vinegar Acid methyl esters are at 0 ° C in 80 ml of methanol, which previously with dry hydrogen chloride gas, dissolved and then 12 Stirred for hours at room temperature. For working up is in a vacuum concentrated, the residue taken up in dichloromethane, washed with water, dried and concentrated in vacuo. The residue is in a high vacuum distilled.

9.3 g (48% of theory) of 2- [3- (2-chloromethyl) -2-thienyl] -2-meth oximino-acetic acid methyl ester are obtained as an oil. The (E) / (Z) isomers can be separated by chromatography on silica gel (mobile phase: dichloromethane).
(E) -2- [3- (2-Chloromethyl) -2-thienyl] -2-methoximino-acetic acid methyl ester
1 H-NMR (CDCl₃ / tetramethylsilane): d = 3.92 (3H); 4.28 (3H); 4.42 (2H); 7.15 (1H); 7.52 (1H) ppm.
(Z) -2- [3- (2-chloromethyl) -2-thienyl] -2-methoximino-acetic acid methyl ester
1 H-NMR (CDCl₃ / tetramethylsilane): d = 3.93 (3H); 4.03 (3H); 4.72 (2H) ppm.

Example IV-2

9.0 g (0.028 mol) of 2- [2- (2-methylphenoxymethyl) -3-thienyl] -2-methoximino vinegar Acid methyl esters are at 0 ° C in 200 ml of methanol, which previously with dry hydrogen chloride gas, dissolved and then 12 Stirred at 0 ° C for hours. For working up, the mixture is concentrated in vacuo Residue taken up in dichloromethane, washed with water, dried and concentrated in vacuo. The residue is distilled in a high vacuum.

5.3 g (75% of theory) of 2- (2-chloromethyl-3-thienyl) -2-methoximi no-acetic acid methyl ester are obtained as an oil. The (E) / (Z) isomers can be separated by chromatography on silica gel (mobile phase: dichloromethane).
(E) -2- (2-chloromethyl-3-thienyl) -2-methoximino-acetic acid methyl ester
1 H-NMR (CDCl₃ / tetrainethyisilane): d = 3.90 (3H); 4.10 (3H); 4.62 (2H); 6.94 - 6.96 (1H); 7.33-7.34 (1H) ppm.
(Z) -2- (2-chloromethyl-3-thienyl) -2-methoximino-acetic acid methyl ester
1 H-NMR (CDCl₃ / tetramethylsilane): d = 3.92 (3H); 4.03 (3H); 5.00 (2H) ppm.

Example IV-3 step 1

15.2 g (0.1 mol) of 2- (3-methyl-2-thienyl) -2-oxo-acetic acid methyl ester and 8.35 g (0.1 mol) of O-methyl-hydroxylamine hydrochloride are used for 16 hours cooked at reflux. The mixture is concentrated, the residue is partitioned between ethyl acetate and water, the mixture is concentrated and 16.8 g of product (78.8% of theory) are distilled at 0.1 Torr between 90 ° C. and 105 ° C. The stereoisomers are in the ratio of E: Z = 4: 3.
1 H-NMR (CDCl₃ / tetramethylsilane):
E isomer: δ = 2.137 (3H); 3,897 (3H); 4.115 (3H); 6.872 / 6.888 (1H); 7.410 / 7426 (1H) ppm.
Z isomer: δ = 2.255 (3H); 3.913 (3H); 3,981 (3H); 6.821 / 6.838 (1H); 7.234 / 7.251 (1H) ppm.

Level 2

10.7 g (0.05 mol) of 2- (3-methyl-2-thienyl) -2-methoximinoacetic acid methyl ester are boiled with 8.9 g (0.05 mol) of N-bromosuccinimide in 50 ml of carbon tetrachloride. After adding 200 mg of azobisisobutyronitrile, the mixture is refluxed for 30 minutes. The mixture is cooled to 0 ° C., the succinimide is filtered off and the solvent is removed in vacuo. 14.6 g (100% of theory) of product are obtained. According to GG / MS analysis, it contains 70% EZ mixture of the monobromo compound.
1 H-NMR (CDCl₃ / tetramethylsilane):
E isomer: δ = 3.918 (3H); 4.146 (3H); 4.304 (2H); 7.144 / 7.161 (1H); 7.482 / 7.499 (1H) ppm.
Z isomer: δ = 3.948 (3H); 4.042 (3H); 4,636 (2H); 7.113 / 7.130 (1H); 7.338 / 7.355 (1H) ppm.

Example IIa-1

(alternative production)

To 1.0 g (0.003 mol) of 2- [3- (2-methylphenoxymethyl) -2-thienyl] -2,2-dimethoxy-es methyl acetate in 3.6 ml dichloromethane is added 0.7 ml concentrated Hydrochloric acid and then stirred for 10 hours at room temperature. For Working up, the reaction mixture is concentrated in vacuo and the Crystallized residue from a little methanol.

0.6 g (70% of theory) of 2-oxo-2- [3- (2-methylphenoxymethyl) -2- methyl thienyl] acetic acid, melting point 94-96 ° C.  

Example XVII-1

To a solution of 1.08 g (0.01 mol) of 2-methylphenol in 10 ml Dimethylformamide is added at 0 ° C 0.3 g (0.01 mol) 80 percent Sodium hydride, then let the batch come to room temperature, then give 3.09 g (0.01 mol) of 2- (3-bromomethyl-2-thienyl) -2,2-dimethoxy-acetic acid methyl ester and then stirred for 12 hours at room temperature. To work up poured the reaction mixture onto water, extracted with chloroform, the organic phase washed twice with 2N sodium hydroxide solution, concentrated in vacuo and the residue by chromatography on silica gel (mobile solvent: Ether / petroleum ether 1: 3).

1.1 g (33% of theory) of 2- [3- (2-methylphenoxymethyl) -2-thienyl] - are obtained 2,2-dimethoxy-acetic acid methyl ester with a melting point of 95-97 ° C.  

Example XVI-1

20 g (0.087 mol) of 2- (3-methyl-2-thienyl) -2,2-dimethoxy-acetic acid methyl ester and 15.5 g (0.087 mol) of N-bromosuccinimide in 90 ml of carbon tetrachloride Boiled, then mixed with 100 mg azodiisobutyrodinitrile (AIBN) and 2 Cooked under reflux for hours. The reaction mixture is worked up cooled to 0 ° C, filtered, the filtrate concentrated in vacuo and the residue distilled in a high vacuum.

19.3 g (72% of theory) of methyl 2- (3-bromomethyl-2-thienyl) -2,2-dimethoxyacetate are obtained.
1 H-NMR (CDCl₃ / tetramethylsilane): δ = 3.321 (6H); 3.805 (3H); 4,643 (2H); 7.083-7.100 (1H); 7.321-7.330 (1H) ppm.

Example XV-1

49.7 g (0.27 mol) of 2- (3-methyl-2-thienyl) -2-oxo-acetic acid methyl ester, 28.7 g (0.27 Mol) trimethyl orthoformate and 8.7 g (0.27 mol) of methanol are ver mixes, mixed with 2.7 g of concentrated sulfuric acid and 2 days at Leave room temperature. For working up, 6 g of triethylamine are added, concentrated in vacuo and distilled the residue in a high vacuum.

48.6 g (78% of theory) of methyl 2- (3-methyl-2-thienyl) -2,2-dimethoxyacetate are obtained from the boiling point 110 ° C. at 1 torr.
1 H-NMR (CDCl₃ / tetramethylsilane): δ = 2.222 (3H); 3.285 (6H); 3,774 (3H); 6.806-6.823 (1H); 7.225-7.241 (1H) ppm.

Example XIII-1

To a suspension of 33.8 g (0.253 mol) aluminum trichloride in 250 ml Dichloromethane is added dropwise at 0 ° C with stirring 31 g (0.253 mol) Oxalic acid methyl ester chloride, stirred for 15 minutes after the addition is complete then also dropwise at 0 ° C 24.8 g (0.253 mol) of 3-methylthiophene to, the mixture is allowed to come to room temperature and is stirred for a further 30 minutes at this temperature. For working up, the mixture is poured onto a mixture from 25 ml of concentrated hydrochloric acid and 250 g of ice, the organic phase is separated off, dry it over sodium sulfate, concentrate in vacuo and distill the residue in a high vacuum.

24.1 g (52% of theory) of methyl 2- (3-methyl-2-thienyl) -2-oxoacetate with a boiling point of 95-100 ° C. at 0.05 torr are obtained.
1 H-NMR (CDCl₃ / tetramethylsilane): δ = 2.606 (3H); 3.758 (3H); 7.01 (1H); 7.65 (1H) ppm.

Example 2

(Method c)

To 0.8 g (0.0026 mol) of (E) -2- [3- (phenoxymethyl) -2-thienyl] -2-methoximino-vinegar Acid methyl ester in 15 ml of methanol gives 2.3 ml (0.02 mol) of 30 percent aqueous methylamine solution, then stirred for 16 hours 18971 00070 552 001000280000000200012000285911886000040 0002004405428 00004 18852en at room temperature and then removes the solvent in vacuo.

0.8 g (100% of theory) of (E) -2- [3- (phenoxymethyl) -2-thienyl] -2-methoximino-acetic acid-N-methylamide is obtained as an oil.
1 H-NMR (CDCl₃ / tetramethylsilane): δ = 2.85 (d, 3H); 4.15 (s. 3H); 5.01 (s, 1H); 6.8-7.6 (m, 7H) ppm.

Example 3

(Method a)

5.0 g (0.0149 mol) of 2- [2- (2-methylphenoxymethyl) -3-thienyl] -2,2-dimethoxy vinegar Acid methyl ester with 5.0 g (0.056 mol) of O-methylhydroxylamine Hydrochloride in a mixture of 50 ml of methanol and 10 ml of water for 4 hours cooked under reflux. The methanol is worked up in vacuo distilled off, the residue was partitioned between dichloromethane and water, the Concentrated dichloromethane solution in vacuo and the residue by adding 4 ml of methanol brought to crystallization.

Filtration gives 0.9 g (19% of theory) of (E) -2- [2- (2-methylphenoxymethyl) -3-thienyl] -2-methoximino-acetic acid methyl ester.
1 H-NMR (CDCl₃ / tretramethylsilane): δ = 2.251 (3H); 3.845 (3H); 4.075 (3H); 5.069 (2H); 6.776-6.803 (1H); 6.879-6.903 (1H); 7.0-7.32 (4H) ppm.

By concentrating the mother liquor, 1.4 g (30% of theory) of (Z) -2- [2- (2-methylphenoxymethyl) -3-thienyl] -2-methoximino-acetic acid methyl ester is obtained.
1 H-NMR (CDCl₃ / tetramethylsilane): δ = 2.317 (3H); 3.909 (3H); 4.006 (3H); 5.390 (2H); 6.7-7.4 (6H) ppm.

Preparation of the starting compounds Example IIb-1

To a solution of 4.33 g (0.04 mol) of 2-methylphenol in 40 ml of tetrahydrofuran are added at 0 ° C 4.5 g (0.04 mol) of potassium tert-butoxide and then 12.4 g (0.04 mol) of 2- (2-bromomethyl-3-thienyl) -2,2-dimethoxy-acetic acid methyl ester and then stir for 2 days at room temperature. For processing the Reaction mixture with water, extracted with diethyl ether, the organic Phase three times with 50 ml of 2N sodium hydroxide solution and then with water washed and concentrated in vacuo.

11.24 g (84% of theory) of 2- [2- (2-methylphenoxymethyl) -3-thienyl] -2,2-dimethoxyacetic acid methyl ester are obtained as an oil.
1 H-NMR (CDCl₃ / tetramethylsilane): δ = 2.307 (3H); 3.302 (6H); 3.75 (3H); 5.418 (2H); 6.9-7.25 (6H) ppm.

Example XVI-2

40 g (0.174 mol) of 2- (2-methyl-3-thienyl) -2,2-dimethoxyacetic acid and 30.9 g (0.174 mol) of N-bromosuccinimide are dissolved in 170 ml of carbon tetrachloride heated to boiling, then mixed with 100 mg of azodiisobutyrodinitrile (AIBN) and 2 Cooked under reflux for hours. The reaction mixture is worked up cooled to 0 ° C, filtered, the filtrate concentrated in vacuo and the residue distilled in a high vacuum.

40.6 g (76% of theory) of methyl 2- (2-bromomethyl-3-thienyl) -2,2-dimethoxyacetate are obtained.
1 H-NMR (CDCl₃ / tetramethylsilane): δ = 3.298 (6H); 3,778 (3H); 4,979 (2H); 7.069-7.087 (1H); 7.276-7.294 (1H) ppm.

Example XV-2

36.7 g (0.2 mol) of 2- (2-methyl-3-thienyl) -2-oxo-acetic acid methyl ester, 21.2 g (0.2 Mol) trimethyl orthoformate and 6.4 g (0.2 mol) of methanol are ver mixes, mixed with 2.1 g of concentrated sulfuric acid and 3 days Leave room temperature. To work up, neutralize with Triethylamine, concentrated in vacuo and the residue distilled in a high vacuum.

41.4 g (90% of theory) of 2- (2-methyl-3-thienyl) -2,2-dimethoxyacetic acid methyl ester with a boiling point of 95 ° C. at 1 torr are obtained.
1 H-NMR (CDCl₃ / tetramethylsilane): δ = 2.479 (3H); 3.259 (6H); 3.751 (3H); 6.99 - 7.008 (1H); 7.095-7.113 (1H) ppm.

Example XIII-2

To 34.7 g (0.23 mol) of 2- (2-methyl-3-thienyl) -2-oxo-acetonitrile in 230 ml of t-butyl methyl ether is added at room temperature with stirring 23.4 g (0.23 mol) Acetic anhydride and then conducts at a temperature between -10 ° C and 0 ° C dry hydrogen chloride gas until saturation. Then stir 24 hours at room temperature, then add 320 ml of methanol and heat for 16 Hours at reflux temperature. The reaction mixture is worked up concentrated, the residue between dichloromethane and water, the The dichloromethane phase was concentrated in vacuo and the residue in a high vacuum distilled.

37.7 g (89% of theory) of 2-oxo-2- (2-methyl-3-thienyl) acetic acid methyl ester with a boiling point of 92 ° C. at 0.6 torr are obtained.
1 H-NMR (CDCl₃ / tetramethylsilane): δ = 2.773 (3H); 3,943 (3H); 7.047-7.065 (1H); 7.486-7.504 (1H) ppm.

To 57 g (0.355 mol) of 2-methyl-thiophene-3-carboxylic acid chloride in 320 ml of dichloro 700 mg of tetrabutylammonium bromide and ethane are added at room temperature finally a solution of 19.1 g (0.389 mol) of sodium was added dropwise while stirring umcyanid in 210 ml water, the temperature of the reaction mixture by External cooling is kept below 25 ° C. After the addition is complete, stir another 60 minutes at room temperature, then separates the phases, extracts the aqueous phase with dichloroethane and then washes the combined organi phases three times with 50 ml of water each. The organic phase will dried and concentrated in vacuo, the residue distilled in a high vacuum.

35.2 g (66% of theory) of 2- (2-methyl-3-thienyl] -2-oxo-acetonitrile with a boiling point of 83 ° C. at 1.5 torr are obtained.
1 H-NMR (CDCl₃ / tetramethylsilane): δ = 2.817 (3H); 7.155-7.174 (1H); 7.598-7.616 (1H) ppm.

To 58.9 g (0.414 mol) of 2-methyl-thiophene-3-carboxylic acid (see, for example, J. Chem. Soc. Perkin Trans. I, 1983, 794) in 414 ml dichloroethane are added at room temperature 123.2 g (1.035 mol) of thionyl chloride and then heated for 2 hours Reflux temperature. For working up, the volatile constituents are removed in the Vacuum and distilled the residue in a water jet vacuum.

58.5 g (88% of theory) of 2-methyl-thiophene-3-carboxylic acid chloride with a boiling point of 92 ° C. at 10 torr are obtained.
1 H-NMR (CDCl₃ / tetramethylsilane): δ = 2.714 (3H); 7.029-7.048 (1H); 7.537-7.556 (1H) ppm.

Example 4

(Method b)

1.7 g (0.01 mol) of 3-chloro-acetophenone oxime are suspended in 0.3 g (0.01 mole) 80 percent. Sodium hydride entered in dimethylformamide. After that there 2.5 g (0.01 mol) of 2- (3-chloromethyl-2-thienyl) -2-methoximino-acetic acid ethyl ester and then stirred for 16 hours at room temperature. To work up water is added, extracted with ethyl acetate and the organic phase is concentrated in Vacuum on. The residue is purified by chromatography on silica gel (Eluent: petroleum ether / ether 1: 1) cleaned.

1.5 g (39% of theory) of (E) -3-chloro-O- [2- (1-methoxycarbonyl-1-methoximino-methyl) -thien-3-ylmethyl] acetophenone oxime are obtained as an oil .
1 H-NMR (CDCl₃ / tetramethylsilane): δ = 2.197 (3H); 3,861 (3H); 4.108 (3H); 5.133 (2H); 7.1-7.63 (6H) ppm
and 0.7 g (18% of theory) of (Z) -3-chloro-O- [2- (1-methoxycarbonyl-1-methoximino-methyl) thien-3-ylmethyl] acetophenone oxime as an oil.
1 H-NMR (CDCl₃ / tetramethylsilane): δ = 2.243 (3H); 3.914 (3H); 4.022 (3H); 5.301 (2H); 7.1-7.9 (6H) ppm.

Example 5

(Method c)

To 0.4 g (0.00105 mol) of 3-chloro-O- [2- (1-methoxycarbonyl-1-methoximino-methyl) - thien-3-ylmethyl] -acetophenone-oxime in 5 ml of tetrahydrofuran are added 2 ml of 40- percent aqueous methylamine solution, then stirred for 2 hours Room temperature, then removes the solvent in vacuo, takes the Residue in ethyl acetate, dried over sodium sulfate and removed Solvent in a vacuum.

0.3 g (75% of theory) of 3-chloro-O- [2- (2-methylamino-2-oxo-1-methoximino-ethyl) -thien-3-ylmethyl] acetophenone oxime is obtained as an oil .
1 H-NMR (CDCl₃ / tetramethylsilane): δ = 2.186 (3H); 2.905-2.917 (3H); 4.018 (3H); 5.109 (2H); 7.141-7.63 (6H) ppm.

Example 6

(Method b)

1.1 g (0.01 mol) of thiophenol are stirred into a suspension of 0.3 g (0.01 mole) 80 percent. Sodium hydride dropped in dimethylformamide. After that there 2.5 g (0.01 mol) of 2- (3-chloromethyl-2-thienyl) -2-methoximino-acetic acid ethyl ester and then stirred for 16 hours at room temperature. To work up water is added, extracted with ethyl acetate and the organic phase is concentrated in Vacuum on.

2.5 g (77% of theory) of 2- [3-phenylthiomethyl) -2-thienyl] -2-meth oximino-acetic acid methyl ester are obtained as an E / Z isomer mixture in a ratio of 2: 1. By chromatography the isomers can be separated in ether / petroleum ether (1: 1).
1 H-NMR (CDCl₃ / tretramethylsilane): δ = 3.863 (3H); 4.093 (3H); 3.950 (2H); 7.0-7.45 (7H) ppm (E isomer).

In a corresponding manner and in accordance with the general information on the manufacture the following 2-oximino-2-thienyl-acetic acid derivatives of the general are obtained Formula (I):

The compound listed as Example 23 in the table above can can be produced for example as follows:

0.007 mol (2.0 g) of ethyl [3- (4-methylphenoxy) thiophen-2-yl] glyoxylate and 0.0175 mol (1.5 g) methoxyammonium chloride are dissolved in 100 ml ethanol and heated under reflux for 10 hours. The solvent is distilled off Residue taken up in ethyl acetate, ge with saturated NaHCO₃ solution wash, dried over Na₂SO₄ and concentrated. Yield: 1.5 g (67%) brown Oil.

The compound listed as Example 24 in the table above can can be produced for example as follows:

To a solution of 0.04 mol (13 g) of 2- [3- (4-methylphenoxy) thiophene-2-yl] -2- methoximinoacetic acid ethyl ester in 200 ml of ethanol is cooled with ice to Saturation initiated methylamine. It will be another 18 hours at 20 ° C touched. The solution is concentrated and the residue from ethanol recrystallized. Yield: 6.7 g (55%) mp: 113 ° C.  

Examples of use

In the following application examples, the Ver bindings used as reference substance:

3-Methoxy-2- (6-phenyl-2-pyridylthio) acrylic acid methyl ester

3-Methoxy-2- [5- (4-chlorophenyl) -3-pyridyloxy] acrylic acid methyl ester

3-Methoxy-2- [n- (6-phenyl-2-pyridyl) -N-methylamino] acrylic acid methyl ester
(all known from EP 383 117).

Example A

Erysiphe test (barley) / protective
Solvent: 10 parts by weight of dimethylformamide
Emulsifier: 0.6 part by weight of alkyl aryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified 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 with spores from Erysiphe graminis f.sp. hordei pollinated.

The plants are grown in a greenhouse at a temperature of approx. 25 ° C and a relative humidity of about 80% set up the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation.

A clear superiority in effectiveness compared to the state of the Technology show in this test z. B. the compounds according to the preparation examples 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 21, which at one Active ingredient concentration of 400 g / ha an efficiency of 79% at 100% demonstrate. The compounds (A) and (B) show none at the same application rate Effect, the compound (C) shows an efficiency of 34%.  

Example B

Erysiphe test (wheat) / protective
Solvent: 10 parts by weight of dimethylformamide
Emulsifier: 0.6 part by weight of alkyl aryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified 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 with spores from Erysiphe graminis f.sp. tritici pollinated.

The plants are grown in a greenhouse at a temperature of approx. 25 ° C and a relative humidity of about 80% set up the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation.

A clear superiority in effectiveness compared to the state of the Technology show in this test z. B. the connections according to the manufacturing play 1, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 21, which are in a Application rate of 400 g / ha show an efficiency of 75% at 100%. The compounds (A) and (B) have no effect at the same application rate, the compound (C) shows an efficiency of 16%.  

Example C

Venturia test (apple) / protective
Solvent: 4.7 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether

A Ge is mixed to produce a suitable preparation of active compound most of the active ingredient with the specified 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 apple scab gers (Venturia inaequalis) and then remain at 20 ° C and for one day 100% relative humidity in an incubation cabin.

The plants are then grown in a greenhouse at 20 ° C and a relative Humidity of approx. 70% set up.

Evaluation is carried out 12 days after the inoculation.

A good effectiveness show in this test z. B. the connections according to the Production examples 1, 7, 8, 10, 11, 12, 14, 16, 18, 19, for an active ingredient concentration of 100 ppm have a 100% efficiency.  

Example D

Erysiphe test (apple) / curative
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 one Concentration.

To test for curative effectiveness, young plants with spores from Erysiphe graminis f.sp. hordei pollinated. 48 hours after inoculation sprayed the plants with the active ingredient preparation dewy.

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

Evaluation is carried out 7 days after the inoculation.

In this test, for example, the connections according to the Production examples 4, 22, 87 and 88 at an application rate of 400 g / ha an efficiency of 100%.  

Example E

Venturia test (apple) / curative
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 one Concentration.

To test for curative effectiveness, young plants are mixed with an aqueous Conidia suspension of the Venturia inaequalis apple scab pathogen inoculated. The Plants stay in one for 1 day at 20 ° C and 100% relative humidity Incubation cabin and are then set up in the greenhouse. After a The number of hours given will be the plants with the active ingredient preparation sprayed soaking wet.

The plants are then grown in a greenhouse at 20 ° C and a relative Humidity of approx. 70% set up.

Evaluation is carried out 12 days after the inoculation.

In this test, for example, the connections according to the Preparation Examples 4, 22, 87 and 88 at an active ingredient concentration of 10 ppm an efficiency of 100%.

Claims (21)

1. 2-oximino-2-thienyl-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, cy ano, nitro, alkyl, alkoxy, alkylthio, alkenyl, alkenyloxy, alkynyl, alkynyloxy, haloalkyl, haloalkoxy, haloalkyl thio, haloalkenyl, haloalkenyloxy, haloalkynyl, halo genalkynyloxy, 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 CH₂-O-, -O-CH₂-, -CH₂-S (O) _n -, S (O) _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 hydrogen, alkyl, haloalkyl, cycloalkyl or cyano,
R⁵ represents alkyl or haloalkyl and
R⁶ and R⁷ are each independently hydrogen, alkyl, Ha logenalkyl or alkoxy, 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 are suitable as substituents in each case:
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, 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, dialkyl amino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroximinoalkyl or alkoximinoalkyl, each with 1 to 6 carbon atoms in the individual alkyl parts, in each case, if appropriate, simply or multiply h, identical or different to the 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 / or ge straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms substituted, each with two bonds alkylene or dioxy alkylene, 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 hetero atoms - 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 haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and / or g 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, benzyloxy, phenylethyl or phenylethoxy,
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 having a rad-chain or branched haloalkyl, haloalkoxy, haloalkylthio each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, each being a 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, each straight-chain or branched alkoxycarbonyl, hydroximinoalkyl or alcohol ximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts and also for each optionally in the phenyl part with one 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 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 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-S (O) _n -, -S (O) _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 hydrogen, 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 and
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 halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, or straight-chain or branched alkoxy having 1 are up 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 different heteroatoms - in particular nitrogen , Oxygen and / or sulfur - is available, the following being 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 ge chain or branched haloalkyl, haloalkoxy, halo genalkylthio, 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, dialkyl amino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroximinoalkyl or alkoximinoalkyl, each with 1 to 4 carbon atoms in the individual alkyl parts, in each case, if necessary, once or more, identically 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, in each case doubly linked alkylene or dioxyalkylene, each with 1 up 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 single 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 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 he straight-chain 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 and
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 are each independently hydrogen, halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkyl thio, 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, in addition, in each case optionally in the phenyl part simply to five times, identically or differently by halo and / or straight-chain or branched alkyl having 1 to 3 carbon atoms Fatty 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 up 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-S (O) _n -, -S (O) _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 hydrogen, 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 stands for straight-chain or branched alkyl with 1 to 6 carbon atoms or for straight-chain or branched haloalkyl with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and
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 are up to 6 carbon atoms, and
n stands for 0, 1 or 2. 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, pyrimidi nyl, 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, methylsulfinyl, methylsulfonyl, allyl, butenyl, allyloxy, butenyloxy, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylmethylamino-methylamino-methylamino-methylamino-methylamino-methylamino Acetyl, acetoxy, methylsulfonyloxy, ethylsulfonyloxy, methoxycarbonyl, ethoxycarbonyl, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, ethoximinomethyl, ethoximinoethyl, propane-1,3-diyl, butane-1,4-diyl, dioxymethylene, dioxyethylene, dioxydioxylene, dioxioxylene , 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 and
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 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, ethoxy carbonyliminoethyl, hydroximino , Methoximinome thyl, methoximinoethyl, ethoximinomethyl, ethoximinoethyl or for each optionally one to three times, identical or different by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy substituted phenyl, phenoxy, benzyl or benzyloxy stand,
A for oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH₂-O-; -O-CH₂-, -CH₂-S (O) _n -, -S (O) _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 hydrogen, methyl, ethyl, trifluoromethyl or cyano,
R⁵ for straight-chain or branched alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or for haloalkyl having 1 to 2 carbon atoms and 1 to 5 same surfaces or different halogen atoms and
R⁶ and R⁷ are each independently of one another hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, for haloalkyl having 1 up to 4 carbon atoms and 1 to 5 identical or different halogen atoms or stand for straight-chain or branched alkoxy with 1 to 4 carbon atoms, and
n stands for 0, 1 or 2. 5. Compounds of formula (I) according to claim 1, in which the group Ar-A and the oximinoacetic acid residue in the thiophene ring are adjacent.   6. Compounds of formula (I) according to claim 5, in which the group Ar-A in 3- or 2-position and the oximinoacetic acid residue in 2- or 3 position in the thiophene ring. 7. pesticide, characterized by a content of at least one compound of formula (I) according to claim 1. 8. A method for controlling pests, characterized in that compounds of formula (I) according to claim 1 on pests and / or let their living space take effect. 9. 2-oximino-2- (halomethyl-2-thienyl) acetic acid derivatives of the formula (IV) in which
R¹, R², R³ and Z have the meaning given in claim 1 and X represents halogen. 10. 2-oximino-2- (halomethyl-2-thienyl) acetic acid derivatives of the formula (IIa) in which
R², R³, Ar, A and Z have the meaning given above,
except the connection
2-Oxo-2- (3-phenoxy-methyl-2-thienyl) acetic acid methyl ester. 11. Ketals of formula (IIb) in which
R², R³, Ar, A and Z have the meaning given in claim 1 and R⁸ represents alkyl. 12. Thiophene carboxylic acid ester of the formula (VIII) in which
R², R³, R⁹ and Ar have the meaning given in claim 1 and
A¹ is oxygen, sulfur or a radical of the formula -C (R⁴) = NO-, where
R⁴ represents alkyl, haloalkyl, cycloalkyl or cyano. 13. Thiophene carboxylic acids of the formula (IX) in which
R², R³, Ar and A¹ have the meaning given in claim 12. 14. Compounds of formula (X) in which
R², R³, Ar and A¹ have the meaning given in claim 12. 15. Compounds of the formula (XI) in which
R², R³, Ar and A¹ have the meaning given in claim 12. 16. ketals of formula (XV) in which
R², R³, R⁵ and R⁸ have the meaning given in claim 12. 17. halomethyl ketals of the formula (XVI), in which
R², R³, R⁵ and R⁸ have the meaning given in claim 12 and
Hal represents halogen, especially chlorine or bromine. 18. ketals of formula (XVII), in which
R², R³, R⁵, R⁸, Ar and A¹ have the meaning given in claim 12. 19. 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-oxothienyl 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-oxothienyl-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 their hydrogen halide adducts, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary or if
• b) 2-oximino-2- (halomethyl-2-thienyl) 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
  A and Ar have the meaning given above and
  if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary or if one
• c) 2-oximino-2-thienyl-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.

20. Use of compounds of formula (I) according to claims 1 to 6 for pest control. 21. Process for the preparation of pesticides, thereby characterized in that compounds of the formula (I) according to the Claims 1 to 6 with extenders and / or surface-active agents mixed.