WO1995001973A1

WO1995001973A1 - 2-oximino-2-thienyl-acetic acid derivatives

Info

Publication number: WO1995001973A1
Application number: PCT/EP1994/002043
Authority: WO
Inventors: Herbert Gayer; Peter Gerdes; Dietmar Kuhnt; Stefan Dutzmann; Heinz-Wilhelm Dehne; Gerd Hänssler
Original assignee: Bayer Aktiengesellschaft
Priority date: 1993-07-05
Filing date: 1994-06-22
Publication date: 1995-01-19
Also published as: EP0707578A1; AU7072794A; DE4405428A1; ZW7994A1; JPH08512295A; TR27776A; IL110170A0

Abstract

New 2-oximino-2-thienyl-acetic acid derivatives of formula (I), in which Ar, A, R?1, R2, R3¿ and Z have the meanings given in the description. Also disclosed are several processes for producing the same, new intermediate products used therefor and their use as pesticides.

Description

2-oximino-2-thienyl acetic acid derivatives

The invention relates to new 2-oximino-2-thienyl-acetic acid derivatives, several processes for their preparation and their use as pesticides. It is known that certain 2-methoxy-acrylic acid esters, such as the compound 3-methoxy-2- (6-phenyl-2-pyridylthio) acrylic acid methyl ester or the compound 3-methoxy-2- [N- (6-phenyl- 2-pyridyl) -N-methylamino] acrylic acid methyl ester or the compound 3-methoxy-2- [5- (4-chlorophenyl) -3-pyridyloxy] acrylic acid methyl ester have fungicidal properties (cf., for example, EP 383 117) . However, the effectiveness of these previously known compounds is not entirely satisfactory in all fields of application, in particular at low application rates and concentrations.

There were new 2-oximino-2-thienyl-acetic acid derivatives of the general formula (I),

in which

Ar represents optionally substituted aryl or heteroaryl,

R ^{1 represents} alkyl or haloalkyl, R ² and R ³ are each independently of one another hydrogen, halogen, cyano, nitro, alkyl, alkoxy, alkylthio, alkenyl, alkenyloxy, alkynyl, alkynyloxy, haloalkyl, haloalkoxy, haloalkylthio, haloalkenyl, haloalkenyloxy, haloalkynyl, haloalkynyloxy, alkoxycarbonyl, hydroximinoalkyl, alkoximinoalkyl or represent in each case 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 -CH ₂ -O-; -O-CH ₂ -, -CH ₂ -S (O) _n -, -S (O) _n -CH ₂ -, SO _n -, - C (R ⁴ ) = NO-, -C (R ⁴ ) = NO-CH ₂ - or -N (R ⁶ ) -, and represents a radical of the formula -OR ⁵ or -NR ⁶ R ⁷ , wherein

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

R ^{5 represents} alkyl or haloalkyl and

R ⁶ and R ⁷ each independently represent hydrogen, alkyl, haloalkyl or alkoxy, and n represents 0, 1 or 2.

Depending on the nature of the substituents, the compounds of the formula (I) can optionally be present as geometric and / or optical isomers or isomer mixtures of different compositions. Both the pure isomers and the isomer mixtures are claimed according to the invention. It was also found that the new 2-oximino-2-thienyl-acetic acid derivatives of the general formula (I)

in which Ar represents optionally substituted aryl or heteroaryl,

R ^{1 represents} alkyl or haloalkyl,

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

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

A represents oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH ₂ -O-; -O-CH ₂ -, -CH ₂ -S (O) _n -, -S (O) _n -CH ₂ -, SO _n -, -

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

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

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

R ^{5 represents} alkyl or haloalkyl and R ⁶ and R ⁷ each independently represent hydrogen, alkyl, haloalkyl or alkoxy, and n represents 0, 1 or 2, is obtained if a) a-oxothienyl acetic acid derivatives of the formula (Ila),

in which

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

or their ketals of the formula (Ilb),

in which

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

R ^{8 represents} alkyl, or mixtures of a-oxothienyl-acetic acid derivatives of the formula (Ila) and their ketals of the formula (Ilb) with hydroxylamines of the formula (III),

H ₂ NOR ¹ (III)

in which

R ^{1 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

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

X represents halogen, with nucleophiles of the formula (V), Ar-A ¹ -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 c) 2-oximino-2-thienyl-acetic acid derivatives of the formula (Ia),

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

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

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

The compounds according to the invention can optionally be present as mixtures of various possible isomeric forms, in particular of E and Z isomers. Both the E and the Z isomers as well as any mixtures of these isomers are 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 derivatives of the general formula (I) according to the invention have a considerably better activity against microorganisms which damage the plants compared to the 2-methoxy-acrylic esters known from the prior art, such as the compound 3-methoxy Methyl 2- (6-phenyl-2-pyridylthio) acrylic acid or the compound 3-methoxy-2- [N- (6-phenyl-2-pyridyl) -N-methylamino] -acrylic acid methyl ester or the compound 3 - Methoxy-2- [5- (4-chlorophenyl) -3-pyridyloxy] -acrylic acid methyl ester, which are chemically and / or functionally obvious compounds.

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 represents optionally mono- or polysubstituted, identical or differently substituted aryl with 6 to 10 carbon atoms or for optionally mono- or polysubstituted, 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 are possible:

Halogen, cyano, nitro, hydroxy, amino, formyl, carbamoyl, thiocarbamoyl, each straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms, each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms , each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 13 identical or different Halogen atoms, each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroximinoalkyl or alkoximinoalkyl, each with 1 to 6 carbon atoms in the individual alkyls, in each case optionally singly or multiply, heal ch or differently substituted by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms , each double-linked alkylene or dioxyalkylene, each with 1 to 6 carbon atoms, cycloalkyl with 3 to 7 carbon atoms, 3- to 7-membered heterocyclyl with 2 to 6 carbon atoms and 1 to 3 identical or different heteroatoms - 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 with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and / or straight-chain or branched alkoxy with 1 to 4 carbon atoms and / or straight-chain or branched haloalkoxy with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms substituted phenyl, Phenoxy, benzyl,

Benzyloxy, phenylethyl or phenylethoxy,

R ^{1 represents} straight-chain or branched alkyl having 1 to 8 carbon atoms or straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, R ² and R ³ each independently of one another 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 tes 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 alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts and, moreover, in each case optionally in the phenyl part, single or multiple, identical or different by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and / or straight-chain or branched alkoxy having 1 to 4 carbon atoms and / or straight chain or branched tes 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 -CH ₂ -O-; -O-CH ₂ -, -CH ₂ -S (O) _n -, -SCO) _n -CH ₂ -, SO _n -,

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

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

R ⁴ for hydrogen, for 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, for

Cycloalkyl having 3 to 8 carbon atoms or cyano,

R ^{5 represents} straight-chain or branched alkyl having 1 to 8 carbon atoms or straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms and R ⁶ and R ⁷ each independently of one another represent hydrogen, for straight-chain or branched alkyl 1 to 8 carbon atoms, represents straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, or represents straight-chain or branched alkoxy having 1 to 8 carbon atoms, and n represents 0, 1 or 2, especially those 2-Oximino-2-thienyl-acetic acid derivatives of the formula (I) are preferred in which the group Ar-A and the oximinoacetic acid residue in the thiophene ring are adjacent.

Particularly preferred are compounds of the formula (I) in which Ar is aryl for 6 to 10 carbon atoms, which may be monosubstituted to pentasily, identically or differently substituted, or for heteroaryl which is monosubstituted to tetrasubstituted, identically or differently, and / or benzo fused with 2 to 10 atoms 9 carbon atoms and 1 to 3 identical or different which are heteroatoms - in particular nitrogen, oxygen and / or sulfur, the following being suitable as substituents:

Halogen, cyano, nitro, hydroxy, amino, formyl, carbamoyl, thiocarbamoyl, each straight-chain or branched alkyl, alkoxy, alkylthio, AUcylsulfinyl or alkylsulfonyl each having 1 to 4 carbon atoms, each straight-chain or branched alkenyl or alkenyloxy each having 2 to 4 carbon atoms , each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight-chain or branched

Haloalkenyl or haloalkenyloxy each having 2 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroximinoalkyl or alkoximinoalkyl each having 1 to 4 carbon atoms in the individual alkyl parts, in each case where appropriate mono- or polysubstituted, 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, in each case double-linked alkylene or dioxyalkylene each 1 to 4 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, 5 to 7-membered, saturated heterocyclyl with 4 to 6 carbon atoms and 1 or 2 identical or different heteroatoms - in particular nitrogen, oxygen and / or Sch sulfur - as well as, if necessary, in the phenyl part through to three, the same or different

Halogen and / or straight-chain or branched alkyl having 1 to 3 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms and / or straight-chain or branched alkoxy having 1 to 3 carbon atoms and / or straight-chain or branched haloalkoxy with 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms sub substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy and

R ^{1 represents} straight-chain or branched alkyl having 1 to 6 carbon atoms or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms,

R ² and R ³ independently of one another each represent hydrogen, halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkylthio, each having 1 to 4 carbon atoms, each straight-chain or branched alkenyl or alkenyloxy each having 2 to 4 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight-chain or branched Alkoxycarbonyl, hydroximinoalkyl or alkoximinoalkyl each having 1 to 4 carbon atoms in the individual alkyl parts and, moreover, in each case optionally in the phenyl part, in one to five times, identically or differently by halogen and / or straight-chain or branched alkyl having 1 to 3 carbon atoms and / or straight-chain or branched haloalkyl with 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms and / or straight-chain or branched alkoxy with 1 to 3 carbon atoms and / or straight-chain or branched haloalkoxy with 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms are substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy,

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

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

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

R ^{5 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

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

n represents 0, 1 or 2, with particular preference being given to 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. 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, methylsulphinyl, methylsulphonyl, allyl, butenyl, allyloxy, butenyloxy, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulphinyl, trifluoromethylamulino, dimethylamethylamino, Acetoxy, Methylsulfonyloxy, ethylsulfonyloxy, methoxycarbonyl, ethoxycarbonyl, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, ethoximinomethyl, ethoximinoethyl, propane-l, 3-diyl, butane-1,4-diyl, dioxymethylene, dioxyethylene, dioxypropylene, difluorodioxylethylene, difluoropropyl, Cyclohexyl, 1-pyrrolidinyl,

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

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

R ² and R ³ are each independently of one another hydrogen, fluorine, chlorine,

Bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio,

Ethylthio, allyl, butenyl, allyloxy, butenyloxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, difluorochloromethylthio, methoxycarbonyl, ethoxycarbonyl, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoxyimino or different in each case, by same, by same as methylimino or different from methyl, ethoximino or different by same,

Chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy substituted phenyl, phenoxy, benzyl or benzyloxy, A represents oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following Groupings -CH ₂ -O-; -O-CH ₂ -, -CH ₂ -S (O) _n -, -S (O) _n -CH ₂ -, SO _n -, -C (R ⁴ ) = NO-, -C (R ⁴ ) = NO-CH ₂ - or -N (R ⁶ ) -, and

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

R ^{4 represents} hydrogen, methyl, ethyl, trifluoromethyl or cyano,

R ⁵ 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 identical or different halogen atoms and R ⁶ and R ⁷ independently of one another each represent 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 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, with particular preference being given to 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.

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

Examples of preferred combinations of the above-defined groups A, Ar, R ¹ , R ² , R ³ and Z are listed below, the combinations each being valid for the formulas (Ib) and (Ic).

If, for example, 2- [3- (2-methylphenoxy-methyl) -2-thienyl] -2-oxo-acetic acid methyl ester and O-methylhydroxylamine hydrochloride are used as starting materials, the reaction sequence of process (a) according to the invention can be represented by the following formula :

If, for example, 2- (3-chloromethyl-2-thienyl) -2-methoximino-acetic acid methyl ester and thiophenol are used as starting materials, the course of the reaction of process (b) according to the invention can be represented by the following formula:

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

The a-oxothienyl acetic acid derivatives required as starting compounds for carrying out the process according to the invention are generally defined by the formula (Ila). In this formula (Ila), R ² , R ³ , Ar, A and Z preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula (I) according to the invention. α-Oxothienyl acetic acid derivatives of the formula (Ila) are known in some cases or can be obtained in analogy to known processes (cf., for example, EP 243 014), for example by using halomethylthiophenecarboxylic acid esters of the formula (VII),

in which

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

X represents halogen and

R ^{9 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-A ¹ -H (V) in which

Ar has the meaning given above and

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

R ^{4 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 ),

in which R ² , R ³ , R ⁹ , Ar and A ^{1 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 obtainable in this way Formula (IX),

in which

R ² , R ³ , Ar and A ^{1 have} the meaning given above, in a subsequent 3rd stage with conventional acid halide formers such as, for example, 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

R ² , R ³ , Ar and A ^{1 have} the meaning given above and shark represents halogen, in particular chlorine or bromine, in a subsequent 4th stage with sodium cyanide, optionally in the presence of a diluent such as dichloroethane / water and optionally in the presence a reaction auxiliary such as tetrabutylammo reacting nium bromide at temperatures between 0 ° C and 50 ° C and then the 2-oxo-2-thienylacetonitriles of the formula (XI) thus obtainable,

in which R ² , R ³ , Ar and A ^{1 have} the meaning given above, in a subsequent 5th stage with acid such as, for example, hydrochloric acid and alcohols of the formula (XII),

R ⁵ -OH (XII) in which R ^{5 has} the meaning given above, optionally in the presence of a diluent such as t-butyl methyl ether and optionally in the presence of a reaction auxiliary such as acetic anhydride at temperatures between 20 ° C and 150 ° C and optionally subsequently the a-oxothienyl acetic acid derivatives of the formula (IIa-1) obtainable in this way,

in which

R ² , R ³ , R ⁵ , Ar and A ^{1 have} the meaning given above, or their ketals of the formula (IIb-1),

in which

R ² , R ³ , R ⁵ , Ar and A ^{1 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 6. Step analogous to carrying out process (c) according to the invention with amines of the formula (VI),

in which R ⁶ and R ^{7 have} the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary. a-oxothienyl acetic acid ester of the formula (IIa-1),

in which R ² , R ³ , R ⁵ , Ar and A ^{1 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

R ² , R ³ and R ^{5 have} the meaning given above, first in a 1st stage with formic acid orthoesters of the formula (XIV),

HC (OR ⁸ ) ₃ (XIV) in which R ^{8 represents} alkyl, in particular methyl or ethyl, optionally in the presence of a diluent such as methanol or ethanol and optionally 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 R ² , R ³ , R ⁵ and R ^{8 have} the meaning given above, in a subsequent second stage with a halogenating agent, such as N-bromosuccinimide, optionally 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 thus obtainable halomethyl ketals of the formula (XVI),

in which

R ² , R ³ , R ⁵ and R ^{8 have} the meaning given above and

Hal represents halogen, in particular chlorine or bromine, in a subsequent third step in analogy to carrying out process (b) according to the invention with nucleophiles of the formula (V),

Ar-A ¹ -H (V) in which

Ar has the meaning given above and

R ^{4 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

R ² , R ³ , R ⁵ , R ⁸ , Ar and A ^{1 have} the meaning given above in a subsequent 4th stage with aqueous acid, such as, for example, hydrochloric acid, if appropriate in the presence of a diluent such as, for example, dichloromethane at temperatures between 20 ° C. and 120 ° C implemented.

Halomethyl-thiophenecarboxylic acid esters of the formula (VII) are known or can be obtained in analogy to known processes (see, 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 can be obtained in analogy to known processes (cf., for example, Org. Prep. Proced. 2, 249-251 [1970]; BE 896054; US 3,622,569 and the preparation examples), for example by reacting the generally known methylthiophenecarboxylic acids with thionyl chloride to give the corresponding acid chlorides; these are in turn reacted with sodium cyanide in a subsequent reaction to give the corresponding a-oxonitriles which are saponified in a conventional manner in a third stage with acids in the presence of an alcohol and are esterified at the same time.

Alcohols of the formula (XII) and formic acid orthoesters of the formula (XIV) are generally known compounds of organic chemistry. The following intermediates are not yet known and are also an object of the invention: thiophenecarboxylic acid esters of the formula (VIII), thiophenecarboxylic acids of the formula (IX), thiophenecarboxylic acid halides of the formula (X), 2-oxo-2-thienylacetonitriles 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 the formula (Ila) and their ketals of the formula (Ilb) with the exception of the compound 2-oxo-2- (3 -phenoxymethyl-2-thieι.yl) ethyl acetate.

Formula (III) provides a general definition of the hydroxylamines further required as starting materials for carrying out process (a) according to the invention. In this formula (III), R ¹ preferably represents those radicals which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula (I) according to the invention.

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

Formula (IV) provides a general definition of the 2-oximino-2- (3-halogenomethyl-2-thienyl) acetic acid derivatives required as starting materials for carrying out process (b) according to the invention. In this formula (IV), R ¹ , R ² , R ³ and Z preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula (I) according to the invention. X preferably represents halogen, especially 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 an object of the invention. They are obtained if the 2-oximino-2-thienyl-acetic acid derivatives of the formula (Ib) obtainable with the aid of processes (a) or (c) according to the invention,

in which

R ¹ , R ² , R ³ , Ar and Z have the meaning given above, with hydrogen halides, such as, for example, hydrogen chloride or hydrogen bromide, if appropriate in the presence of a diluent such as, for example, methanol at temperatures between 0 ° C. and 80 ° C.

The compounds of the formula (IV) can also be reacted by reacting compounds of the formula (XIII) - above - with hydroxylamines of the formula (III) - above - (analogously to process (a)) and then with halogenating agents, e.g. N-chloro- or N-bromosuccinimide can be obtained by customary methods (cf. the preparation examples).

Formula (V) provides a general definition of the nucleophiles which are further required as starting materials for carrying out process (b) according to the invention and for synthesizing the precursors of the formula (II). In this formula (V) Ar preferably represents those radicals which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula (I) according to the invention. A ¹ preferably represents oxygen, sulfur or a radical of the formula -C (R ⁴ ) = NO-, where R ⁴ preferably represents those radicals which are already preferred in connection with the description of the compounds of the formula (I) according to the invention for this substituent. The nucleophiles of the formula (V) are generally known compounds of organic chemistry.

Formula (Ia) provides a general definition of the 2-oximino-2-thienyl-acetic acid derivatives required as starting materials for carrying out process (c) according to the invention. In this formula (Ia), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and A preferably represent those radicals which have already been associated with the Be the compounds of formula (I) according to the invention were mentioned as preferred for these substituents.

The 2-oximino-2-thienyl-acetic acid derivatives of the formula (Ia) are compounds according to the invention and can be obtained with the aid of processes (a) and (b) according to the invention. Formula (VI) provides a general definition of the amines which are further required as starting materials for carrying out process (c) according to the invention. In this formula (VI), R ¹⁰ and R ¹¹ preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula (I) according to the invention. The amines of the formula (VI) are generally known compounds of organic chemistry.

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

Process (a) according to the invention is preferably carried out in the presence of a suitable reaction auxiliary. All conventional inorganic or organic bases are suitable as such. These include, for example, alkaline earth or Alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or bicarbonates, such as sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate , Sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononediazene (dababicyclononediazene) (DBU). The reaction temperatures can be varied within a substantial range when carrying out process (a) according to the invention. In general, temperatures between 0 ° C and + 150 ° C, preferably at temperatures between 20 ° C and + 120 ° C.

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

To carry out process (a) according to the invention, generally 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol, of hydroxylamine of the formula (1) are employed per mol of a-oxothienyl acetic acid derivative of the formula (II) III) or a corresponding hydrohalide and optionally 1.0 to 6.0 mol, preferably 1.0 to 3.0 mol, of reaction auxiliaries. The reaction is carried out, worked up and isolated by known processes.

Inert organic solvents are suitable as diluents for carrying out process (b) according to the invention. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water. If appropriate, the process according to the invention (b) can also be carried out in a two-phase system, such as, for example, water / toluene or water / dichloromethane, if appropriate in the presence of a suitable phase transfer catalyst. Examples of such catalysts are: tetrabutylammonium iodide, tetrabutylammomum bromide, tetrabutylammonium chloride, tributyl-methylphosphonium bromide, trimethyl-C ₁₃ / C ₁₅ -alkylammonium chloride, trimethyl-C ₁₃ / C ₁₅ -alkylammonium bromide, dibenzyl-dimethyl- ₁₂ -ammonium / ammonium-bromide _14- alkyl-benzylammonium chloride, dimethyl-C ₁₂ / C ₁₄ -alkyl-benzylammonium bromide, tetrabutylammonium hydroxide, triethylbenzylammonium chloride, jlethyltrioctylammonium chloride, trimethylbenzylammonium chloride, 15-crown-5, 18-crown-6 or troxy [2- (2) methyl ] -amin.

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

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

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

To carry out process (b) according to the invention, generally 1.0 to 3.0 mol, preferably 1.0, are employed per mole of 2-oximino-2- (3-halogenomethyl-2-thienyl) acetic acid derivative of the formula (IV) to 2.0 moles of nucleophile of the formula (V) and optionally 1.0 to 3.0 moles, preferably 1.0 to 2.0 moles, of reaction auxiliaries. The reaction is carried out, worked up and isolated by known processes.

Inert organic solvents are suitable as diluents for carrying out process (c) according to the invention. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide or sulfoxides such as dimethyl sulfoxide. Process (c) according to the invention is preferably carried out in the presence of a suitable reaction auxiliary. All conventional inorganic or organic bases are suitable as such. These include, for example, alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethyl, potassium tert-butyl lat, sodium hydroxide, potassium hydroxide, ammonium hydroxide , Sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicycl ), Diazabicyclonones (DBN) or diazabicycloundecene (DBU).

It is also possible to use the amine of the formula (III) used as the reactant in a corresponding excess at the same time as a reaction auxiliary. The reaction temperatures can be varied within a substantial range when carrying out process (c) according to the invention. In general, temperatures between -30 ° C and + 150 ° C, preferably at temperatures between -20 ° C and + 120 ° C.

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

To carry out process (c) according to the invention, generally 1.0 to 3.0 mol, preferably 1.0 to 1.5 mol, of amine are used per mole of 2-oximino-2-thienyl-acetic acid derivative of the formula (Ia) Formula (VI) and optionally 0.1 to 3.0 mol, preferably 0.5 to 1.5 mol, of base used as reaction auxiliary. In a special embodiment, it is also possible to use the 2-oximino-2-thienyl-acetic acid derivatives of the formula (Ia) used as starting products to produce in an upstream reaction in the reaction vessel and then to implement it further without isolation directly in a so-called "one-pot reaction" according to process (c) according to the invention. The reaction is carried out, worked up and isolated in each case analogously to known processes (see, for example, EP 398 692 and the preparation examples).

The end products of the formula (I) are purified using customary methods, for example by column chromatography or by recrystallization.

The characterization is carried out using the melting point or, in the case of non-crystallizing compounds, using the refractive index or proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR).

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

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

The active compounds according to the invention can be used with particularly good success to combat diseases in fruit and vegetable cultivation, such as, for example, against the pathogen of apple scab (Venturia inaequalis) or to combat cereal diseases, for example against the pathogen of powdery mildew (Erysiphe graminis) or against Pathogen of the barley mesh spot disease (Pyrenophora teres) or against the pathogen of the brown fur of the wheat (Leptosphaeria nodorum) or against the pathogen of the barley spot disease of the barley or of the wheat (Cochliobolus sativus) or against Fusarium species or for combating rice diseases such as against the pathogen Rice spot disease (Pyricularia oryzae) can be used. In addition, the active compounds according to the invention have good in vitro activity. Depending on their respective physical and / or chemical properties, the active ingredients can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV Cold and warm mist formulations. These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes, or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide or dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; Solid carrier materials are suitable: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates; Solid carriers for granules are possible: for example broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; The following may be used as dispersants: for example lignin sulfite waste liquor and methyl cellulose. Adhesives such as carboxymethyl cellulose, natural and synthetic, powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils. Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used. The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

As such, the active compounds according to the invention can also be used in their formulations in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the spectrum of activity or to prevent the development of resistance. In many cases, synergistic effects occur.

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'-trifluoro-methyl-1,3-thizole-5- carboxanilide 2,6-dichloro-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, ampropylfos, anilazine, azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,

Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,

Dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,

Edifenphos, epoxyconazole, ethirimol, etridiazole,

Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetate, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Futrianolide, Futrianol, Futin Furmecyclox, Guazatine,

Hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan,

Kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,

Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol,

Methasulf ocarb, methfuroxam, metiram, metsulfovax, myclobutanil,

Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,

Ofurace, oxadixyl, oxamocarb, oxycarboxin,

Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin,

Probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilone,

Quintozen (PCNB),

Sulfur and sulfur preparations,

Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol,

Triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforin, triticonazole,

Validamycin A, vinclozolin,

Zineb, Ziram bactericides:

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

Insecticides / acaricides / nematicides:

Abamectin, Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin, Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyluthrin, Bifenthrin,

BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin,

Butyl pyridaben,

Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chloretoxyfos, Chlorfenvinphos,

Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin,

Cypermethrin, cyromazine,

Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron,

Dimethoate,

Dimethylvinphos, dioxathione, disulfoton,

Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etofenprox, Etrimphos,

Fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,

Fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil,

Fluazinam, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate,

Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,

HCH, heptenophos, hexaflumuron, hexythiazox,

Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin,

Lamda-cyhalothrin, Lufenuron,

Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos,

Methamidophos, methidathione, methiocarb, methomyl, metolcarb, milbemectin,

Monocrotophos, moxidectin,

Naled, NC 184, NI 25, Nitenpyram

Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,

Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M,, Primiphos A, Profenofos, Profenophos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothiophos, Prothosincl, Pothophos, Pyrothicos , Pyraclophos, Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos,

RH 5992,

Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,

Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomenethriazonium, Triomenethriazonium, Tri

Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin.

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

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.

In the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range: they are 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 of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required. When treating the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action. Manufacturing examples:

Example 1:

(Method a) 5.23 g (0.018 mol) of 2-oxo-2- [3- (2-methylphenoxymethyl) -2-thienyl] acetic acid methyl ester and 1.5 g (0.018 mol) of O-methylhydroxylamine hydrochloride in 27 ml Methanol is heated to the reflux temperature for 4 hours, then concentrated in vacuo and the residue is partitioned between chloroform and water. The chloroform phase is separated off, concentrated and the residue is purified by chromatography on silica gel (mobile solvent: dichloromethane).

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

¹ H NMR (CDCl ₃ / 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 2.9 g at room temperature with stirring

(0.028 mol) acetic anhydride and then introduces dry hydrogen chloride gas at a temperature between - 10 ° C and 0 ° C until saturation. The mixture is then stirred for 24 hours at room temperature, then 40 ml of methanol are added and the mixture is heated at the reflux temperature for 10 hours. For working up, the reaction mixture is cooled, precipitated solid is filtered off, taken up in 150 ml of dichloromethane, filtered, the filtrate is washed with water and concentrated in vacuo.

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

Example XI-1:

To 8.5 g (0.032 mol) of 3- (2-methylphenoxymethyl) thiophene-2-carboxylic acid chloride in 28.8 ml of dichloroethane are added 100 mg of tetrabutylammonium bromide at room temperature and then a solution of 1.7 g is added dropwise with stirring

(0.035 mol) sodium cyanide in 20 ml water, the temperature of the reaction mixture being kept below 25 ° C. by external cooling. When the addition is complete, the mixture is stirred at room temperature for a further 60 minutes, the phases are then separated, the aqueous phase is extracted with dichloroethane and the combined organic phases are then washed 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] -2-oxo-acetonitrile are obtained as an oil.

¹ H NMR (CDCl ₃ / tetramethylsilane): 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:

10.1 g (0.085 mol) of thionyl chloride are added to 8.4 g (0.034 mol) of 3- (2-methylphenoxymethyl) thiophene-2-carboxylic acid in 40 ml of dichloromethane and the mixture is then heated at the reflux temperature for 2 hours. For working up, the volatile constituents are removed in vacuo.

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

¹ H NMR (CDCl ₃ / 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:

9.4 g (0.106 mol) of 45% aqueous sodium hydroxide solution are added to 13.8 g (0.0526 mol) of methyl 3- (2-methylphenoxymethyl) thiophene-2-carboxylic acid in 50 ml of methanol at room temperature and the mixture is then stirred one hour at 60 ° C. For working up, the mixture is concentrated in vacuo, the residue is acidified with 2N hydrochloric acid, the precipitate which has separated out is filtered off and dried.

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

¹ H NMR (DMSO-d ₆ / 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:

1.94 g (0.065 mol) of 80 percent sodium hydride are added in portions to 7.0 g (0.065 mol) of 2-methylphenol in 65 ml of dimethylformamide with stirring and cooling, and the mixture is stirred until the evolution of gas has ended. Then 15.2 g (0.065

Mol) of 3-bromomethylthiophene-2-carboxylic acid methyl ester (cf. e.g. J. Org. Chem 51, 235 [1986]) and then stirred for 30 minutes at room temperature. For working up, the mixture is concentrated in vacuo, the residue is partitioned between dichloromethane and water, the dichloromethane phase is separated off, dried and concentrated in vacuo.

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

¹ H NMR (CDCl ₃ / 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-acetic acid methyl ester are dissolved at 0 ° C. in 80 ml of methanol, which was previously saturated with dry hydrogen chloride, and then 12

Stirred for hours at room temperature. For working up, the mixture is concentrated in vacuo, the residue is taken up in dichloromethane, washed with water, dried and concentrated in vacuo. The residue is distilled in a high vacuum. 9.3 g (48% of theory) of 2- [3- (2-chloromethyl) -2-thienyl] -2-methoximino-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 (CDCl ₃ / 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 (CDCl ₃ / 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-acetic acid methyl ester are dissolved at 0 ° C. in 200 ml of methanol, which has previously been saturated with dry hydrogen chloride, and then 12

Stirred at 0 ° C for hours. For working up, the mixture is concentrated in vacuo, the residue is 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-methoximino-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 (CDCl ₃ / tetramethylsilane): 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 (CDCl ₃ / tetramethylsilane): d = 3.92 (3H); 4.03 (3H); 5.00 (2H) ppm.

Example IV-3: Stage 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 (CDCl ₃ / tetramethylsilane):

E isomer: δ = 2.137 (3H); 3,897 (3H); 4.115 (3H); 6.872 / 6.888 (1H);

7.410 / 7.426 (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, boil 30

Minutes at reflux. 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% E-Z mixture of the monobromo compound.

¹ H NMR (CDCl ₃ / 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 Ila-1:

(alternative production)

To 1.0 g (0.003 mol) of 2- [3- (2-methylphenoxymethyl) -2-thienyl] -2,2-dimethoxyacetic acid methyl ester in 3.6 ml of dichloromethane is added 0.7 ml of concentrated

Hydrochloric acid and then stirred for 10 hours at room temperature. For working up, the reaction mixture is concentrated in vacuo and the residue is recrystallized from a little methanol.

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

Example XVII-1:

0.3 g (0.01 mol) of 80 percent sodium hydride is added to a solution of 1.08 g (0.01 mol) of 2-methylphenol in 10 ml of dimethylformamide at 0 ° C. The mixture is then allowed to come to room temperature. then adds 3.09 g (0.01 mol) of methyl 2- (3-bromomethyl-2-thienyl) -2,2-dimethoxyacetate and then stirred for 12 hours at room temperature. For working up, the reaction mixture is poured onto water, extracted with chloroform, the organic phase is washed twice with 2N sodium hydroxide solution, concentrated in vacuo and the residue is chromatographed on silica gel (mobile solvent:

Ether / petroleum ether 1: 3).

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

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 are heated to boiling in 90 ml of carbon tetrachloride, then with 100 mg Azodiisobutyrodinitrile (AIBN) added and 2

Cooked under reflux for hours. For working up, the reaction mixture is cooled to 0 ° C., filtered, the filtrate is concentrated in vacuo and the residue is distilled in a high vacuum.

19.3 g (72% of theory) of 2- (3-bromomethyl-2-thienyl) -2,2-dimethoxyacetic acid methyl ester are obtained.

¹ H NMR (CDCl ₃ / 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) of trimethyl orthoformate and 8.7 g (0.27 mol ) Methanol are mixed, mixed with 2.7 g of concentrated sulfuric acid and at 2 days

Leave room temperature. For working up, 6 g of triethylamine are added, the mixture is concentrated in vacuo and the residue is distilled in a high vacuum.

48.6 g (78% of theory) of 2- (3-methyl-2-thienyl) -2,2-dimethoxyacetic acid methyl ester having a boiling point of 110 ° C. at 1 torr are obtained.

¹ H NMR (CDCl ₃ / 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) of aluminum trichloride in 250 ml of dichloromethane is added dropwise at 0 ° C with stirring 31 g (0.253 mol) of methyl oxalate chloride, the mixture is stirred for 15 minutes after the end of the addition and then also added dropwise at 0 ° C 24 , 8 g (0.253 mol) of 3-methylthiophene allows the mixture to come to room temperature and stirred for a further 30 minutes at this temperature. For working up, the mixture is poured onto a mixture of 25 ml of concentrated hydrochloric acid and 250 g of ice, the organic phase is separated off, dried over sodium sulfate, concentrated in vacuo and the residue is distilled in a high vacuum.

24.1 g (52% of theory) of 2- (3-methyl-2-thienyl) -2-oxo-acetic acid methyl ester with a boiling point of 95-100 ° C. at 0.05 torr are obtained.

¹ H NMR (CDCl ₃ / tetramethylsilane): δ = 2.606 (3H); 3.758 (3H); 7.01 (1H);

7.65 (1H) ppm.

Example 2:

(Method c)

2.3 ml (0.02 mol) are added to 0.8 g (0.0026 mol) of (E) -2- [3- (phenoxymethyl) -2-thienyl] -2-methoximino-acetic acid methyl ester in 15 ml of methanol. 30 percent aqueous methylamine solution, then stirred for 16 hours 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 (CDCl ₃ / 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-dimethoxyacetic acid methyl ester are mixed with 5.0 g (0.056 mol) of O-methylhydroxylamine

Hydrochloride in a mixture of 50 ml of methanol and 10 ml of water boiled under reflux for 4 hours. For working up, the methanol is distilled off in vacuo, the residue is partitioned between dichloromethane and water, the dichloromethane solution is concentrated in vacuo and the residue is crystallized by adding 4 ml of methanol.

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 (CDCl ₃ / tetramethylsilane): 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 (CDCl ₃ / 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:

4.5 g (0.04 mol) of potassium tert-butoxide and then 12.4 g are added to a solution of 4.33 g (0.04 mol) of 2-methylphenol in 40 ml of tetrahydrofuran at 0 ° C

(0.04 mol) of 2- (2-bromomethyl-3-thienyl) -2,2-dimethoxy-acetic acid methyl ester and then stirred for 2 days at room temperature. For working up, the reaction mixture is mixed with water, extracted with diethyl ether, the organic phase is washed three times with 50 ml of 2N sodium hydroxide solution and then with water and concentrated in vacuo.

11.24 g (84% of theory) of 2- [2- (2-methylρhenoxymethyl) -3-thienyl] -2,2-dimethoxyacetic acid methyl ester are obtained as an oil.

¹ H NMR (CDCl ₃ / 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-dimethoxy-acetic acid methyl ester and 30.9 g (0.174 mol) of N-bromosuccinimide are heated to boiling in 170 ml of carbon tetrachloride, then with 100 mg Azodiisobutyrodinitrile (AIBN) added and 2

40.6 g (76% of theory) of methyl 2- (2-bromomethyl-3-thienyl) -2,2-dimethoxyacetate are obtained.

¹ H NMR (CDCl ₃ / 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) of trimethyl orthoformate and 6.4 g (0.2 mol) Methanol is mixed, mixed with 2.1 g of concentrated sulfuric acid and 3 days

Leave room temperature. For working up, the mixture is neutralized with triethylamine, concentrated in vacuo and the residue is distilled in a high vacuum.

41.4 g (90% of theory) of 2- (2-methyl-3-thienyl) -2,2-dimethoxy-acetic acid methyl ester with a boiling point of 95 ° C. at 1 torr are obtained.

¹ H NMR (CDCl ₃ / 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, 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. The mixture is then stirred for 24 hours at room temperature, then 320 ml of methanol are added and the mixture is heated at the reflux temperature for 16 hours. For working up, the reaction mixture is concentrated, the residue is partitioned between dichloromethane and water, the dichloromethane phase is concentrated in vacuo and the residue is distilled in a high vacuum.

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 (CDCl ₃ / 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 dichloroethane are added 700 mg of tetrabutylammonium bromide at room temperature and then dropwise with stirring a solution of 19.1 g (0.389 mol) of sodium cyanide in 210 ml of water, whereby the temperature of the reaction mixture

External cooling is kept below 25 ° C. When the addition is complete, the mixture is stirred for a further 60 minutes at room temperature, the phases are then separated, the aqueous phase is extracted with dichloroethane and the combined organic phases are then washed three times with 50 ml of water each time. The organic phase is dried and concentrated in vacuo, the residue is 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 (CDCl ₃ / 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 of dichloroethane, 123.2 g are added at room temperature ( 1.035 mol) of thionyl chloride and then heated at reflux temperature for 2 hours. For working up, the volatile constituents are removed in the

Vacuum and vacuum distill the residue in a water jet.

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 (CDCl ₃ / 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 a suspension of 0.3 g (0.01 mol) of 80 percent. Sodium hydride entered in dimethylformamide. Then 2.5 g (0.01 mol) of 2- (3-chloromethyl-2-thienyl) -2-methoximino-acetic acid methyl ester are added and the mixture is then stirred for 16 hours at room temperature. For working up, water is added, extracted with ethyl acetate and the organic phase is concentrated in vacuo. The residue is purified by chromatography on silica gel (mobile phase: petroleum ether / ether 1: 1).

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 (CDCl ₃ / 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 (CDCl ₃ / tetramethylsilane): δ = 2.243 (3H); 3.914 (3H); 4.022 (3H);

5.301 (2H); 7.1-7.9 (6H) ppm.

Example 5:

(Method c)

2 ml are added 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 40 percent aqueous methylamine solution, then stirred for 2 hours at room temperature, then removes the solvent in vacuo, takes up the residue in ethyl acetate, dries over sodium sulfate and removes the solvent in vacuo. 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 (CDCl ₃ / 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 mol) of 80 percent. Sodium hydride dropped in dimethylformamide. Then 2.5 g (0.01 mol) of 2- (3-chloromethyl-2-thienyl) -2-methoximino-acetic acid methyl ester are added and the mixture is then stirred for 16 hours at room temperature. For working up, water is added, extracted with ethyl acetate and the organic phase is concentrated in vacuo. 2.5 g (77% of theory) of 2- [3-phenylthiomethyl) -2-thienyl] -2-methoximino-acetic acid methyl ester are obtained as an E / Z isomer mixture in a ratio of 2: 1. Chromatography in Ether / petroleum ether (1: 1) the isomers can be separated.

¹ H NMR (CDCl ₃ / tetramethylsilane): δ = 3.863 (3H); 4.093 (3H); 3.950 (2H);

7.0-7.45 (7H) ppm (E isomer).

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

*) The ¹ H-NMR spectra were recorded in deuterochloroform (CDCl ₃ ) or hexadeuterodimethyl sulfoxide (DMSO-d ₆ ) with tetramethylsilane (TMS) as the internal standard. The chemical shift is given as a d-value in ppm.

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

0.007 mol (2.0 g) of [3- (4-methylphenoxy) thiophen-2-yl] glyoxylate and 0.0175 mol (1.5 g) of methoxy ammonium chloride are dissolved in 100 ml of ethanol and heated under reflux for 10 hours . The solvent is distilled off, the residue is taken up in ethyl acetate, washed with saturated NaHCO ₃ solution, dried over Na ₂ SO ₄ and concentrated. Yield: 1.5 g (67%) brown oil.

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

To a solution of 0.04 mol (13 g) of 2- [3- (4-methylphenoxy) -thiophen-2-yl] -2-methoximinoacetic acid ethyl ester in 200 ml of ethanol, methylamine is introduced with ice cooling until saturated. The mixture is stirred at 20 ° C. for a further 18 hours. The solution is concentrated and the residue is recrystallized from ethanol. Yield: 6.7 g (55%) mp: 113 ° C. Examples of use:

In the following application examples, the compounds listed below were used as reference substances:

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 N-methyl-pyrrolidone

Emulsifier: 0.6 part by weight of alkyl aryl polyglycol ether

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

To test for protective efficacy, young plants are sprayed with the preparation of active compound as dewy. After the spray coating has dried on, the plants are covered with spores from Erysiphe graminis f.sp. hordei pollinated.

The plants are placed in a greenhouse at a temperature of approx. 25 ° C and a relative humidity of approx. 80% in order to promote the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, for example, the compounds according to Preparation Examples 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 21 show a clear superiority in effectiveness compared to the prior art with an active ingredient concentration of 400 g / ha show an efficiency of 75% at 100%. The compounds (A) and (B) show no effect at the same application rate, the compound (C) shows an efficiency of 34%.

Example B

Erysiphe test (wheat) / protective

Solvent: 10 parts by weight of N-methylpyrrolidone

Emulsifier: 0.6 part by weight of alkyl aryl polyglycol ether

To test for protective efficacy, young plants are sprayed with the preparation of active compound as dewy. After the spray coating has dried on, the plants are covered with spores from Erysiphe graminis f.sp. tritici pollinated.

Evaluation is carried out 7 days after the inoculation.

In this test, for example, the compounds according to Preparation Examples 1, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 21 show a clear superiority in effectiveness over the prior art which show an efficiency of 75% to 100% at a rate of 400 g / ha. The compounds (A) and (B) show 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

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

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

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

Evaluation is carried out 12 days after the inoculation.

In this test, for example, the compounds according to Preparation Examples 1, 7, 8, 10, 11, 12, 14, 16, 18, 19, which have a 100% efficiency at an active ingredient concentration of 100 ppm, show good activity.

Example D

Erysiphe test (barley) / curative

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

Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To test for curative effectiveness, young plants with spores of Erysiphe graminis f.sp. hordei pollinated. 48 hours after the inoculation, the plants are sprayed with the preparation of active compound with dew.

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

Evaluation is carried out 7 days after the inoculation.

In this test, for example, the compounds according to Preparation Examples 4, 22, 87 and 88 show an efficiency of 100% at a rate of 400 g / ha.

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 test for curative effectiveness, young plants are inoculated with an aqueous conidia suspension of the Venturia inaequalis apple scab pathogen. The plants remain in an incubation cabin at 20 ° C. and 100% relative atmospheric humidity for 1 day and are then placed in the greenhouse. After a specified number of hours, the plants are sprayed to runoff point with the active compound preparation.

Evaluation is carried out 12 days after the inoculation.

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

Claims

claims

1. 2-oximino-2-thienyl-acetic acid derivatives of the general formula (I)

in which Ar represents optionally substituted aryl or heteroaryl,

R ^{1 represents} alkyl or haloalkyl,

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

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

CCHH. ₂ -, SO _n -, -C (R ⁴ ) = NO-, -C (R ⁴ ) = NO-CH ₂ - or N (R ⁶ ) -, and for a radical of the formula -OR ⁵ or -NR ⁶ R ⁷ stands, whereby

R represents hydrogen, alkyl, haloalkyl, cycloalkyl or cyano, R ^{5 represents} alkyl or haloalkyl and R ⁶ and R ⁷ each independently represent hydrogen, alkyl, haloalkyl or alkoxy, and n represents 0, 1 or 2.

2. Compounds of formula (I) according to claim 1, in which Ar for optionally single or multiple, identical or differently substituted aryl having 6 to 10 carbon atoms or for optionally single or multiple, identical or differently substituted and / or benzo-fused heteroaryl with 2 to 9 carbon atoms and 1 to 5 identical or different heteroatoms, where the following are suitable as substituents:

Halogen, cyano, nitro, hydroxy, amino, formyl, carbamoyl, thiocarbamoyl, each straight-chain or branched alkyl, alkoxy, alkylthio, AUcylsulfinyl or alkylsulfonyl, each with 1 to 6 carbon atoms, each straight-chain or branched alkenyl or alkenyloxy, each with 2 to 6 carbon atoms , each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 13 identical or different Halogen atoms, each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroximinoalkyl or alkoximinoalkyl, each having 1 to 6 carbon atoms in the individual alkyl parts, each optionally one or more times, eq Eich 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 , in each case two-linked alkylene or dioxy alkylene each having 1 to 6 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, 3- to 7-membered heterocyclyl having 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 Phenyl part single or multiple, identical or different by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and / or straight-chain or branched alkoxy 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 phenylethoxy, R ¹ for straight-chain or branched alkyl having 1 to 8 carbon atoms or for straight-chain or branched halogen enalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms,

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

Alkylthio each having 1 to 6 carbon atoms, each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms, each straight-chain or branched alkynyl or alkynyloxy each having 2 to 6 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio each having 1 to 6 Carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched haloalkenyl or haloalkenyloxy each with 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 alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts and, moreover, in each case optionally in the phenyl part, once or several 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 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and / or straight-chain or branched alkoxy with 1 to 4 carbon atoms and / or straight-chain or branched haloalkoxy with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms substituted phenyl, phenoxy, Are benzyl, benzyloxy, phenylethyl or phenylethyloxy,

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

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

R ^{4 represents} 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,

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

R ⁶ and R ⁷ independently of one another each represent hydrogen, for straight-chain or branched alkyl having 1 to 8 carbon atoms, for straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogenato men stands for straight-chain or branched alkoxy having 1 to 8 carbon atoms, and n stands for 0, 1 or 2.

3. Compounds of formula (I) according to claim 1, in which Ar is aryl for 6 to 10 carbon atoms, which is optionally monosubstituted to pentasily, identically or differently, or for heteroaryl which is monosubstituted to tetrasubstituted, identically or differently, and / or benzo-fused with 2 up to 9 carbon atoms and 1 to 3 identical or different heteroatoms - in particular nitrogen, oxygen and / or sulfur -, 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 identical or different halogen atoms, each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroximinoalkyl or alkoximinoalkyl each having 1 to 4 carbon atoms in the individual alkyl parts, in each case where appropriate mono- or polysubstituted, 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, in each case double-linked alkylene or dioxyalkylene 1 to 4 each 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 in the phenyl part in one to three times , identical or different by halogen and / or straight-chain or branched alkyl having 1 to 3 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms and / or straight-chain or branched alkoxy having 1 to 3 carbon Atoms and / or straight-chain or branched haloalkoxy with 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy and R ¹ for straight-chain or branched alkyl with 1 to 6 carbon atoms or for straight-chain or branched haloalkyl has 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms,

R ² and R ³ independently of one another each represent hydrogen, halogen, cyano, nitro, 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, in each case 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 each

Are alkyl parts and also for each optionally in the phenyl part from one to five times, identical or different by halogen and / or straight-chain or branched alkyl having 1 to 3 Koh Lenstoffatomen and / or straight-chain or branched haloalkyl with 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms and / or straight-chain or branched alkoxy with 1 to 3 carbon atoms and / or straight-chain or branched haloalkoxy with 1 to 3 carbon atoms and 1 to 7 the same or different halogen atoms are substituted phenyl, phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy,

A represents oxygen, ethene-1,2-diyl, ethyne-1,2-diyl or one of the following groups -CH ₂ -O-; -O-CH ₂ -, -CH ₂ -S (O) _n -,

-SS ((OO)) _nn --CCH ₂ -, SO _n -, -C (R ⁴ ) = NO-, -C (R ⁴ ) = NO-CH ₂ - or -N (R ⁶ ) -, and represents a radical of the formula -OR ⁵ or -NR ⁶ R ⁷ , wherein

R ^{4 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,

R ⁵ for straight-chain or branched alkyl having 1 to 6 carbon atoms or for straight-chain or branched haloalkyl having 1 to

4 carbon atoms and 1 to 9 identical or different halogen atoms and

R ⁶ and R ⁷ each independently represent hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms or straight-chain or branched alkoxy having 1 to 6 carbon atoms 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 identically or differently or for each optionally monosubstituted to trisubstituted or identical or differently substituted and / or benzo-fused furanyl, thienyl, pyrrolyl,

Oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyrazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl or triazinyl, where the following are suitable in each case:

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, dimethylamino, diethylamino, acetyl, methoxyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyethyloxyoxyoxy Methoximinoethyl, ethoximinomethyl, ethoximinoethyl, propane-1,3-diyl, butane-1,4-diyl, dioxymethylene, dioxyethylene, dioxypropylene,

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

R ^{1 represents} straight-chain or branched alkyl having 1 to 4 carbon atoms or haloalkyl having 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms, R ² and R ³ each independently of one another 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, ethoxycarbonyl, Hydroximinomethyl, Hydroximinoethyl, methoximinomethyl, methoximinoethyl, ethoximinomethyl, ethoximinoethyl, or represents in each case optionally mono- to trisubstituted by identical or different fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy substituted phenyl, phenoxy, benzyl or benzyloxy, A is oxygen, ethene-1,2-diyl, ethyne-1,2 -diyl or one of the following groupings -CH ₂ -O-; -O-CH ₂ -, -CH ₂ -S (O) _n -, -S (O) _n -CH ₂ -, SO _n -, -C (R ⁴ ) = NO-, -C (R ⁴ ) = NO-CH ₂ - or -N (R ⁶ ) -, and

Z represents a radical of the formula -OR ⁵ or -NR ⁶ R ⁷ , where R ^{4 represents} hydrogen, methyl, ethyl, trifluoromethyl or cyano,

R ⁵ 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 identical or different halogen atoms and R ⁶ and R ⁷ each independently represent hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl stands for haloalkyl with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms or stands 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 the 3- or 2-position and the oximinoacetic acid residue in the 2- or 3-position in the thiophene ring.

7. pesticide, characterized by a content of at least one compound of the formula (I) according to claim 1.

8. A method for controlling pests, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on pests and / or their habitat.

9. 2-oximino-2- (halomethyl-2-thienyl) acetic acid derivatives of the formula (IV)

in which

R ¹ , R ² , R ³ 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 (Ila)

in which

R ² , R ³ , Ar, A and Z have the meaning given above, with the exception of the compound 2-Oxo-2- (3-phenoxy-methyl-2-thienyl) acetic acid methyl ester.

11.Ketals of the formula (Ilb)

in which

R ² , R ³ , Ar, A and Z have the meaning given in claim 1 and

R ^{8 represents} alkyl.

12. Thiophene carboxylic acid ester of the formula (VIII)

in which R ² , R ³ , R ⁹ and Ar have the meaning given in claim 1 and

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

13. Thiophene carboxylic acids of the formula (IX)

in which

R ² , R ³ , Ar and A ^{1 have} the meaning given in claim 12.

14. Compounds of formula (X)

in which

R ² , R ³ , Ar and A ^{1 have} the meaning given in claim 12.

15. Compounds of the formula (XI)

in which

R ² , R ³ , Ar and A ^{1 have} the meaning given in claim 12.

16. ketals of formula (XV)

in which

R ² , R ³ , R ⁵ and R ^{8 have} the meaning given in claim 12.

17. halomethyl ketals of the formula (XVI),

in which

R ² , R ³ , R ⁵ and R ^{8 have} the meaning given in claim 12 and

Shark represents halogen, especially chlorine or bromine.

18. ketals of formula (XVII),

in which

R ² , R ³ , R ⁵ , R ⁸ , Ar and A ^{1 have} the meaning given in claim 12.

19. Process for the preparation of compounds of formula (I)

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

in which

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

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

H ₂ NOR ¹ (III) in which

in which

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

X represents halogen, with nucleophiles of the formula (V),

Ar-A ¹ -H (V) in which

in which

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

in which

R ⁶ and R ^{7 have} the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary.

20. Use of compounds of formula (I) according to claims 1 to 6 for controlling pests.

21. A process for the preparation of pesticides, characterized in that compounds of the formula (I) according to Claims 1 to 6 are mixed with extenders and / or surface-active agents.