# US 2010/0167931 A1 · Heterocyclically substituted heterocyclylcarboxylic acid derivatives

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- Number: US 2010/0167931 A1
- Document ID: US20100167931A1
- Status: Published application
- Kind: A1
- Application number: 12/663,218
- Filed: 2008-05-31
- Published: 2010-07-01
- Earliest claimed: 2007-06-13
- Assignees: Bayer CropScience AG
- Inventors: Michael Müller; Welf-Burkhard Wiese; Thomas Schenke; Hans-Georg Schwarz; Heinz-Jûrgen Wroblowsky; Reiner Fischer; Eva-Maria Franken; Olga Malsam; Christian Arnold; Kerstin Ilg; Arnd Voerste; Ulrich Görgens
- Web page: https://patentgrep.com/patent/US20100167931A1

## CPC

- C07D 487/04: Ortho-condensed systems
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

The present invention relates to heterocyclic carboxylic acid derivatives of the formula (I) below to a process for their preparation, to the use of the heterocyclic carboxylic acid derivatives according to the invention for controlling animal pests and/or phytopathogenic harmful fungi, to methods and compositions for controlling animal pests and/or phytopathogenic harmful fungi in and/or on plants or in and/or on seed of plants, to processes for preparing such compositions and to treated seed and also to the use thereof for controlling pests and/or phytopathogenic harmful fungi in agriculture, horticulture and forestry, in animal health, in the protection of materials and in the domestic and hygiene field.

## Claims

### Claim 1

Heterocyclic carboxylic acid derivatives of the formula (I),
in which the symbols have the following meaning:
X represents hydrogen, halogen, cyano, hydroxyl, optionally substituted alkyl, haloalkyl, optionally substituted alkoxy, optionally substituted phenyl, optionally substituted alkylthio, optionally substituted alkylsulphinyl or optionally substituted alkylsulphonyl;
Het represents one of the radicals
U, V and W independently of one another represent hydrogen, fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, heptafluoroisopropyl, heptafluoron-propyl, carboxyl and/or carboxymethyl;
Z represents hydroxyl, halogen or in each case optionally substituted alkoxy, alkylthio, alkylsulphonyl or the group
Y represents hydrogen, halogen, optionally substituted alkyl, haloalkyl, or optionally substituted cycloalkyl, O—(C1-C4)-alkyl or S(O)0-2(C1-C4)-alkyl;
R1 represents hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, haloalkyl, optionally substituted cycloalkyl or optionally substituted heterocyclyl, hydroxyl, optionally substituted alkoxy, amine, optionally substituted alkylamine or optionally substituted dialkylamine;
R2 represents hydrogen or alkyl;
or
R1 and R2 together with the nitrogen atom to which they are attached represent an optionally substituted heterocyclic ring;
R3 represents
COOH, CO—O−M1;
R4 represents hydrogen, in each case optionally substituted alkyl, alkenyl or alkynyl, haloalkyl, in each case optionally substituted saturated or unsaturated cycloalkyl which may optionally be interrupted by heteroatoms, in each case optionally substituted phenyl, heteroaryl, arylalkyl, heteroarylalkyl;
M1 represents a cation, such as, for example, mono- or divalent metal atoms, or an optionally alkyl- or arylalkyl-substituted ammonium ion;
R5 represents the groups COR6, S(O)1-2R6, cyano, COOR6; or
R4 and R5 together with the nitrogen atom to which they are attached represent an optionally substituted saturated, unsaturated or aromatic ring which may optionally be interrupted by further heteroatoms;
R6 represents hydrogen, in each case optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, represents in each case optionally substituted cycloalkylalkyl, cycloalkyl or cycloalkenyl, in each case optionally substituted aryl, heteroaryl, arylalkyl or heteroarylalkyl;
or
R4 and R6 together with the N—CO or N—S(O)1-2 group to which they are attached form a 4- to 8-membered cycle which may contain one or more heteroatoms from the group consisting of sulphur, oxygen and/or nitrogen, where oxygen atoms must not be adjacent;
and agrochemically active salts thereof.

### Claim 2 (depends on 1)

Heterocyclic carboxylic acid derivatives of the formula (I) according to claim 1 in which the symbols have the following meaning:
X represents hydrogen, fluorine, chlorine, bromine, cyano, hydroxyl, alkoxy having 1 to 4 carbon atoms or alkythio having 1 to 4 carbon atoms, C1-C6-alkyl or C1-C4-haloalkyl having 1 to 9 halogen atoms;
Het represents one of the radicals
U, V and W independently of one another represent hydrogen, fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, heptafluoroisopropyl, heptafluoron-propyl, carboxyl and/or carboxymethyl;
Z represents hydroxyl, chlorine, bromine, represents straight-chain or branched C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkylsulphonyl, each of which is optionally substituted by 1 to 7 halogen atoms, or represents the group
Y represents hydrogen, halogen, C1-C4-alkyl which is optionally substituted by 1 to 9 halogen atoms, C3-C6-cycloalkyl which is optionally substituted by 1 to 9 halogen atoms, SCH3, SC2H5, SOCH3, SOC2H5, SO2CH3, SO2C2H5, OCH3 or OC2H5;
R1 represents hydrogen, alkyl having 1 to 10 carbon atoms which is unsubstituted or mono- to pentasubstituted by identical or different substituents from the group consisting of cyano, hydroxyl, alkoxy having 1 to 4 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, mercapto, alkylthio having 1 to 4 carbon atoms, amino, mono- or dialkylamino having in each case 1 to 4 carbon atoms; or
R1 represents alkenyl having 3 to 10 carbon atoms which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group consisting of halogen, cyano, hydroxyl, alkoxy having 1 to 4 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, mercapto, alkylthio having 1 to 4 carbon atoms, amino, mono- or dialkylamino having in each case 1 to 4 carbon atoms; or
R1 represents alkynyl having 3 to 10 carbon atoms which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group consisting of halogen, cyano, hydroxyl, alkoxy having 1 to 4 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, mercapto, alkylthio having 1 to 4 carbon atoms, amino, mono- or dialkylamino having in each case 1 to 4 carbon atoms; or
R1 represents haloalkyl having 1 to 10 carbon and 1 to 21 halogen atoms; or
R1 represents cycloalkyl having 3 to 10 carbon atoms which is unsubstituted or mono-to trisubstituted by identical or different substituents from the group consisting of halogen and alkyl, haloalkyl having in each case 1 to 4 carbon atoms; or
R1 represents saturated or unsaturated heterocyclyl having 3 to 10 ring members and 1 to 3 heteroatoms, such as nitrogen, oxygen and/or sulphur, where the heterocyclyl is unsubstituted or mono- or polysubstituted by halogen, alkyl having 1 to 4 carbon atoms, alkoxyl having 1 to 4 carbon atoms, cyano, nitro, cycloalkyl having 3 to 6 carbon atoms, hydroxyl, alkoxy, alkenyloxy, alkynyloxy having 1 to 6 carbon atoms or mercapto;
R2 represents hydrogen or alkyl having 1 to 6 carbon atoms; or
R1 and R2 together with the nitrogen atom to which they are attached represent a saturated or unsaturated heterocyclic ring having 3 to 8 ring members, where the heterocycle optionally contains a further nitrogen, oxygen or sulphur atom as ring member and where the heterocycle may be unsubstituted or up to trisubstituted by fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 fluorine and/or chlorine atoms, hydroxyl, alkoxy having 1 to 4 carbon atoms, haloalkoxy having 1 to 4 carbon atoms and 1 to 9 fluorine and/or chlorine atoms, mercapto, thioalkyl having 1 to 4 carbon atoms and/or haloalkylthio having 1 to 4 carbon atoms and 1 to 9 fluorine and/or chlorine atoms;
R3 represents
COOH, CO—O−M1;
R4 represents hydrogen,
represents C1-C10-alkyl, C3-C10-alkenyl or C3-C10-alkynyl, each of which is optionally mono- or polysubstituted by fluorine, chlorine, C1-C4-alkoxy, C1-C4-alkylthio, cyano, CO2—H or CO—O—C1-C4-alkyl, represents C3-C8-cycloalkyl which is optionally mono- or polysubstituted by fluorine, chlorine, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, CN, CO2H or CO—O—C1-C4-alkyl and which may optionally be interrupted by an oxygen or sulphur atom,
represents phenyl, pyridyl, thiazolyl, pyrimidyl, benzyl, phenethyl, pyridinylmethyl or thiazolylmethyl, each of which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4alkoxy, C1-C4-haloalkoxy, nitro or cyano;
M1 represents cations from the group of the alkali metals or alkaline earth metals or ammonium ions NH4, mono-(C1-C10)-alkylammonium, di-(C1-C10)-alkylammonium, tri-(C1-C10)-alkylammonium, tetra-(C1-C10)-alkylammonium, where the alkyl radicals of the ammonium ions may be substituted by aryl or hydroxyl, or cholinium;
R5 represents the groups CO—R6, S(O)1-2R6, cyano, COOR6;
R4 and R5 together with the nitrogen atom to which they are attached represent a saturated or unsaturated 5- or 6-membered ring which is optionally mono- or polysubstituted by C1-C4-alkyl and which may optionally be interrupted by oxygen or sulphur;
R6 represents hydrogen, represents C1-C10-alkyl, C3-C10-alkenyl or C3-C10-alkynyl, each of which is optionally mono- or polysubstituted by fluorine, chlorine, C1-C4-alkoxy, C1-C4-alkylthio, cyano, CO2—H or CO—O—C1-C4-alkyl, represents C1-C10-haloalkyl having 1 to 21 fluorine and/or chlorine atoms, represents C3-C8-cycloalkyl, C3-C6-cycloalkyl-C1-C2-alkyl or C5-C8-cycloalkenyl, each of which is optionally mono- or polysubstituted by fluorine, chlorine, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, CN, CO2H or CO—O—C1-C4-alkyl and which may optionally be interrupted by an oxygen or sulphur atom,
represents phenyl, pyridyl, thiazolyl, pyrimidyl, benzyl, phenethyl, pyridinylmethyl or thiazolylmethyl, each of which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, nitro or cyano;
or
R4 and R6 together with the N—CO or N—S(O)1-2 group to which they are attached form a 4- to 8-membered cycle which may contain one or more heteroatoms from the group consisting of sulphur, oxygen and nitrogen, where oxygen atoms must not be adjacent.

### Claim 3 (depends on 1, 2)

Heterocyclic carboxylic acid derivatives of the formula (I) according to claim 1 or 2 in which the symbols have the following meaning:
X represents hydrogen, fluorine, chlorine, bromine, cyano, C1-C4-alkyl or C1-C2-haloalkyl which may be substituted by one to five fluorine and/or chlorine atoms;
Het represents one of the radicals
U, V and W independently of one another represent hydrogen, fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, heptafluoroisopropyl, heptafluoron-propyl, carboxyl and/or carboxymethyl;
Z represents chlorine, bromine, represents straight-chain or branched C1-C4-alkoxy, C1-C4-alkylthio, each of which is optionally substituted by 1 to 3 halogen atoms, or represents the group
Y represents hydrogen, halogen, (C1-C4)-alkyl which is optionally substituted by 1 to 9 halogen atoms, cyclopropyl which is optionally substituted by 1 to 5 halogen atoms; SCH3, SC2H5, SOCH3, SOC2H5, SO2CH3, SO2C2H5, OCH3 or OC2H5;
R1 represents hydrogen, alkyl having 1 to 8 carbon atoms which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group consisting of cyano, alkoxy having 1 to 3 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, alkylthio having 1 to 3 carbon atoms; or
R1 represents alkenyl having 3 to 8 carbon atoms which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, cyano, alkoxy having 1 to 3 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, alkylthio having 1 to 3 carbon atoms; or
R1 represents alkynyl having 3 to 8 carbon atoms which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, cyano, alkoxy having 1 to 3 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, alkylthio having 1 to 3 carbon atoms; or
R1 represents cycloalkyl having 3 to 8 carbon atoms which is unsubstituted or mono-to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine and alkyl, haloalkyl, alkoxy having in each case 1 or 2 carbon atoms; or
R1 represents haloalkyl having 1 to 8 carbon and 1 to 17 fluorine and/or chlorine atoms; or
R1 represents saturated or unsaturated heterocyclyl having 3 to 8 ring members and 1 or 2 heteroatoms, such as nitrogen, oxygen and/or sulphur, where the heterocyclyl is unsubstituted or mono- or disubstituted by hydroxyl, fluorine, chlorine, alkyl having 1 to 3 carbon atoms, alkoxy having 1 to 3 carbon atoms, cyano, nitro or cycloalkyl having 3 to 6 carbon atoms;
R2 represents hydrogen or alkyl having 1 to 6 carbon atoms; or
R1 and R2 together with the nitrogen atom to which they are attached represent a saturated or unsaturated heterocyclic ring having 3 to 6 ring members, where the heterocycle optionally contains a further nitrogen, oxygen or sulphur atom as ring member and where the heterocycle may be unsubstituted or up to trisubstituted by fluorine, chlorine, bromine, alkyl having 1 to 3 carbon atoms, haloalkyl having 1 to 3 carbon atoms and 1 to 5 fluorine and/or chlorine atoms, alkoxy having 1 to 3 carbon atoms, haloalkoxy having 1 to 3 carbon atoms and 1 to 5 fluorine and/or chlorine atoms, thioalkyl having 1 to 3 carbon atoms and/or haloalkylthio having 1 to 3 carbon atoms and 1 to 5 fluorine and/or chlorine atoms;
R3 represents
COOH, CO—O−M1;
R4 represents hydrogen,
represents C1-C8-alkyl, C3-C8-alkenyl or C3-C8-alkynyl, each of which is optionally mono- to trisubstituted by fluorine, chlorine, C1-C3-alkoxy, C1-C3-alkylthio, cyano, CO2H or CO—O—C1-C3-alkyl, represents C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, each of which is optionally mono- to trisubstituted by fluorine, chlorine, C1-C3-alkyl, C1-C2-haloalkyl, C1-C3-alkoxy, CN, CO2H or CO—O—C1-C3-alkyl and which may optionally be interrupted by an oxygen or sulphur atom,
represents phenyl, pyridyl, thiazolyl, pyrimidyl, benzyl, phenethyl, pyridinylmethyl or thiazolylmethyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, C1-C3-alkyl, C1-C3-haloalkyl, C1-C3-alkoxy, C1-C3-haloalkoxy, nitro or cyano;
M1 represents Na+, K+, ½ Ca2+, ½ Mg2+, NH4+, NH3CH3+, NH2(CH3)2+, NH(CH3)3+, NH(C2H5)3+, NH2(C2H5)2+, NH3C2H5+, NH3i-C3H7+, NH2(i-C3H7)2+, NH3—CH2—C6H5+, N(CH3)3—H2—C6H5+,
R5 represents the groups COR6, S(O)1-2R6, cyano, COOR6;
R4 and R5 together with the nitrogen atom to which they are attached represent a saturated or unsaturated 5- or 6-membered ring which is optionally mono- or disubstituted by C1-C2-alkyl and which may optionally be interrupted by oxygen or sulphur;
R6 represents hydrogen, represents C1-C8-alkyl, C3-Cg-alkenyl or C3-C8-alkynyl, each of which is optionally mono- to pentasubstituted by fluorine, chlorine, C1-C3-alkoxy, C1-C3-alkylthio, cyano, CO2H or CO—O—C1-C3-alkyl, represents C1-C8-haloalkyl having 1 to 17 fluorine and/or chlorine atoms, represents C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl or C5-C6-cycloalkenyl, each of which is optionally mono- to trisubstituted by fluorine, chlorine, C1-C4-alkyl, C1-C2-haloalkyl, C1-C2-alkoxy, CN, CO2H or CO—O—C1-C2-alkyl and which may optionally be interrupted by an oxygen or sulphur atom,
represents phenyl, pyridyl, thiazolyl, pyrimidyl, benzyl, phenethyl, pyridinylmethyl or thiazolylmethyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, C1-C3-alkyl, C1-C3-haloalkyl, C1-C3-alkoxy, C1-C3-haloalkoxy, nitro or cyano;
or
R4 and R6 together with the N—CO or N—S(O)1-2 group to which they are attached form a 4- to 6-membered cycle which may contain one or more heteroatoms from the group consisting of sulphur, oxygen and nitrogen, where oxygen atoms must not be adjacent.

### Claim 4 (depends on 1, 2, 3)

Heterocyclic carboxylic acid derivatives of the formula (I) according to any of claims 1 to 3, in which the symbols have the following meanings:
X represents hydrogen, chlorine, bromine, methyl or trifluoromethyl;
Het represents one of the radicals
U, V and W independently of one another represent hydrogen, fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, heptafluoroisopropyl, heptafluoron-propyl, carboxyl and/or carboxymethyl;
Z represents chlorine, methoxy, ethoxy, methylthio, ethylhio or the group
Y represents hydrogen, chlorine, bromine, alkyl having 1 or 2 carbon atoms, haloalkyl having 1 or 2 carbon and 1 to 5 halogen atoms or cyclopropyl;
R1 represents hydrogen, alkyl having 1 to 4 carbon atoms which is unsubstituted or mono- to tetrasubstituted by identical or different substituents from the group consisting of methyl, ethyl, methoxy, ethoxy, cyclopropyl, cyclopentyl, cyclohexyl, methylthio and ethylthio; or
R1 represents alkenyl having 3 to 6 carbon atoms which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, methoxy, ethoxy, methylthio and ethylthio; or
R1 represents alkynyl having 3 to 6 carbon atoms which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, methoxy, ethoxy, methylthio and ethylthio; or
R1 represents cycloalkyl having 3 to 6 carbon atoms which is unsubstituted or mono-to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, methyl, ethyl, methoxy and trifluoromethyl;
R1 represents haloalkyl having 1 to 4 carbon atoms which is substituted by 1 to 9 fluorine and/or chlorine atoms;
R2 represents hydrogen, alkyl having 1 or 2 carbon atoms; or
R1 and R2 together with the nitrogen atom to which they are attached represent a saturated or unsaturated heterocyclic ring having 3 to 6 ring members, where the heterocycle optionally contains a further nitrogen, oxygen or sulphur atom as ring member and where the heterocycle may be unsubstituted or up to disubstituted by fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy or ethoxy;
R3 represents
COOH, CO—O−M1;
R4 represents hydrogen;
M1 represents Na+, K+, ½ Ca2+, ½ Mg2+, NH4+, NH3CH3+, NH2(CH3)2+, NH(CH3)3+, NH(C2H5)3+, NH2(C2H5)2+, NH3C2H5+, NH3i-C3H7+, NH2(i-C3H7)2+, NH3—CH2—C6H5+ or N(CH3)3—H2—C6H5+;
R5 represents the groups COR6, S(O)R6, S(O)2R6, cyano, COOR6;
R6 represents hydrogen, represents alkyl having 1 to 3 carbon atoms or cyclopropyl, each of which is optionally mono- to trisubstituted by methoxy, ethoxy, methylthio, ethylthio, cyano, CO—O-methyl or CO—O-ethyl, represents haloalkyl having 1 to 3 carbon and 1 to 7 fluorine and/or chlorine atoms.

### Claim 5 (depends on 1, 2, 3, 4)

Heterocyclic carboxylic acid derivatives of the formula (I) according to any of claims 1 to 4 in which the symbols are as defined below:
X represents hydrogen, chlorine, bromine, methyl or trifluoromethyl;
Het represents pyridinyl which is attached in the 2-, 3- or 4-position and may be mono- or disubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, carboxyl and carboxymethyl or
represents pyrazinyl which is attached in the 2-position and may be mono- or disubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, carboxyl and carboxymethyl or
represents pyrazolyl which is attached in the 1-position and may be mono- or disubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, heptafluoroisopropyl, heptafluoro-n-propyl, carboxyl and carboxymethyl or
represents pyrazolyl which is attached in the 4- or 5-position and may be mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, carboxyl and carboxymethyl or
represents thiazolyl which is attached in the 4-position and may be mono- or disubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, carboxyl and carboxymethyl;
Z represents chlorine, methoxy, ethoxy, methylthio, ethylhio or the group
Y represents hydrogen, chlorine, bromine, methyl, ethyl, trifluoromethyl or cyclopropyl;
R1 represents hydrogen, alkyl having 1 to 4 carbon atoms which is unsubstituted or mono- to tetrasubstituted by identical or different substituents from the group consisting of methyl, ethyl, methoxy, ethoxy, cyclopropyl, cyclopentyl, cyclohexyl, methylthio and ethylthio; or
R1 represents alkenyl having 3 to 6 carbon atoms which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, methoxy, ethoxy, methylthio and ethylthio; or
R1 represents alkynyl having 3 to 6 carbon atoms which is unsubstituted or mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, methoxy, ethoxy, methylthio and ethylthio; or
R1 represents cycloalkyl having 3 to 6 carbon atoms which is unsubstituted or mono-to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, methyl, ethyl, methoxy and trifluoromethyl;
R1 represents haloalkyl having 1 to 4 carbon atoms which is substituted by 1 to 9 fluorine and/or chlorine atoms;
R2 represents hydrogen, methyl or ethyl; or
R1 and R2 together with the nitrogen atom to which they are attached represent a saturated or unsaturated heterocyclic ring having 3 to 6 ring members, where the heterocycle optionally contains a further nitrogen, oxygen or sulphur atom as ring member and where the heterocycle may be unsubstituted or up to disubstituted by fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy or ethoxy;
R3 represents
COOH, CO—O−M1;
R4 represents hydrogen;
M1 represents Na+, K+, ½ Ca2+, ½ Mg2+, NH4+, NH3CH3+, NH2(CH3)2+, NH(CH3)3+, NH(C2H5)3+, NH2(C2H5)2+, NH3C2H5+, NH3i-C3H7+, NH2(i-C3H7)2+, NH3—CH2—C6H5+ or N(CH3)3—H2—C6H5+;
R5 represents S(O)R6, S(O)2R6,
R6 represents hydrogen, represents alkyl having 1 to 3 carbon atoms or cyclopropyl, each of which is optionally mono- to trisubstituted by fluorine, chlorine, methoxy, ethoxy, methylthio, ethylthio, cyano, CO—O-methyl or CO—O-ethyl, represents haloalkyl having 1-3 carbon and 1 to 7 fluorine and/or chlorine atoms.

### Claim 6 (depends on 1)

Process for preparing heterocyclic carboxylic acid derivatives of the general formula (I), characterized in that
(A) compounds of the formula (II)
in which R7 represents C1-C4-alkyl and
Y has the meanings given in claim 1
are reacted with compounds of the formula (III)
in which R8 represents C1-C8-alkyl or aryl and
Het has the meanings given in claim 1,
to give compounds of the formula (IV)
and
(B) the compounds of the formula (IV), as defined above, are then converted into compounds of the formula (V)
in which R7 represents C1-C4-alkyl and
Het and Y have the meanings given in claim 1,
and
(C) the compounds of the formula (V), as defined above, are then reacted with compounds of the formula HNR1R2, in which R1 and R2 are as defined in claim 1, to give compounds of the formula (VI)
in which R7 represents C1-C4-alkyl and
R1, R2, Het and Y have the meanings given in claim 1,
and
(D) the compounds of the formula (VI), as defined above, are then converted in the presence of base into compounds of the formula (I-a)
in which R1, R2, Het and Y have the meanings given in claim 1, and
(E) the compounds of the formula (I-a), as defined above, are then converted into compounds of the formula (VII)
in which R1, R2, Het and Y have the meanings given in claim 1, and
(F) the compounds of the formula (VII), as defined above, are then reacted with compounds of the formula (VIII)
in which R4 and R5 have the meanings given in claim 1, to give compounds of the formula (I-b)
in which R1, R2, R4, R5, Het and Y have the meanings given in claim 1.

### Claim 7 (depends on 1, 2, 3, 4, 5)

Mixture, comprising at least one of the compounds defined in any of claims 1 to 5 and/or at least one of the agrochemically active salts thereof and a further active compound selected from the group consisting of insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulators, herbicides, safeners, fertilizers and semiochemicals for controlling animal pests and/or phytopathogenic harmful fungi.

### Claim 8 (depends on 1, 2, 3, 4, 5, 7)

Use according to any of claims 1 to 5 and 7 for controlling animal pests and phytopathogenic harmful fungi.

### Claim 9 (depends on 1, 2, 3, 4, 5, 7, 8)

Use according to any of claims 1 to 5 and 7 and 8 for treating plants or for treating seed of plants.

### Claim 10 (depends on 9)

Use according to claim 9, where the plants are selected from the group of the transgenic plants.

### Claim 11 (depends on 1, 2, 3, 4, 5, 7)

Composition for controlling animal pests and/or phytopathogenic harmful fungi in and/or on plants or in and/or on seed of plants, where the composition mentioned comprises at least one compound defined in any of claims 1 to 5 and/or at least one of its agrochemically active salts or a mixture as defined in claim 7 and agrochemically customary auxiliaries and/or additives.

### Claim 12 (depends on 11)

Composition according to claim 11 where the auxiliaries and/or additives are selected from the group consisting of extenders and/or surfactants.

### Claim 13 (depends on 1, 2, 3, 4, 5, 6)

Composition for controlling animal pests in and/or on plants or in and/or on seed of plants, where the composition mentioned comprises at least one compound as defined in any of claims 1 to 6 and/or at least one of its agrochemically active salts and at least one salt of the formula (XV)
in which
Q represents nitrogen or phosphorus,
R26, R27, R28 and R29 independently of one another represent hydrogen or in each case optionally substituted C1-C8-alkyl or mono- or polyunsaturated, optionally substituted C1-C8-alkylene, where the substituents may be selected from the group consisting of halogen, nitro and cyano,
n represents 1, 2, 3 or 4,
R30 represents an inorganic or organic anion.

### Claim 14 (depends on 11, 12, 13)

Composition according to one or more of claims 11 to 13, characterized in that Q represents nitrogen.

### Claim 15 (depends on 14)

Composition according to claim 14, characterized in that R30 represents bicarbonate, tetraborate, fluoride, bromide, iodide, chloride, monohydrogenphosphate, dihydrogenphosphate, hydrogensulphate, tartrate, sulphate, nitrate, thiosulphate, thiocyanate, formate, lactate, acetate, propionate, butyrate, pentanoate, citrate or oxalate.

### Claim 16 (depends on 13, 14, 15)

Composition according to any of claims 13 to 15, characterized in that it comprises at least one penetrant.

### Claim 17 (depends on 1, 2, 3, 4, 5, 7, 11, 12, 13, 14, 15, 16)

Method for controlling animal pests in and/or on plants or in and/or on seed of plants, which comprises bringing the pests mentioned directly or indirectly into contact with at least one compound as defined in any of claims 1 to 5 and/or at least one of the agrochemically active salts thereof or a mixture as defined in claim 7 or a composition as defined in any of claims 11 to 16.

### Claim 18 (depends on 1, 2, 3, 4, 5, 7, 11, 12, 13, 14, 15, 16)

Seed treated with at least one compound as defined in any of claims 1 to 5 and/or at least one of its agrochemically active salts or a mixture as defined in claim 7 or a composition as defined in any of claims 11 to 16.

### Claim 19 (depends on 6)

Malonic esters of the formula (III)
in which
R8 has the meaning given in claim 6 and
Het1 is pyrazolyl which is attached in the 1-position and may be mono- or disubstituted by identical or different substituents from the group consisting of haloalkyl having 1 to 7 fluorine and/or chlorine atoms, in particular trifluoromethyl, trichloromethyl, pentafluoroethyl, heptafluoroisopropyl and heptafluoro-n-propyl, or
represents 4-chloropyrazol-1-yl.

### Claim 20 (depends on 19)

Process for preparing malonic esters of the formula (III) as defined in claim 19, characterized in that heterocyclylacetic esters of the formula (IX)
are reacted with compounds of the formula (X)
in the presence of base.