EP2158204A2 - Dérivés d'acide hétérocyclyl-carboxylique à substitution hétérocyclique - Google Patents

Dérivés d'acide hétérocyclyl-carboxylique à substitution hétérocyclique

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Publication number
EP2158204A2
EP2158204A2 EP08801444A EP08801444A EP2158204A2 EP 2158204 A2 EP2158204 A2 EP 2158204A2 EP 08801444 A EP08801444 A EP 08801444A EP 08801444 A EP08801444 A EP 08801444A EP 2158204 A2 EP2158204 A2 EP 2158204A2
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
chlorine
alkyl
fluorine
substituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP08801444A
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German (de)
English (en)
Inventor
Michael Müller
Welf-Burkhard Wiese
Thomas Schenke
Hans-Georg Schwarz
Heinz-Jürgen Wroblowsky
Reiner Fischer
Eva-Maria Franken
Olga Malsam
Christian Arnold
Kerstin Ilg
Arnd Voerste
Ulrich Görgens
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
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Bayer CropScience AG
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Filing date
Publication date
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Priority to EP08801444A priority Critical patent/EP2158204A2/fr
Publication of EP2158204A2 publication Critical patent/EP2158204A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems

Definitions

  • the present invention relates to heterocyclic carboxylic acid derivatives of the following formula (I)
  • the present invention further relates to the enhancement of the action of crop protection agents containing in particular heterocyclic carboxylic acid derivatives of the formula (I), by the addition of ammonium or phosphonium salts and, optionally, penetration promoters, the corresponding compositions, processes for their preparation and their use in crop protection as insecticides and / or acaricides and / or fungicides.
  • X is hydrogen, halogen, cyano, hydroxy, optionally substituted alkyl, haloalkyl, optionally substituted alkoxy, optionally substituted phenyl, optionally substituted alkylthio, optionally substituted alkylsulfinyl or optionally substituted alkylsulfonyl;
  • Het-21 Het-22 Het-23 Het-24 Het-25 Het-26 U, V and W independently of one another represent hydrogen, fluorine, chlorine, bromine, cyano,
  • Z is hydroxy, halogen or in each case optionally substituted alkoxy, alkylthio,
  • Y is hydrogen, halogen, optionally substituted alkyl, haloalkyl or optionally substituted cycloalkyl, O- (Cj-C4) -alkyl or S (0) o_2 (Ci-C4) -alkyl;
  • R 1 represents hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, haloalkyl, optionally substituted cycloalkyl or optionally substituted heterocyclyl, hydroxy, optionally substituted alkoxy, amine, optionally substituted alkylamine or optionally substituted dialkylamine;
  • R 2 is hydrogen or alkyl
  • R! and R 2 together with the nitrogen atom to which they are attached represent an optionally substituted heterocyclic ring
  • R 3 is CO-N, CO-N M 1 , COOH, C0 ° M 1
  • R 4 is 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;
  • M 1 represents a cation such as monovalent or divalent metal atoms or an ammonium ion optionally substituted by alkyl or arylalkyl;
  • R 5 is the group COR 6 , S (O) i _ 2 R 6 , cyano, COOR 6 ; or - A -
  • R ⁇ and R ⁇ 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;
  • R is hydrogen, in each case optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, in each case optionally substituted cycloalkyl-alkyl, cycloalkyl or
  • Cycloalkenyl each optionally substituted aryl, heteroaryl, arylalkyl or heteroarylalkyl;
  • Inventive heterocyclic carboxylic acid derivatives of the formula (I) and their agrochemically active salts are very suitable as pesticides, in particular for
  • insects such as mites, spider mites and / or ticks
  • nematodes such as mites, spider mites and / or ticks
  • They are also suitable for controlling phytopathogenic harmful fungi.
  • compounds show a strong insecticidal and / or acaricidal and / or nematicidal and / or fungicidal activity and can be used both in crop protection, in the area of household and hygiene as well as in the protection of materials.
  • the compounds of the formula (I) can be used both in pure form and as mixtures of various possible isomeric forms, in particular of stereoisomers, such as E and Z, threo and erythro, and optical isomers, such as R and S isomers or Atropisomers, but optionally also of tautomers.
  • the invention includes both the pure isomers and their mixtures.
  • the compounds of formula (I) may optionally be present in different polymorphic forms or as a mixture of different polymorphic forms. Both the pure polymorphs and the polymorph mixtures are the subject of the invention and can be used according to the invention.
  • the compounds of formula (I) have acidic or basic properties and may form salts, optionally also internal salts. If the compounds of the formula (I) bear hydroxy, carboxy or other groups which induce acidic properties, these compounds can be reacted with bases to form salts.
  • Suitable bases are, for example, hydroxides, carbonates, bicarbonates of the alkali and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, furthermore ammonia, primary, secondary and tertiary amines having (C r C 4 -) - alkyl radicals, mono-, di and trialkanolamines of (C 1 -C 4 ) -alkanols, choline and chlorocholine. If the compounds of the formula (I) bear amino, alkylamino or other basic-property-inducing groups, these compounds can be reacted with acids to form salts.
  • Suitable acids are, for example, mineral acids, such as hydrochloric, sulfuric and phosphoric acids, organic acids, such as acetic acid or oxalic acid, and acidic salts, such as NaHSO 4 and KHSO 4 .
  • the salts thus obtainable also have insecticidal and / or fungicidal properties.
  • Optionally substituted groups may be monosubstituted or polysubstituted, with multiple substituents the substituents may be the same or different.
  • Alkyl is defined as branched or unbranched C MO alkyl, such as, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, n-hexyl, n- Heptyl, n-octyl, n-nonyl, n-decyl and the like, preferably as Ci.g alkyl, particularly preferably as Ci -4 alkyl.
  • Alkenyl is defined as branched or unbranched C 3 . 1 0 alkenyl containing at least one double bond, for example vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butanedienyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1,3-pentanedienyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1,4-hexanedienyl and the like, preferably as C 3-8 alkenyl, more preferably as C 1 * Alkenyl.
  • Alkynyl is defined as C 3 -10 alkynyl containing at least one triple bond and optionally one or more double bonds such as ethynyl, 1-propynyl, propargyl and the like, preferably as C 3-8 alkynyl, more preferably as C 3-6 alkynyl ,
  • Cycloalkyl is defined as C 3 .i 0 cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like, preferably as C 3- cycloalkyl g.
  • Heterocycloalkyl is defined as cycloalkyl containing a 3-10 membered ring wherein the ring contains one, two or more heteroatoms such as nitrogen, oxygen and / or sulfur, such as tetrahydrofuran, thiolane, pyrrolidine, oxathiolane, oxazolidine, Tetrahydropuranes, piperidine, dioxane, and the like, preferably tetrahydrofuran.
  • Aryl is defined as an unsaturated C 5 -C] 2 cycloalkyl, such as phenyl, ⁇ - or ß-naphthyl, preferably phenyl.
  • Heteroaryl is defined as an aryl containing a 3-10 membered ring wherein the ring contains one, two or more heteroatoms such as nitrogen, oxygen and / or sulfur, such as furan, thiophene, pyrrole, oxazole, thiazole , Pyrazole, pyridine, pyrimidine, pyrazole and the like.
  • arylalkyl is defined as benzyl, phenethyl or ⁇ -methylbenzyl, preferably benzyl.
  • Halogen is defined as fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
  • the compounds according to the invention namely the heterocyclic carboxylic acid derivatives are generally defined by the formula (I).
  • the present invention thus relates
  • X is hydrogen, halogen, cyano, hydroxy, optionally substituted alkyl, haloalkyl, optionally substituted alkoxy, optionally substituted phenyl, optionally substituted alkylthio, optionally substituted alkylsulfinyl or optionally substituted alkylsulfonyl;
  • U, V and W independently represent hydrogen, fluorine, chlorine, bromine, cyano. Hydroxy, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximino-methyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, heptafluoroisopropyl, heptafluoro-n-propyl, carboxy and / or carboxymethyl; Z is hydroxyl, halogen or in each case optionally substituted alkoxy,
  • Y is hydrogen, halogen, optionally substituted alkyl, haloalkyl, or optionally substituted cycloalkyl, O- (Cj-C4) -alkyl or S (0) o_2 (Ci-C4) -alkyl;
  • R.1 is hydrogen, optionally substituted alkyl, optionally substituted
  • Alkenyl optionally substituted alkynyl, haloalkyl, optionally substituted cycloalkyl or optionally substituted heterocyclyl,
  • R 2 is hydrogen or alkyl
  • R! and R 2 together with the nitrogen atom to which they are attached represent an optionally substituted heterocyclic ring
  • R 3 is CO-N, CO-N M 1 , COOH, C0 ° M 1
  • R ⁇ is hydrogen, in each case optionally substituted alkyl, alkenyl or
  • M 1 represents a cation such as monovalent or divalent metal atoms or an ammonium ion optionally substituted by alkyl or arylalkyl;
  • R 5 represents the groups COR 6 , S (O) I-2R 6 , cyano, COOR 6 ;
  • R ⁇ and R ⁇ 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;
  • R ⁇ is hydrogen, in each case optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, in each case optionally substituted cycloalkyl-alkyl, cycloalkyl or cycloalkenyl, in each case optionally substituted aryl, heteroaryl, arylalkyl or heteroarylalkyl;
  • R.4 and R together with the N-CO or NS (O) j.2 group to which they are attached form a 4- to 8-membered cycle containing one or more heteroatoms selected from sulfur, oxygen and or may contain nitrogen, wherein oxygen atoms may not be adjacent;
  • an agent for controlling animal pests and / or phytopathogenic harmful fungi in and / or on plants or in and / or on seed of plants said agent comprising at least one compound as defined under (1) and / or at least one of their agrochemically active salts or as in (2) mixture and agrochemically customary auxiliaries and / or additives;
  • X is preferably hydrogen, fluorine, chlorine, bromine, cyano, hydroxy, alkoxy having 1 to 4 carbon atoms or alkylthio having 1 to 4 carbon atoms, Cj-Cg-alkyl or C ⁇ -C4-haloalkyl having 1 to 9 halogen atoms;
  • Het is preferably one of the radicals
  • U, V and W are preferably each independently hydrogen, fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroxyminomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, Heptafluoro-isopropyl, heptafluoro-n-propyl, carboxy and / or carboxymethyl;
  • Z is preferably hydroxy, chlorine, bromine, in each case optionally 1 to 7
  • Y is preferably hydrogen, halogen, optionally substituted by 1 to 9 halogen atoms substituted Cj-C4-alkyl, optionally substituted by 1 to 9 halogen atoms C 3 -C 6 cycloalkyl, SCH 3 , SC 2 H 5 , SOCH 3 , SOC 2 H 5 , SO 2 CH 3 , SO 2 C 2 H 5 , OCH 3 or OC 2 H 5 ;
  • R 1 is preferably hydrogen, alkyl of 1 to 10 carbon atoms which is unsubstituted or monosubstituted to five times, identically or differently substituted by cyano, hydroxy, alkoxy of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, mercapto, alkylthio 1 to 4 carbon atoms, amino, mono- or dialkylamino each having 1 to 4 carbon atoms; or
  • R 1 is preferably alkenyl of 3 to 10 carbon atoms which is unsubstituted or monosubstituted to trisubstituted, identically or differently substituted by halogen, cyano, hydroxy, alkoxy of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, mercapto, alkylthio 1 to 4 carbon atoms, amino, mono- or dialkylamino each having 1 to 4 carbon atoms; or
  • R! is preferably alkynyl of 3 to 10 carbon atoms, which is unsubstituted or monosubstituted to trisubstituted, identically or differently substituted by halogen, cyano, hydroxy, 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 each having 1 to 4 carbon atoms; or
  • R 1 is preferably haloalkyl having 1 to 10 carbon atoms and 1 to 21 halogen atoms;
  • R! preferably represents cycloalkyl having 3 to 10 carbon atoms which is unsubstituted or monosubstituted to trisubstituted, identically or differently substituted by halogen and / or alkyl, haloalkyl having in each case 1 to 4 carbon atoms; or
  • R! is preferably saturated or unsaturated heterocyclyl having 3 to 10 ring members and 1 to 3 heteroatoms, such as nitrogen, oxygen and / or sulfur, where the heterocyclyl is unsubstituted or monosubstituted or polysubstituted by halogen,
  • R 1 is preferably hydrogen or alkyl of 1 to 6 carbon atoms
  • R! and R ⁇ are preferably taken together with the nitrogen atom to which they are attached, for a saturated or unsaturated heterocyclic ring having 3 to 8 ring members, wherein the heterocycle optionally contains another nitrogen, oxygen or sulfur atom as ring member and wherein the heterocycle may be unsubstituted or substituted up to three times 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, hydroxy, 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;
  • R 3 is preferably M 1 , COOH, C0 ° M 1 ;
  • R ⁇ is preferably hydrogen
  • M 1 is preferably cations from the series of the alkali or alkaline earth metals or ammonium ions NH4, mono- (Ci-Cio) -alkylammonium, di- (C] -Cio) alkylammonium, tri (Ci-Cio) alkylammonium, tetra Ci-Ci Q ⁇ alkylammonium, wherein the alkyl radicals of the ammonium ions may be substituted by aryl or hydroxy, or cholinium,
  • R 5 preferably represents the groups CO-R 6 , S (O) 1-2 R 6 , cyano, COOR 6 ;
  • R 4 and R 5 are preferably taken together with the nitrogen atom to which they are attached, for a mono- or polysubstituted by C 1 -C 4 -alkyl-substituted saturated or unsaturated 5- or 6-ring, which may be interrupted by oxygen or sulfur can;
  • R 6 preferably represents hydrogen, in each case optionally mono- to polysubstituted by fluorine, chlorine, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, cyano, CO 2 -H or CO-OC j- C 1 -alkyl-substituted C 1 -C 12 -alkyl , C3-C j o-alkenyl or C3-CjQ-alkynyl, for Ci-Ci 0 - haloalkyl having 1 to 21 fluorine and / or chlorine atoms, each optionally mono- to polysubstituted by fluorine, chlorine, C j -C ⁇
  • Alkoxy, CN, CO2H or CO-OC i-C4-alkyl substituted C3-Cg-cycloalkyl, C3-C6-cycloalkyl-Ci-C 2 -alkyl or C5-Cg-cycloalkenyl, which may be interrupted by an oxygen or sulfur atom can be interrupted by an oxygen or sulfur atom.
  • R 4 and R 6 preferably together with the N-CO or NS (O) i_ 2 group to which they are attached form a 4- to 8-membered cycle which contains one or more heteroatoms from the series sulfur, oxygen and / or or nitrogen, wherein oxygen atoms may not be adjacent;
  • X particularly preferably represents hydrogen, fluorine, chlorine, bromine, cyano, C 1 -C 4 -alkyl or C 1 -C 2 -haloalkyl which may be substituted by one to five fluorine and / or chlorine atoms;
  • Het is particularly preferably one of the radicals
  • U, V and W are particularly preferably independently of one another hydrogen, fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl Heptafluoro-isopropyl, heptafluoro-n-propyl, carboxy and / or carboxymethyl;
  • Z is particularly preferably chlorine, bromine, in each case optionally 1 to 3
  • Y is particularly preferably hydrogen, halogen, optionally substituted by 1 to 9 halogen atoms substituted (C] -C 4 ) alkyl, optionally by 1 to 5 halogen atoms substituted cyclopropyl; SCH 3 , SC 2 H 5 , SOCH 3, SOC 2 H 5 , SO 2 CH 3 , SO 2 C 2 H 5 , OCH 3 or OC 2 H 5 ;
  • R 1 particularly preferably represents hydrogen, alkyl having 1 to 8 carbon atoms, which is unsubstituted or monosubstituted to trisubstituted, identically or differently, by cyano, alkoxy having 1 to 3 carbon atoms, cycloalkyl having 3 to 6 carbon atoms,
  • R * particularly preferably represents alkenyl having 3 to 8 carbon atoms which is unsubstituted or monosubstituted to trisubstituted, identically or differently substituted by 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
  • R! is particularly preferably alkynyl of 3 to 8 carbon atoms which is unsubstituted or monosubstituted to trisubstituted, identically or differently substituted by 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
  • R! particularly preferably represents cycloalkyl having 3 to 8 carbon atoms which is unsubstituted or monosubstituted to trisubstituted, identically or differently substituted by fluorine, chlorine and / or alkyl, haloalkyl, alkoxy having in each case 1 to 2 carbon atoms; or
  • R 1 particularly preferably represents halogenoalkyl having 1 to 8 carbon atoms and 1 to 17 fluorine and / or chlorine atoms; or
  • R! is particularly preferably saturated or unsaturated heterocyclyl having 3 to 8 ring members and 1 to 2 heteroatoms, such as nitrogen, oxygen and / or sulfur, wherein the heterocyclyl is unsubstituted or monosubstituted or disubstituted by hydroxy, fluorine, chlorine, alkyl with 1 to 3 carbon atoms, alkoxy of 1 to 3 carbon atoms, cyano, nitro or cycloalkyl of 3 to 6 carbon atoms;
  • R 1 particularly preferably represents hydrogen or alkyl having 1 to 6 carbon atoms
  • R! and R ⁇ are particularly preferably taken together with the nitrogen atom to which they are attached, for a saturated or unsaturated heterocyclic ring having 3 to 6 ring members, wherein the heterocycle optionally contains a further nitrogen, oxygen or sulfur atom as ring member and wherein the heterocycle is unsubstituted or may be substituted up to three times by fluorine, chlorine, bromine, alkyl having 1 to 3 carbon atoms, halogenoalkyl having 1 to 3 carbon atoms and 1 to 5 fluoro and / or Chlorine atoms, alkoxy having 1 to 3 carbon atoms, halogenoalkoxy having 1 to 3 carbon atoms and 1 to 5 fluorine and / or chlorine atoms, thioalkyl having 1 to 3 carbon atoms and / or halogenoalkylthio having 1 to 3 carbon atoms and 1 to 5 fluorine and / or chlorine atoms;
  • R 3 particularly preferably represents CO-N, CO-N M 1 , COOH, CO ° M 1 ;
  • R 4 particularly preferably represents hydrogen
  • M 1 particularly preferably represents Na + , K + , V 2 Ca 2+ , V 2 Mg 2+ , NH 4 + , NH 3 CH 3 + , NH 2 (CH 3 ) 2 + , NH (CH 3 ) 3 + , NH (C 2 H 5 ) 3 + , NH 2 (C 2 H 5 ) 2 + , NH 3 C 2 H 5 + , NH 3 JC 3 H 7 + , NH 2 (iC 3 H 7 ) 2 + ,
  • R 5 particularly preferably represents the groups COR 6 , S (O) R 6 , cyano, COOR 6 ;
  • R 4 and R 5 are particularly preferably together with the nitrogen atom to which they are attached, for a saturated or unsaturated 5- or 6-membered ring optionally substituted once or twice by C 1 -C 2 -alkyl, which is optionally interrupted by oxygen or sulfur can be;
  • R ⁇ particularly preferably represents hydrogen, represents in each case optionally mono- to pentasubstituted by fluorine, chlorine, C, -C 3 alkoxy, C r C 3 alkylthio, cyano, CO 2 H or CO-OC, -C 3 alkyl substituted Ci-Cg-alkyl, C 3 -C 8 -alkenyl or C 3 -C 8 -alkynyl, for C r C 8 -haloalkyl with
  • fluorine and / or chlorine atoms each optionally optionally mono- to trisubstituted by fluorine, chlorine, C r C 4 alkyl, C r C 2 haloalkyl, C, -C 2 alkoxy, CN, CO 2 H or CO - O-Ci-C 2 alkyl substituted C 3 -C 6 cycloalkyl, C 3 -C 6 -cycloalkyl-methyl, or C 5 -C 6 - cycloalkenyl, which may be optionally interrupted by an oxygen or sulfur atom,
  • R 4 and R 6 particularly preferably form, with the N-CO or NS (O) 1-2 group to which they are attached, a 4- to 6-membered cycle containing one or more heteroatoms from the group consisting of sulfur, oxygen and or may contain nitrogen, wherein oxygen atoms may not be adjacent;
  • the compounds of the invention are generally defined by the formula (I). Very particularly preferred substituents, fragments or ranges of the radicals listed in the formulas mentioned above and below are explained below for a very particularly preferred embodiment of the present invention:
  • X is very particularly preferably hydrogen, chlorine, bromine, methyl or trifluoromethyl
  • Het very particularly preferably represents one of the radicals
  • U, V and W very particularly preferably independently of one another represent hydrogen, fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio,
  • Z is very particularly preferably chlorine, methoxy, ethoxy, methylthio, ethythio or the
  • Y very particularly preferably represents hydrogen, chlorine, bromine, alkyl having 1 to 2 carbon atoms, halogenoalkyl having 1 to 2 carbon atoms and 1 to 5 halogen atoms or cyclopropyl;
  • R 1 most preferably represents hydrogen, alkyl of 1 to 4 carbon atoms, which is unsubstituted or monosubstituted, monosubstituted or differently substituted by methyl, ethyl, methoxy, ethoxy, cyclopropyl, cyclopentyl, cyclohexyl, methylthio or ethylthio; or
  • R.1 very particularly preferably represents alkenyl having 3 to 6 carbon atoms which is unsubstituted or monosubstituted to trisubstituted, identically or differently substituted by fluorine, chlorine, methoxy, ethoxy, methylthio or ethylthio; or
  • R! very particularly preferably represents alkynyl having 3 to 6 carbon atoms which is unsubstituted or monosubstituted to trisubstituted, identically or differently substituted by fluorine, chlorine, methoxy, ethoxy, methylthio or ethylthio; or
  • R! very particularly preferably represents cycloalkyl having 3 to 6 carbon atoms which is unsubstituted or monosubstituted to trisubstituted, identically or differently substituted by fluorine, chlorine, methyl, ethyl, methoxy or trifluoromethyl;
  • R 1 very particularly preferably represents halogenoalkyl having 1 to 4 carbon atoms which is substituted by 1 to 9 fluorine and / or chlorine atoms; or
  • R ⁇ is most preferably hydrogen, alkyl of 1 to 2 carbon atoms
  • R! and R ⁇ are most preferably taken together with the nitrogen atom to which they are attached, for a saturated or unsaturated heterocyclic ring having 3 to 6 ring members, wherein the heterocycle optionally contains a further nitrogen, oxygen or sulfur atom as a ring member and wherein the Heterocycle may be unsubstituted or substituted up to two times by fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy or ethoxy; R 3 very particularly preferably represents CO-N, CO-N M 1 , COOH, CO ° M 1 ;
  • R 4 is very particularly preferably hydrogen
  • M 1 very particularly preferably represents Na + , K + , Vi Ca 2+ , V 2 Mg 2+ , NH 4 + , NH 3 CH 3 + , NH 2 (CHj) 2 + , NH (CH 3 ) 3 + , NH (C 2 Hj) 3 + , NH 2 (C 2 Hs) 2 + , NH 3 C 2 H 5 + , NH 3 IC 3 H 7 + , NH 2 (IC 3 Hy) 2 + , NH 3 -CH 2 -C 6 H 5 + or N (CHj) 3 -H 2 -C 6 H 5 + ;
  • R 5 very particularly preferably represents the groups COR 6 , S (O) R 6 , S (O 1 R 6 , cyano, COOR 6 ,
  • R 6 very particularly preferably represents hydrogen, in each case optionally monosubstituted to trisubstituted by methoxy, ethoxy, methylthio, ethylthio, cyano, CO-O-methyl or CO-O-ethyl, alkyl having 1 to 3 carbon atoms or cyclopropyl, for
  • Haloalkyl having 1 to 3 carbon and 1 to 7 fluorine and / or chlorine atoms.
  • the compounds of the invention are generally defined by the formula (I). Especially particularly preferred substituents, fragments or ranges of the radicals listed in the formulas mentioned above and below are explained below for a very particularly preferred embodiment of the present invention:
  • X is particularly particularly preferably hydrogen, chlorine, bromine, methyl or trifluoromethyl
  • pyrazinyl which is linked in the 2-position and may be monosubstituted, monosubstituted or differently substituted by fluorine, chlorine, bromine, cyano, hydroxy, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl , Hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, carboxy and / or carboxymethyl or
  • pyrazolyl which is linked in the 1-position and may be mono- to disubstituted, identical or different, by fluorine, chlorine, bromine, Cyano, hydroxy, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, heptafluoroisopropyl, heptafluoro-n-propyl, carboxy and / or carboxymethyl or
  • pyrazolyl which is linked in the 4- or 5-position and may be monosubstituted to trisubstituted, identically or differently by fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, Methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, carboxy and / or carboxymethyl or
  • thiazolyl which is linked in the 4-position and may be monosubstituted, disubstituted or differently substituted by fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl , Hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, carboxy and / or carboxymethyl;
  • Z is particularly particularly preferably chlorine, methoxy, ethoxy, methylthio,
  • Y is particularly particularly preferably hydrogen, chlorine, bromine, methyl, ethyl, trifluoromethyl or cyclopropyl;
  • R 1 particularly particularly preferably represents hydrogen, alkyl having 1 to 4 carbon atoms, which is unsubstituted or monosubstituted, monosubstituted or differently substituted by methyl, ethyl, methoxy, ethoxy, cyclopropyl, cyclopentyl, cyclohexyl, methylthio or ethylthio; or
  • R * is particularly particularly preferably alkenyl having 3 to 6 carbon atoms which is unsubstituted or monosubstituted to trisubstituted, identically or differently substituted by fluorine, chlorine, methoxy, ethoxy, methylthio or ethylthio; or
  • R! in particular, very particular preference is given to alkynyl having 3 to 6 carbon atoms which is unsubstituted or monosubstituted to trisubstituted, identically or differently substituted by fluorine, chlorine, methoxy, ethoxy, methylthio or ethylthio; or R 1 particularly particularly preferably represents cycloalkyl having 3 to 6 carbon atoms which is unsubstituted or monosubstituted to trisubstituted, identically or differently substituted by fluorine, chlorine, methyl, ethyl, methoxy or trifluoromethyl;
  • R 1 very particularly preferably represents halogenoalkyl having 1 to 4 carbon atoms which is substituted by 1 to 9 fluorine and / or chlorine atoms; or
  • R ⁇ is particularly particularly preferably hydrogen, methyl or ethyl
  • R! and R 1 are particularly particularly preferably taken together with the nitrogen atom to which they are bonded, for a saturated or unsaturated heterocyclic ring having 3 to 6 ring members, where the heterocycle is optionally a further nitrogen,
  • Oxygen or sulfur atom as ring member and wherein the heterocycle may be unsubstituted or substituted up to two times by fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy or ethoxy;
  • R 3 particularly particularly preferably represents CO-N, CO-NM 1 , COOH,
  • R 4 is particularly particularly preferably hydrogen
  • M 1 is most particularly preferably Na + , K + , Vi Ca 2+ , Vi Mg 2+ , NH 4 + , NH 3 CH 3 + , NH 2 (CH 3 ) A NH (CH 3 ) 3 + , NH (C 2 H 5 ) 3 + , NH 2 (C 2 Hs) 2 + , NH 3 C 2 H 5 + , NH 3 JC 3 H 7 + , NH 2 (iC 3 H 7 ) 2 + , NH 3 -CH 2 -C 6 H 5 + or N (CH 3 ) 3 -H 2 -C 6 H 5 + ;
  • R 1 particularly particularly preferably represents S (O) R 1, S (O) 2 R 1,
  • R 6 particularly particularly preferably represents hydrogen, in each case optionally monosubstituted to trisubstituted by fluorine, chlorine, methoxy, ethoxy, methylthio, ethylthio, cyano,
  • Cyclopropyl for haloalkyl having 1 to 3 carbon and 1 to 7 fluorine and / or chlorine atoms.
  • R 1 is hydrogen, alkyl of 1 to 10 carbon atoms which is unsubstituted or monosubstituted to pentavalent, identical or different, by cyano, hydroxy, alkoxy of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, mercapto, alkylthio of 1 to 4 Carbon atoms, amino, mono- or dialkylamino each having 1 to 4 carbon atoms and haloalkyl having 1 to 10 carbon and 1 to 21
  • Halogen atoms and R 2 is hydrogen.
  • Het is pyridinyl which is linked in the 2-, 3- or 4-position and may be monosubstituted, disubstituted or differently substituted by fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio , Hydroximinomethyl, Hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, carboxy and / or carboxymethyl or
  • pyrazinyl which is linked in the 2-position and may be monosubstituted, disubstituted or differently substituted by fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, Methoximinoethyl, trifluoromethyl, carboxy and / or carboxymethyl or
  • pyrazolyl which is linked in the 1-position and may be monosubstituted, disubstituted or differently substituted by fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximino methyl, methoximinoethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, heptafluoro-isopropyl, heptafluoro-n-propyl, carboxy and / or carboxymethyl or
  • pyrazolyl which is linked in the 4- or 5-position and may be monosubstituted to trisubstituted, identically or differently substituted by fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl , Methoxymino-methyl, methoximinoethyl, trifluoromethyl, carboxy and / or carboxymethyl or
  • thiazolyl which is linked in the 4-position and may be monosubstituted, disubstituted or differently substituted by fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, Methoximinoethyl, trifluoromethyl, carboxy and / or carboxymethyl
  • Het is pyridinyl which is linked in the 2-, 3- or 4-position and may be monosubstituted, disubstituted or differently substituted by fluorine, chlorine, bromine, cyano,
  • Het is pyrazinyl which is linked in the 2-position and may be monosubstituted, disubstituted or differently substituted by fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, Methoximinomethyl, methoximinoethyl, trifluoromethyl, carboxy and / or carboxymethyl stands.
  • Methoximinomethyl methoximinoethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl,
  • Het is pyrazolyl which is linked in the 4- or 5-position and may be monosubstituted to trisubstituted, identically or differently, by fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, Hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl, carboxy and / or carboxymethyl stands.
  • Het for thiazolyl which is linked in the 4-position and may be monosubstituted, disubstituted or differently substituted by fluorine, chlorine, bromine, cyano, hydroxyl, mercapto,
  • Methoximinomethyl, methoximinoethyl, trifluoromethyl, carboxy and / or carboxymethyl stands.
  • R ⁇ is S (O) R ⁇ and R ⁇ is Alkyi having 1 to 3 carbon atoms and / or haloalkyl having 1 to 3 carbon and 1 to 5 fluorine and / or chlorine atoms and / or cyclopropyl.
  • R 1 is S (O) 2 R "and R" is alkyl having 1 to 3 carbon atoms and / or haloalkyl having 1 to 3 carbon atoms and 1 to 5 fluorine and / or chlorine atoms and / or cyclopropyl.
  • R 1 represents S (O) R ** and R 1 denotes alkyl having 1 to 3 carbon atoms and / or haloalkyl having 1 to 3 carbon atoms and 1 to 5 fluorine and / or Chlorine atoms and / or cyclopropyl stands.
  • R 5 for S (O) R 6 or S (O) 2 R 6 and R 6 is hydrogen, each optionally optionally monosubstituted to pentavalent by fluorine, chlorine, C, -C 3 alkoxy, C r C 3 alkylthio, cyano , CO 2 H or CO-OC, - C 3 alkyl-substituted C, -C 8 alkyl, C 3 -C 8 -alkenyl or C 3 -C 8 -alkynyl is C 8 - haloalkyl having 1 to 17 fluorine and / or chlorine atoms, in each case optionally mono- to trisubstituted by fluorine, chlorine, Q-Gi-alkyl, Ci-C 2 haloalkyl, QC 2 -alkoxy,
  • Het is pyridinyl which is linked in the 2-, 3- or 4-position and may be monosubstituted, disubstituted or differently substituted by fluorine, chlorine, bromine, cyano,
  • pyrazinyl which is linked in the 2-position and may be monosubstituted, disubstituted or differently substituted by fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, Methoximinoethyl, trifluoromethyl, carboxy and / or carboxymethyl or
  • pyrazolyl which is linked in the 1-position and may be monosubstituted, disubstituted or differently substituted by fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, methoximinomethyl, Methoximinoethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, heptafluoro-isopropyl, heptafluoro-n-propyl, carboxy and / or carboxymethyl or
  • pyrazolyl which is linked in the 4- or 5-position and may be monosubstituted to trisubstituted, identically or differently substituted by fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl , Methoximinomethyl, methoximinoethyl, trifluoromethyl, carboxy and / or carboxymethyl or
  • thiazolyl which is linked in the 4-position and may be monosubstituted, disubstituted or differently substituted by fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl, Methoximinomethyl, methoximinoethyl, trifluoromethyl, carboxy and / or carboxymethyl stands.
  • Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl
  • heteroatoms e.g. in alkoxy, as far as possible, in each case straight-chain or branched.
  • optionally substituted radicals may be monosubstituted or polysubstituted, with multiple substituents the substituents being the same or different.
  • the malonic esters of the formula (III) are known in some cases and can be prepared by methods known from the literature (for example WO 04/006913, WO 04/005876).
  • R8 has the meaning given above and
  • Het 1 for pyrazolyl which is linked in 1-position and may be monosubstituted or disubstituted by identical or different haloalkyl having 1 to 7 fluorine and / or chlorine atoms, in particular trifluoromethyl, trichloromethyl, pentafluoroethyl, heptafluoroisopropyl or heptafluoro-n -propyl, or
  • heterocyclylmalonic esters of the formula (III) can be prepared by reacting heterocyclyl unsubstituted esters of the formula (TLC) in the presence of a base with carbonates of the formula (X).
  • the Heterocyclylessigester of formula (DC), when Het 1 is pyrazol-1-yl, can be prepared, for example, by reacting heterocycles of the formula (XI) in the presence of a base with bromoacetic esters of the formula (XII), or
  • V and W independently of one another are hydrogen, halogenoalkyl having 1 to 7 fluorine and / or chlorine atoms, in particular trifluoromethyl, trichloromethyl, pentafluoroethyl, heptafluoroisopropyl or heptafluoro-n-propyl, and R 8 are each as defined above.
  • the stepwise reaction of the starting compounds of the formula (II) and (HI) to the amine of the formula (VI) can be carried out, for example, analogously to the processes specified in WO 04/000844 and in WO 05/082907.
  • saponification of the ester function in compounds of the formula (VI) compounds of the formula (I-a) are obtained. From these can z. B. by the action of oxalyl chloride, the acid chlorides of the formula (VII) are formed.
  • the compounds of the formula (VIH) used for the further reaction of the acid chlorides of the formula (VII) are known. They are commercially available or can be prepared by known methods familiar to the person skilled in the art, as described, for example, in Houben-Weyl, Methods of Organic Chemistry.
  • the compounds of formula (I) can be obtained in various ways.
  • the present invention therefore also relates to a process for the preparation of heterocyclic carboxylic acid derivatives of the general formula (I) as defined above, characterized in that in process (1)
  • Het and Y are as defined above and R is alkyl, halogenated and
  • Het and Y are as defined above, X is halogen and R is alkyl,
  • the present invention also relates to a process for the preparation of compounds of the general formula (IV) as defined above, characterized
  • Het is as defined above and R 8 is alkyl or aryl;
  • Het 2 stands for six-membered heterocycles and Hal stands for bromine or iodine
  • a base preferably under the action of a base and in the presence of catalytically active amounts of a transition metal of transition group VIII of the Periodic Table (Group 10 according to IUPAC), for.
  • a transition metal of transition group VIII of the Periodic Table Group 10 according to IUPAC
  • nickel palladium or platinum, especially in the presence of a palladium catalyst (suitable palladium catalysts containing ligands, such as, for example, phosphines), and
  • Her 2 represents six-membered heterocycles, hydrolyzed in the presence of acid or base and
  • Het 2 represents six-membered heterocycles
  • R 7 is alkyl, preferably C r C 4 alkyl.
  • R 8 is alkyl, preferably C r C 8 alkyl or aryl.
  • X is halogen, preferably chlorine or bromine.
  • the compounds of the formula (VHT), (XX), (XXI) and (XVU) are known. They are commercially available or can be prepared by known methods familiar to the person skilled in the art, as described, for example, in Houben-Weyl, Methods of Organic Chemistry.
  • the compounds of the formula (II) are known from the literature (see, for example, US-A 3,515,715, US-A 3,634,391 and WO 05/082907).
  • Suitable reaction auxiliaries are, if appropriate, the customary inorganic or organic bases or acid acceptors. These include, preferably, alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, sodium, potassium or calcium acetate, lithium, sodium, potassium or Calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or calcium bicarbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium potassium or calcium hydroxide, sodium or potassium methoxide.
  • Suitable diluents are virtually all inert organic solvents. These include, preferably, aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers, such as diethyl - and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl or methyl isobutyl ketone, esters such as methyl acetate or e
  • reaction temperatures can be varied within a substantial range in the processes according to the invention. In general, one operates at temperatures between 0 0 C and 250 0 C, preferably at temperatures between 1O 0 C and 185 ° C.
  • the processes according to the invention are generally carried out under normal pressure. However, it is also possible to work under elevated or reduced pressure.
  • the starting materials needed in each case are generally used in approximately equimolar amounts. However, it is also possible to use one of the components used in each case in a larger excess.
  • the work-up is carried out in the inventive method in each case by customary methods (cf., the preparation examples).
  • ammonium sulfate as a formulation aid is described for certain active ingredients and applications (WO 92/16108), but it is there to stabilize the formulation, not to increase the effect.
  • the present invention thus relates to the use of ammonium or phosphonium salts for increasing the efficacy of plant protection products containing insecticidally and / or acaricidally active heterocyclic carboxylic acid derivatives (I) as active ingredient.
  • the invention also relates to compositions containing insecticidally and / or acaricidally active heterocyclic carboxylic acid derivatives (I) and the activity-enhancing ammonium or phosphonium salts, both formulated active ingredients and ready-to-use agents (spray liquors). Finally, the invention further relates to the use of these agents for controlling noxious insects and / or spider mites.
  • Ammonium and phosphonium salts which, according to the invention, enhance the action of crop protection agents containing heterocyclic carboxylic acid derivatives (I) are defined by formula (XV)
  • Q is nitrogen or phosphorus
  • R 26 , R 27 , R 28 and R 29 independently of one another are hydrogen or in each case optionally substituted C 1 -C 6 -alkyl or mono- or polyunsaturated, optionally substituted C 1 -C 6 -alkylene, where the substituents are selected from halogen, nitro and cyano can, R 26 , R 27 , R 28 and R 29 preferably independently of one another represent hydrogen or in each case optionally substituted C 1 -C 4 -alkyl, where the substituents can be selected from halogen, nitro and cyano,
  • R 26 , R 27 , R 28 and R 29 more preferably independently of one another are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl,
  • R 26 , R 27 , R 28 and R 29 most preferably represent hydrogen
  • R 26 , R 27 , R 28 and R 29 furthermore very particularly preferably mean at the same time methyl or simultaneously ethyl
  • n 1, 2, 3 or 4
  • n is preferably 1 or 2
  • R 30 is an inorganic or organic anion
  • R 30 is preferably hydrogencarbonate, tetraborate, fluoride, bromide, iodide, chloride, monohydrogenphosphate, dihydrogenphosphate, hydrogensulphate, tartrate, sulphate, nitrate, thiosulphate, thiocyanate, formate, lactate, acetate, propionate, butyrate, pentanoate, citrate or oxalate,
  • R 30 furthermore preferably represents carbonate, pentaborate, sulfite, benzoate, hydrogen oxalate, hydrogen citrate, methyl sulfate or tetrafluoroborate,
  • R 30 particularly preferably represents lactate, sulfate, nitrate, thiosulphate, thiocyanate, citrate, oxalate, acetate or formate,
  • R 30 is also particularly preferred for monohydrogen phosphate or dihydrogen phosphate
  • R 30 is very particularly preferred for thiocyanate, dihydrogen phosphate, monohydrogen phosphate or sulfate.
  • the ammonium and phosphonium salts of the formula (XV) can be used in a wide concentration range for increasing the effect of crop protection agents containing heterocyclic carboxylic acid derivatives (I).
  • the ammonium or phosphonium salts in the ready-to-use crop protection agent are in a concentration of 0.5 to 80 mmol / l, preferably 0.75 to 37.5 mmol / l, particularly preferably 1.5 to 25 mmol / 1 used.
  • the ammonium and / or phosphonium salt concentration in the formulation is selected to be in the specified general, preferred or most preferred ranges after dilution of the formulation to the desired drug concentration.
  • the concentration of the salt in the formulation is usually 1-50 wt .-%.
  • the concentration of the active ingredient in the formulation is usually 0.01-50 wt .-%.
  • a penetration promoter is added to the crop protection agents to increase the effect. It can be described as completely surprising that even in these cases an even greater increase in activity can be observed.
  • the present invention thus also relates to the use of a combination of penetration promoters and ammonium and / or phosphonium salts to increase the efficacy of crop protection agents containing insecticidally and / or acaricidally active heterocyclic carboxylic acid derivatives (I) as active ingredient.
  • the invention also relates to compositions containing insecticidally and / or acaricidally active heterocyclic carboxylic acid derivatives (I), penetrants and ammonium and / or phosphonium salts, both formulated active ingredients and ready-to-use agents (spray liquors).
  • the subject matter of the invention is the use of these agents for controlling harmful insects.
  • Suitable penetration promoters in the present context are all those substances which are usually used to improve the penetration of agrochemical active substances into plants.
  • Penetration promoters are in this context defined by the fact that they can penetrate from the aqueous spray mixture and / or from the spray coating in the cuticle of the plant and thereby increase the material mobility (mobility) of active ingredients in the cuticle.
  • the method described in the literature can be used to determine this property.
  • Suitable penetration promoters are, for example, alkanol alkoxylates.
  • Penetration promoters according to the invention are alkanol alkoxylates of the formula
  • R is straight-chain or branched alkyl having 4 to 20 carbon atoms
  • R 1 is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl or n-hexyl
  • AO stands for an ethylene oxide radical, a propylene oxide radical, a butylene oxide radical or mixtures of ethylene oxide and propylene oxide radicals or butylene oxide radicals and
  • v stands for numbers from 2 to 30.
  • a preferred group of penetration enhancers are alkanol alkoxylates of the formula
  • n stands for numbers from 2 to 20.
  • Another preferred group of penetration enhancers are alkanol alkoxylates of the formula
  • EO stands for -CH 2 -CH 2 -O-
  • q stands for numbers from 1 to 10.
  • Another preferred group of penetration promoters are alkanol alkoxylates of the formula RO - (- PO-) r - (EO-) s -R '(XVI-c) in which
  • R has the abovementioned meaning, R 'has the abovementioned meaning, EO stands for -CH 2 -CH 2 -O-,
  • r is a number from 1 to 10 and s is a number from 1 to 10.
  • alkanol alkoxylates of the formula RO - (- EO-) p - (- BO-) q -R '(XVI-d) in which
  • R and R 1 have the meanings given above, EO 2 -CH 2 -O- is CH, BO - CH CH ⁇ ⁇ TCH is 0;
  • CH CH
  • p numbers from 1 to 10
  • q represents numbers from 1 to 10.
  • Another preferred group of penetration enhancers are alkanol alkoxylates of the formula
  • EO is CH 2 -CH 2 -O-
  • s stands for numbers from 1 to 10.
  • Another preferred group of penetration promoters are alkanol alkoxylates of the formula
  • u stands for numbers from 6 to 17.
  • R is preferably butyl, isobutyl, n-pentyl, i-pentyl, neopentyl, n-hexyl, i-hexyl, n-octyl, i-octyl, 2-ethylhexyl, nonyl, i-nonyl, decyl, n-butyl Dodecyl, i-dodecyl, lauryl, myristyl, i-tridecyl, trimethyl-nonyl, palmityl, stearyl or eicosyl.
  • alkanol alkoxylate of the formula (XVI-c) is 2-ethyl-hexyl alkoxylate of the formula
  • EO is -CH 2 CH 2 -O-
  • EO is CH 2 -CH 2 -O-
  • BO stands for - CH-CH ⁇ -CH-O
  • the numbers 10, 6 and 2 represent average values called.
  • alkanol alkoxylates of the formula (XVI-f) are compounds of this formula in which
  • alkanol alkoxylate of the formula (XVI-f-1) Particular preference is given to alkanol alkoxylate of the formula (XVI-f-1)
  • u stands for the average 8.4.
  • alkanol alkoxylates are generally defined by the above formulas. These substances are mixtures of substances of the specified type with different chain lengths. For the indices, therefore, average values are calculated, which can also differ from whole numbers.
  • alkanol alkoxylates of the formulas given are known and are in some cases commercially available or can be prepared by known methods (compare WO 98/35 553, WO 00/35 278 and EP-A 0 681 865).
  • substances which promote the availability of the compounds of the formula (I) in the spray coating are also suitable as penetration promoters.
  • These include, for example, mineral or vegetable oils. Suitable oils are all mineral or vegetable, optionally modified, oils which can usually be used in agrochemical compositions. Examples include sunflower oil, rapeseed oil, olive oil, castor oil, rapeseed oil, corn kernel oil, cottonseed oil and soybean oil or the esters of said oils. Rape oil, sunflower oil and their methyl or ethyl esters are preferred.
  • the concentration of penetration promoter can be varied within a wide range in the agents according to the invention.
  • a formulated crop protection agent it is generally from 1 to 95% by weight, preferably from 1 to 55% by weight, more preferably from 15 to 40% by weight.
  • the concentration is generally between 0.1 and 10 g / l, preferably between 0.5 and 5 g / l.
  • Plant protection agents according to the invention may also contain other components, for example surfactants or dispersing aids or emulsifiers.
  • Suitable nonionic surfactants or dispersing agents are all substances of this type which can usually be used in agrochemical compositions. Preference is given to polyethylene oxide-polypropylene oxide block copolymers, polyethylene glycol ethers of linear alcohols, reaction products of fatty acids with ethylene oxide and / or propylene oxide, furthermore polyvinyl alcohol, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and polyvinylpyrrolidone and copolymers of (meth) acrylic acid and (meth) acrylic esters , furthermore alkyl ethoxylates and alkylaryl ethoxylates, which may optionally be phosphated and optionally neutralized with bases, wherein sorbitol ethoxylates may be mentioned by way of example, and polyoxyalkyleneamine derivatives.
  • Suitable anionic surfactants are all substances of this type conventionally usable in agrochemical compositions. Preference is given to alkali metal and alkaline earth metal salts of alkyl sulfonic acids or alkylaryl sulfonic acids.
  • anionic surfactants or dispersing agents are salts of polystyrenesulfonic acids which are sparingly soluble in vegetable oil, salts of polyvinylsulfonic acids, salts of naphthalenesulfonic acid-formaldehyde condensation products, salts of condensation products of naphthalenesulfonic acid, phenolsulfonic acid and formaldehyde and salts of lignosulfonic acid.
  • additives which may be included in the formulations of the invention are emulsifiers, antifoaming agents, preservatives, antioxidants, dyes and inert fillers into consideration.
  • Preferred emulsifiers are ethoxylated nonylphenols, reaction products of alkylphenols with ethylene oxide and / or propylene oxide, ethoxylated arylalkylphenols, furthermore ethoxylated and propoxylated arylalkylphenols, and sulfated or phosphated arylalkyl ethoxylates or ethoxy-propoxylates, sorbitan derivatives such as polyethylene oxide sorbitan fatty acid esters and sorbitan Fatty acid esters, may be mentioned as examples.
  • the active compounds according to the invention are suitable for plant tolerance, favorable warm-blood toxicity and good environmental compatibility for the protection of plants and plant organs, for increasing crop yields, improving the quality of the crop and for controlling animal pests, in particular insects, arachnids, helminths, nematodes and
  • Mollusks used in agriculture horticulture, animal husbandry, forests, gardens and
  • Anoplura e.g. Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.
  • arachnids e.g. Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp.
  • Eriophyes spp. Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp. Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici.
  • Starchus spp. Symphyletes spp., Tenebrio molitor, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp.
  • Gastropoda e.g. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.
  • helminths from the class of helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp , Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Lo
  • protozoa such as Eimeria
  • Eimeria protozoa
  • Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp., Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana, Trichoplusia spp ..
  • Orthoptera e.g. Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.
  • siphonaptera e.g. Ceratophyllus spp., Xenopsylla cheopis.
  • Symphyla e.g. Scutigerella immaculata.
  • Thysanoptera e.g. Basothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.
  • Thysanura e.g. Lepisma saccharina.
  • the plant parasitic nematodes include, for example, Anguina spp., Aphelenchoides spp., Belonoaimus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heliocotylenchus spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Rotylenchus spp., Trichodorus spp., Tylenchorhynchus spp., Tylenchulus spp., Tylenchulus semipenetrans, Xiphinema spp.
  • the compounds of the formula (I) according to the invention are notable in particular for their potent action against insects, parasites of the subclass of Acari (Acarina) (such as mites, spider mites and / or ticks) and / or nematodes.
  • insects parasites of the subclass of Acari (Acarina) (such as mites, spider mites and / or ticks) and / or nematodes.
  • the compounds of the invention have a strong fimgicidal action and can be used for controlling phytopathogenic harmful fungi in plant and material protection.
  • Fungicides can be used in crop protection to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
  • Blumeria species such as Blumeria graminis
  • Podosphaera species such as Podosphaera leucotricha
  • Sphaerotheca species such as Sphaerotheca fuliginea
  • Uncinula species such as Uncinula necator
  • Gymnosporangium species such as Gymnosporangium sabinae
  • Hemileia species such as Hemileia vastatrix
  • Phakopsora species such as Phakopsora pachyrhizi and Phakopsora meibomiae
  • Puccinia species such as Puccinia recondita
  • Uromyces species such as Uromyces appendiculatus
  • Bremia species such as Bremia lactucae
  • Peronospora species such as Peronospora pisi or P. brassicae
  • Phytophthora species such as Phytophthora infestans
  • Plasmopara species such as Plasmopara viticola
  • Pseudoperonospora species such as Pseudoperonospora humuli or
  • Pythium species such as Pythium ultimum
  • Alternaria species such as Alternaria solani;
  • Cercospora species such as Cercospora beticola
  • Cladosporium species such as Cladosporium cucumerinum
  • Cochliobolus species such as Cochliobolus sativus
  • Colletotrichum species such as Colletotrichum lindemuthanium
  • Cycloconium species such as cycloconium oleaginum
  • Diaporthe species such as Diaporthe citri;
  • Elsinoe species such as Elsinoe fawcettii
  • Gloeosporium species such as, for example, Gloeosporium laeticolor
  • Glomerella species such as Glomerella cingulata
  • Guignardia species such as Guignardia bidwelli;
  • Leptosphaeria species such as Leptosphaeria maculans
  • Magnaporthe species such as Magnaporthe grisea
  • Mycosphaerella species such as Mycosphaerella graminicola and Mycosphaerella fijiensis;
  • Phaeosphaeria species such as Phaeosphaeria nodorum
  • Pyrenophora species such as, for example, Pyrenophora teres
  • Ramularia species such as Ramularia collo-cygni
  • Rhynchosporium species such as Rhynchosporium secalis
  • Septoria species such as Septoria apii
  • Typhula species such as Typhula incarnata
  • Venturia species such as Venturia inaequalis
  • Corticium species such as Corticium graminearum
  • Fusarium species such as Fusarium oxysporum
  • Gaeumannomyces species such as Gaeumannomyces graminis
  • Rhizoctonia species such as Rhizoctonia solani
  • Tapesia species such as Tapesia acuformis
  • Thielaviopsis species such as Thielaviopsis basicola
  • Ear and panicle diseases caused by e.g. Alternaria species, such as Alternaria spp .;
  • Aspergillus species such as Aspergillus flavus
  • Cladosporium species such as Cladosporium cladosporioides
  • Claviceps species such as Claviceps purpurea
  • Fusarium species such as Fusarium culmorum
  • Gibberella species such as Gibberella zeae
  • Monographella species such as Monographella nivalis
  • Tilletia species such as Tilletia caries
  • Urocystis species such as Urocystis occulta
  • Ustilago species such as Ustilago nuda
  • Aspergillus species such as Aspergillus flavus
  • Botrytis species such as Botrytis cinerea
  • Penicillium species such as Penicillium expansum and Penicillium purpurogenum
  • Sclerotinia species such as Sclerotinia sclerotiorum
  • Verticilium species such as Verticilium alboatrum
  • Fusarium species such as Fusarium culmorum
  • Phytophthora species such as Phytophthora cactorum
  • Pythium species such as Pythium ultimum
  • Rhizoctonia species such as Rhizoctonia solani
  • Sclerotium species such as Sclerotium rolfsii
  • Nectria species such as Nectria galligena
  • Monilinia species such as Monilinia laxa
  • Taphrina species such as Taphrina deformans
  • Degenerative diseases woody plants caused by eg.
  • Esca species such as Phaeomoniella chlamydospora and Phaeoacremonium aleophilum and Fomitiporia mediterranea;
  • Botrytis species such as Botrytis cinerea
  • Rhizoctonia species such as Rhizoctonia solani
  • Helminthosporium species such as Helminthosporium solani
  • Xanthomonas species such as Xanthomonas campestris pv. Oryzae;
  • Pseudomonas species such as Pseudomonas syringae pv. Lachrymans;
  • Erwinia species such as Erwinia amylovora
  • the following diseases of soybean beans can be controlled:
  • Alternaria leaf spot (Alternaria spec. Atrans tenuissima), Anthracnose (Colletotrichum gloeosporoides dematium var. Truncatum), Brown spot (Septoria glycines), Cercospora leaf spot and blight (Cercospora kikuchii), Choanephora leaf blight (Choanephora infundibulifera trispora (Syn.)) , Dactuliophora leaf spot (Dactuliophora glycines), Downy Mildew (Peronospora manshurica), Drechslera blight (Drechslera glycini), Frogeye leaf spot (Cercospora sojina), Leptosphaerulina leaf spot (Leptosphaerulina trifolii), Phyllostica leaf spot (Phyllosticta sojaecola), Pod and Stem Blight (Phomopsis sojae), Powdery Milde
  • Black Root Red (Calonectria crotalariae), Charcoal Red (Macrophomina phaseolina), Fusarium Blight or Wiit, Root Red, and Pod and Collar Red (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), Mycoleptodiscus Root Red (Mycoleptodiscus terrestris), Neocosmospora (Neocosmopspora vasinfecta), Pod and Star Blight (Diaporthe phaseolorum), Star Canker (Diaporthe phaseolorum var.
  • Phytophthora red (Phytophthora megasperma), Brown Stem Red (Phialophora gregata), Pythium red (Pythium aphanidermatum, Pythium irregular, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), Rhizoctonia Root Red, Stem Decay, and Damping Off (Rhizoctonia solani), Sclerotinia Stem Decay (Sclerotinia sclerotiorum), Sclerotinia Southern Blight (Sclerotinia rolfsii), Thielaviopsis Root Red (Thielaviopsis basicola).
  • the compounds of the invention also have a strong tonic effect in plants. They are therefore suitable for mobilizing the plant's own defenses against attack by undesired phytopathogenic harmful fungi.
  • plant-strengthening (resistance-inducing) compounds are to be understood as meaning substances which are capable of stimulating the defense system of plants in such a way that the treated plants, upon subsequent inoculation with unwanted plant-pathogenic harmful fungi, display extensive resistance to these plant-pathogenic harmful fungi.
  • the compounds of the invention can therefore be used to protect plants within a certain period of time after the treatment against the infestation by said pathogens.
  • the period of time within which protection is afforded generally extends from 1 to 10 days, preferably 1 to 7 days after the treatment of the plants with the active substances.
  • the good plant tolerance of the compounds in the necessary concentrations for controlling plant diseases allows treatment of above-ground parts of plants, of plant and seed, and the soil.
  • the compounds according to the invention can be used with particularly good success for controlling cereal diseases, such as e.g. against Puccinia species and diseases in the wine, fruit and vegetable growing, such. against Botrytis, Venturia or Alternaria species.
  • the compounds according to the invention are also suitable for increasing crop yield. They are also low toxicity and have good plant tolerance.
  • the compounds according to the invention may optionally also be used in certain concentrations or application rates as herbicides, safeners, growth regulators or agents for improving plant properties, or as microbicides, for example as fungicides, Antifungals, bactericides, viricides (including anti-viral agents) or as agents against MLO (Mycoplasma-like-organism) and RLO (Rickettsia-like-organism). If appropriate, they can also be used as intermediates or precursors for the synthesis of further active ingredients.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, scattering granules, suspension-emulsion concentrates, active substance-impregnated natural substances, active substance impregnated synthetic materials, fertilizers and micro-encapsulants in polymeric materials.
  • customary formulations such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, scattering granules, suspension-emulsion concentrates, active substance-impregnated natural substances, active substance impregnated synthetic materials, fertilizers and micro-encapsulants in polymeric materials.
  • formulations are prepared in a known manner, e.g. by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents.
  • extenders ie liquid solvents and / or solid carriers
  • surface-active agents ie emulsifiers and / or dispersants and / or foam-forming agents.
  • Excipients which can be used are those which are suitable for imparting special properties to the composition itself and / or preparations derived therefrom (for example spray liquor, seed dressing), such as certain technical properties and / or specific biological properties.
  • Typical auxiliaries are: extenders, solvents and carriers.
  • polar and non-polar organic chemical liquids e.g. from the classes of aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), alcohols and polyols (which may also be substituted, etherified and / or esterified), ketones (such as acetone, cyclohexanone), Esters (including fats and oils) and (poly) ethers, simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide).
  • aromatic and non-aromatic hydrocarbons such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes
  • alcohols and polyols which may also be substituted, etherified and / or esterified
  • ketones such
  • organic solvents can also be used as auxiliary solvents.
  • AJs liquid solvents are essentially in question: aromatics such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, eg petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol as well as their ethers and esters, Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethyl sulfoxide, and water.
  • Suitable solid carriers are:
  • Ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as fumed silica, alumina and silicates, as solid carriers for granules are suitable: e.g. crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as paper, sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: e.g.
  • nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates;
  • suitable dispersants are non-ionic and / or ionic substances, e.g.
  • Adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-type polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids may be used in the formulations.
  • Dyes such as inorganic pigments, e.g. 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.
  • inorganic pigments e.g. 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.
  • additives may be fragrances, mineral or vegetable optionally modified oils, waxes and nutrients (also trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • Stabilizers such as cold stabilizers, preservatives, antioxidants, light stabilizers or other chemical and / or physical stability-improving agents may also be present.
  • the formulations generally contain between 0.01 and 98% by weight of active ingredient, preferably between 0.5 and 90%.
  • the active ingredient according to the invention may be present in its commercial formulations as well as in the formulations prepared from these formulations in admixture with other active ingredients such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, safeners, fertilizers or semiochemicals.
  • active ingredients such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, safeners, fertilizers or semiochemicals.
  • a mixture with other known active ingredients, such as herbicides, fertilizers, growth regulators, safeners, semiochemicals, or with agents for improving the plant properties is possible.
  • the active compounds according to the invention can furthermore be present in mixtures with synergists when used as insecticides or fungicides in their commercial formulations and in the forms of use prepared from these formulations.
  • synergists are compounds which increase the effect of the active ingredients without the added synergist itself having to be active.
  • the active compounds according to the invention may also be present in their commercial formulations and in the forms of use prepared from these formulations in mixtures with inhibitors which inhibit degradation of the active ingredient after application in the environment of the plant, on the surface of parts of plants or in plants Reduce tissue.
  • the active substance content of the application forms prepared from the commercial formulations can vary within wide ranges.
  • the active ingredient concentration of the use forms may be from 0.00000001 up to 95% by weight of active compound, preferably between 0.00001 and 1% by weight.
  • the application is done in a custom forms adapted to the application.
  • plants and parts of plants can be treated.
  • plants are understood as meaning all plants and plant populations, such as desirable and undesired wild plants or crop plants (including naturally occurring plants)
  • Crop plants can be plants produced by conventional breeding and Optimization methods or by biotechnological and genetic engineering methods or combinations of these methods can be obtained, including the transgenic plants and including protected by plant breeders' rights or non-protectable plant varieties.
  • Plant parts are to be understood as meaning all aboveground and underground parts and organs of the plants, such as shoot, leaf, flower and root, by way of example leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds and roots, tubers and rhizomes.
  • the plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.
  • the treatment according to the invention of the plants and plant parts with the active ingredients is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, e.g. by dipping, pouring, spraying, evaporating, nebulizing, spreading, brushing, injecting and propagating material, in particular in seeds, further by single or multi-layer wrapping.
  • plants and their parts can be treated.
  • wild-type or plant species obtained by conventional biological breeding methods such as crossing or protoplast fusion
  • plant cultivars and their parts are treated.
  • transgenic plants and plant cultivars obtained by genetic engineering if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated.
  • the terms "parts” or “parts of plants” or “plant parts” have been explained above.
  • Plant varieties are understood to be plants having new traits which have been bred either by conventional breeding, by mutagenesis or by recombinant DNA techniques, which may be varieties, biotypes and genotypes.
  • the treatment according to the invention may also give rise to superadditive ("synergistic") effects, for example reduced application rates and / or extensions of the activity spectrum and / or a Enhancement of the effect of the substances and agents that can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to Dryness or against water or soil salt content, increased flowering power, easier harvest, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or workability of the harvested products possible, which go beyond the actual expected effects ,
  • the preferred plants or plant cultivars to be treated according to the invention include all plants which have obtained genetic material by the genetic engineering modification which gives these plants particularly advantageous valuable properties ("traits") Examples of such properties are better plant growth. increased tolerance to high or low temperatures, increased tolerance to dryness or to bottoms, increased flowering efficiency, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or machinability Further and particularly emphasized examples of such properties are an increased defense of the plants against animal and microbial pests, such as insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance of the plants against certain herbicidal active substances.
  • microbial pests such as insects, mites, phytopathogenic fungi, bacteria and / or viruses
  • transgenic plants are the important crops such as cereals (wheat, rice), corn, soybeans, potatoes, sugar beets, tomatoes, peas and other vegetables, cotton, tobacco, oilseed rape and fruit plants (with the fruits apples, pears, citrus fruits and Grapes), with particular emphasis on maize, soya, potato, cotton, tobacco, rice, canola and oilseed rape.
  • Bt plants are the increased defense of the plants against insects, arachnids, nematodes and snails by toxins produced in the plants, in particular those which are produced by the genetic material from Bacillus thuringiensis (eg by the genes Cry ⁇ A (a) , Cry ⁇ A (b), Cry ⁇ A (c), CryllA, CrylllA, CryfflB2, Cry9c Cry2Ab, Cry3Bb and CrylF, and combinations thereof) in the plants (hereinafter "Bt plants”).
  • Bacillus thuringiensis eg by the genes Cry ⁇ A (a) , Cry ⁇ A (b), Cry ⁇ A (c), CryllA, CrylllA, CryfflB2, Cry9c Cry2Ab, Cry3Bb and CrylF, and combinations thereof
  • Traits also highlight the increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins.
  • SAR systemic acquired resistance
  • systemin phytoalexins
  • elicitors elicitors
  • resistance genes correspondingly expressed proteins and toxins.
  • the increased tolerance of the plants to certain herbicidal active compounds for example imidazolinones, sulfonylureas, glyphosates or phosphinotricin (eg "PAT" gene).
  • PAT phosphinotricin
  • Bt plants are maize varieties, cotton varieties, soybean varieties and potato varieties, which are marketed under the trade names YIELD GARD® (eg maize, cotton, soya), KnockOut® (eg maize), StarLink® (eg corn), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato).
  • YIELD GARD® eg maize, cotton, soya
  • KnockOut® eg maize
  • StarLink® eg corn
  • Bollgard® cotton
  • Nucotn® cotton
  • NewLeaf® potato
  • herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties, which are sold under the trade names Roundup Ready® (tolerance to glyphosate eg corn, cotton, soya), Liberty Link® (tolerance to phosphinotricin, eg rapeseed), EVII® (tolerance against imidazolinone) and STS® (tolerance to sulfonylureas eg corn).
  • Roundup Ready® tolerance to glyphosate eg corn, cotton, soya
  • Liberty Link® tolerance to phosphinotricin, eg rapeseed
  • EVII® tolerance against imidazolinone
  • STS® tolerance to sulfonylureas eg corn.
  • Clearfield® varieties eg corn
  • the listed plants can be treated particularly advantageously according to the invention with the compounds of the general formula I or the active substance mixtures according to the invention.
  • the preferred ranges given above for the active compounds or mixtures also apply to the treatment of these plants.
  • Particularly emphasized is the plant treatment with the compounds or mixtures specifically mentioned in the present text.
  • the present invention therefore also relates, in particular, to a method for protecting seed and germinating plants from the infestation of animal pests and / or phytopathogenic harmful fungi by treating the seed with an agent according to the invention.
  • the invention also relates to the use of the agents according to the invention for the treatment of seed for the protection of the seed and the germinating plant from animal pests and / or phytopathogenic harmful fungi.
  • the invention relates to seed which has been treated with an agent according to the invention for protection against animal pests and / or phytopathogenic harmful fungi.
  • One of the advantages of the present invention is that because of the particular systemic properties of the agents according to the invention, the treatment of the seeds with these agents not only protects the seed itself, but also the resulting plants after emergence from animal pests and / or phytopathogenic harmful fungi. In this way, the immediate treatment of the culture at the time of sowing or shortly afterwards can be omitted.
  • mixtures according to the invention can also be used in particular in the case of transgenic seed.
  • compositions according to the invention are suitable for the protection of seeds of any plant variety used in agriculture, in the greenhouse, in forests or in horticulture.
  • these are seeds of cereals (such as wheat, barley, rye, millet and oats), corn, cotton, soy, rice, potatoes, sunflower, bean, coffee, turnip (eg sugarbeet and fodder), peanut, vegetables ( like tomato, cucumber, onions and lettuce), lawn and ornamental plants.
  • cereals such as wheat, barley, rye, millet and oats
  • corn such as wheat, barley, rye, millet and oats
  • peanut like tomato, cucumber, onions and lettuce
  • the agent according to the invention is applied to the seed alone or in a suitable formulation.
  • the seed is treated in a condition that is so stable that no damage occurs during the treatment.
  • the treatment of the seed can be done at any time between harvesting and sowing.
  • seed is used which has been separated from the plant and freed from flasks, shells, stems, hull, wool or pulp.
  • seed may be used which has been harvested, cleaned and dried to a moisture content below 15% by weight.
  • seed may also be used which, after drying, e.g. treated with water and then dried again.
  • the agents according to the invention can be applied directly, ie without containing further components and without being diluted.
  • suitable formulations and methods for seed treatment are known to those skilled in the art and are described e.g. in the following documents: US 4,272,417 A, US 4,245,432 A, US 4,808,430 A, US 5,876,739 A, US 2003/0176428 A1, WO 2002/080675 A1, WO 2002/028186 A2.
  • the active compound combinations that can be used according to the invention can be converted into the customary seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other seed coating compositions, as well as ULV formulations.
  • formulations are prepared in a known manner by mixing the active ingredients or combinations of active ingredients with conventional additives, such as conventional extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also Water.
  • conventional additives such as conventional extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also Water.
  • Dyes which may be present in the seed dressing formulations which can be used according to the invention are all dyes customary for such purposes. Both water-insoluble pigments and water-soluble dyes are useful in this case. Examples which may be mentioned under the names rhodamine B, CI. Pigment Red 112 and CI. Solvent Red 1 known dyes.
  • Suitable wetting agents which may be present in the seed dressing formulations which can be used according to the invention are all wetting-promoting substances customary for the formulation of agrochemical active compounds.
  • Preferably used are alkylnaphthalene sulfonates, such as diisopropyl or diisobutyl naphthalene sulfonates.
  • Suitable dispersants and / or emulsifiers which may be present in the seed dressing formulations which can be used according to the invention are all nonionic, anionic and cationic dispersants customary for the formulation of agrochemical active compounds.
  • Preferably usable are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants.
  • Particularly suitable nonionic dispersants are, in particular, ethylene oxide-propylene oxide, block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ethers and their phosphated or sulfated derivatives.
  • overall Suitable anionic dispersants are in particular lignosulfonates, polyacrylic acid salts and arylsulfonate-formaldehyde condensates.
  • Defoamers which may be present in the seed-dressing formulations which can be used according to the invention are all foam-inhibiting substances customary for the formulation of agrochemical active compounds.
  • Preferably usable are silicone defoamers and magnesium stearate.
  • Preservatives which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Examples include dichlorophen and Benzylalkoholhemiformal.
  • Suitable secondary thickeners which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Preference is given to cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and highly dispersed silicic acid.
  • Suitable adhesives which may be present in the seed dressing formulations which can be used according to the invention are all customary binders which can be used in pickling agents.
  • Preferably mentioned are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose.
  • the gibberellins are known (see R. Wegler "Chemie der convinced- und Swdlingsbekungsstoff", Vol. 2, Springer Verlag, 1970, pp. 401-412).
  • the seed dressing formulations which can be used according to the invention can be used either directly or after prior dilution with water for the treatment of seed of various kinds.
  • the concentrates or the preparations obtainable therefrom by dilution with water can be used for dressing the seeds of cereals such as wheat, barley, rye, oats and triticale, as well as the seeds of corn, rice, rape, peas, beans, cotton, sunflowers and beets or even vegetable seeds of various nature.
  • the seed dressing formulations which can be used according to the invention or their diluted preparations can also be used for pickling seeds of transgenic plants. In this case, additional synergistic effects may occur in interaction with the substances formed by expression.
  • the seed dressing formulations which can be used according to the invention or the preparations prepared therefrom by the addition of water
  • all are customary Suitable for mixing equipment used for the pickling.
  • the seed is placed in a mixer which adds the desired amount of seed dressing formulations, either as such or after prior dilution with water, and mixes until evenly distributed the formulation on the seed.
  • a drying process follows.
  • the application rate of the seed dressing formulations which can be used according to the invention can be varied within a relatively wide range. It depends on the respective content of the active ingredients in the formulations and on the seed.
  • the application rates of active ingredient combination are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 15 g per kilogram of seed.
  • the active compounds of the invention not only against plant, hygiene and storage pests, but also in the veterinary sector against animal parasites (ecto- and endoparasites) such as ticks, leather ticks, mange mites, running mites, flies (stinging and licking), parasitic fly larvae, lice , Hair pieces, featherlings and fleas.
  • animal parasites ecto- and endoparasites
  • ticks ecto- and endoparasites
  • leather ticks such as ticks, leather ticks, mange mites, running mites, flies (stinging and licking), parasitic fly larvae, lice , Hair pieces, featherlings and fleas.
  • flies stinging and licking
  • parasitic fly larvae such as ticks, leather ticks, mange mites, running mites, flies (stinging and licking), parasitic fly larvae, lice , Hair pieces, featherlings and fleas.
  • Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
  • Trimenopon spp. Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.
  • Nematocerina and Brachycerina e.g. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp , Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Glossina spp., Chrysomyia spppp
  • siphonaptrida e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
  • Actinedida Prostigmata
  • Acaridida e.g. Acarapis spp., Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp , Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.
  • the active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which are farm animals, such as e.g. Cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as e.g. Dogs, cats, caged birds, aquarium fish and so-called experimental animals, such. Hamsters, guinea pigs, rats and mice.
  • arthropods are farm animals, such as e.g. Cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as e.g. Dogs, cats, caged birds, aquarium fish and so-called experimental animals, such. Hamsters, guinea pigs, rats and mice.
  • the use of the active compounds according to the invention takes place in the veterinary sector and in animal husbandry in a known manner by enteral administration in the form of, for example, tablets, capsules, infusions, drenches, granules, pastes, boilies, the feed-through process, suppositories, by parenteral administration, as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, by nasal application, by dermal application in the form of, for example, diving or bathing (dipping), spraying, pouring (pour-on and spot-on ), washing, powdering and with the aid of active substance-containing moldings, such as collars, ear tags, tail marks, limb bands, holsters, marking devices, etc.
  • enteral administration in the form of, for example, tablets, capsules, infusions, drenches, granules, pastes, boilies, the feed-through process, suppositories
  • parenteral administration as by injections (intr
  • the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowable agents) which contain the active ingredients in an amount of from 1 to 80% by weight, directly or apply after 100 to 10,000 times dilution or use as a chemical bath.
  • formulations for example powders, emulsions, flowable agents
  • the compounds according to the invention show a high insecticidal activity against insects which destroy industrial materials.
  • insects By way of example and preferably without limiting however, the following insects are mentioned:
  • Hymenoptera such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur;
  • Termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes' darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus;
  • Non-living materials such as preferably plastics, adhesives, glues, papers and cardboard, leather, wood, wood processing products and paints.
  • the ready-to-use agents may optionally contain further insecticides and optionally one or more fungicides.
  • the compounds according to the invention can be used to protect against fouling of objects, in particular hulls, sieves, nets, structures, quay systems and signal systems, which come into contact with seawater or brackish water.
  • the compounds according to the invention can be used alone or in combinations with other active substances as antifoaming agents.
  • the active compounds are also suitable for controlling animal pests in household, hygiene and storage protection, in particular of insects, arachnids and mites, which occur in enclosed spaces, such as apartments, factories, offices, vehicle cabs, etc. You can fight these pests alone or in combination with other active ingredients and adjuvants in household insecticide products. They are effective against sensitive and resistant species and against all stages of development. These pests include:
  • Acarina e.g. Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae.
  • Opiliones e.g. Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.
  • Zygentoma e.g. Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.
  • Anthrenus spp. From the order of Coleoptera, for example, Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.
  • Lepidoptera e.g. Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
  • Ctenocephalides canis Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
  • Hymenoptera e.g. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
  • Heteroptera e.g. Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.
  • Application is in aerosols, non-pressurized sprays, e.g. Pump and atomizer sprays, misting machines, foggers, foams, gels, evaporator products with cellulose or plastic evaporator plates, liquid evaporators, gel and membrane evaporators, propeller driven evaporators, energyless or passive evaporation systems, moth papers, moth cakes and moth gels, as granules or dusts, in litter or bait stations.
  • Pump and atomizer sprays misting machines, foggers, foams, gels, evaporator products with cellulose or plastic evaporator plates, liquid evaporators, gel and membrane evaporators, propeller driven evaporators, energyless or passive evaporation systems, moth papers, moth cakes and moth gels, as granules or dusts, in litter or bait stations.
  • the active compounds of the formula (I) according to the invention may optionally also be used in certain concentrations and application rates as herbicides, for influencing plant growth, and for controlling unwanted microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials. If appropriate, they can also be used as intermediates and precursors for the synthesis of other active ingredients.
  • mycotoxins include: deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2 and HT2 toxin, fumonisins, zearalenone, moniliformin, fusarin, diaceotoxyscirpenol (DAS) , Beauvericin, enniatine, fusaroproliferin, fusarenol, ochratoxins, patulin, ergot alkaloids and aflatoxins, which may be caused, for example, by the following fungi: Fusarium spec., Such as Fusarium acuminatum, F.
  • the compounds of the formula (I) according to the invention are suitable for suppressing the growth of tumor cells in humans and mammals. This is based on an interaction of the compounds according to the invention with tubulin.
  • an effective amount of one or more compounds of the formula (I) or pharmaceutically acceptable salts thereof can be administered.
  • carboxylic acid methyl ester were stirred in 2 mL dioxane and treated with 1.27 mL 2N potassium hydroxide solution. The mixture was stirred at 50 ° C. for 2 h. It was then made acidic with 1 N hydrochloric acid (about pH 1) and the mixture was concentrated to dryness. The product was extracted from the solid with a mixture of ethyl acetate / methanol. 82 mg of the title compound were obtained.
  • the basic solution was adjusted to pH 6 and then pH 1 with IN HCl and washed in each case with ethyl acetate.
  • the HCl-acidic water phase was concentrated to dryness and the product was extracted from the solid with a mixture of dichloromethane and MeOH. 890 mg of product were obtained.
  • the calibration was carried out with unbranched alkan-2-ones (having 3 to 16 carbon atoms) whose logP values are known (determination of the logP values by means of the retention times by linear interpolation between two consecutive alkanones).
  • the lambda max values were determined on the basis of the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals.
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Chinese cabbage leaf discs ⁇ Brassica pekinensis are sprayed with an active compound preparation of the desired concentration and, after drying, are populated with larvae of the horseradish leaf beetle ⁇ Phaedon cochleariae).
  • the effect is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.
  • the following compounds of the preparation examples with an application rate of 500 g / ha have an efficacy of> 80%: 1-3, 1-4, 1-6, 1-8, 1-10, 1-14, 1 -15, 1-16, I-19, 1-30, 1-32, 1-34, 1-38, 1-39, 1-45, 1-50, 1-51, 1-60, 1-63 ,
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Chinese cabbage leaf discs (ßrassica pekinensis) infected by all stages of the green peach aphid (Myzus persicae) are sprayed with an active compound preparation of the desired concentration.
  • the effect is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
  • the following compounds of the preparation examples with an application rate of 500 g / ha have an efficacy of> 80%: 1-2, 1-3, 1-4, 1-5, 1-9, 1-10 , 1-12, 1-13, 1-15, 1-16, 1-18, 1-19, 1-29, 1-30, 1-32, 1-34, 1-36, 1-38, 1 -39, 1-40, 1-41, 1-43, 1-44, 1-45, 1-47, 1-48, 1-49, 1-50, 1-51, 1-54, 1-58 , 1-60, 1-62, 1-63.
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Bean leaf discs Phaseolus vulgaris infected by all stages of the common spider mite ⁇ Tetranychus urticae) are sprayed with an active compound preparation of the desired concentration.
  • the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
  • the following compounds of the preparation examples with an application rate of 500 g / ha have an activity of> 80%: 1-2, 1-19, 1-29, 1-32, 1-38, 1-40 , 1-49, 1-51, 1-56.
  • Vessels are filled with sand, drug solution Meloidogyne incognita egg larvae suspension and lettuce seeds.
  • the lettuce seeds germinate and the plantlets develop.
  • the galls develop at the roots.
  • the nematicidal activity is determined by means of bile formation in%. 100% means that no bile was found; 0% means that the number of bile on the treated plants corresponds to that of the untreated control.
  • the following compounds of the preparation examples with a concentration of 20 ppm or 40 ppm * show an efficacy of> 80%: 1-2, 1-5 *, 1-7, 1-15, 1-16, I - 36.
  • Vessels containing horsemeat treated with the preparation of active compound of the desired concentration are infested with Lucilia cuprina larvae.
  • the kill is determined in%. 100% means that all larvae have been killed; 0% means that no larvae have been killed.
  • the drug solution is injected into the abdomen (Boophilus microplus), the animals are transferred to trays and stored in an air-conditioned room.
  • the effect is determined in%. 100% means that no ticks have laid fertile eggs.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Botrytis test (cucumber) / protective
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the following compounds of the preparation examples with a concentration of 500 ppm show an efficacy of> 70%: 1-1, 1-2, 1-3, 1-4, 1-5, 1-8, 1-9 , 1-10, 1-11, 1-12, 1-13, 1-14, 1-15, 1-16, 1-18, 1-22, 1-26, 1-31, 1-32, 1 -33, 1-34, 1-38, 1-39, 1-43, 1-44, 1-45, 1-46, 1-50.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the following compounds of the preparation examples with a concentration of 500 ppm show an efficacy of> 70%: 1-3, 1-4, 1-10, 1-11, 1-15, 1-16, 1-26 , 1-31, 1-32, 1-39, 1-41, 1-45.
  • Emulsifier 2 parts by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • emulsifier-containing water 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • ammonium salts or ammonium salts and penetration enhancers these are pipetted in each case to the finished preparation solution in a concentration of 1000 ppm after dilution.
  • Paprika plants (Capsicum annuum) which are heavily infested with the green peach aphid ⁇ Myzus persicaei) are treated by spraying with the preparation of active compound in the desired concentration.
  • the kill is determined in%. 100% means that all animals have been killed; 0% means that no animals were killed.
  • the cuticles were placed with tweezers in the middle of the silicone grease-coated edges of the diffusion cells and sealed with a likewise greased ring.
  • the arrangement was chosen so that the morphological outside of the cuticles was directed outward, ie towards the air, while the original inner side faced the interior of the diffusion cell.
  • the diffusion cells were filled with a 30% ethylene glycol / water solution.
  • 5 ⁇ l of the spray mixture of the following composition were applied to the outside of the cuticle.
  • the preparation of the spray mixture erfoigt with local tap water medium water hardness.
  • Cuticle was adjustable by a slight air flow on the cuticle with the spray coating (20 ° C, 60% rh). At regular intervals aliquots were taken from an autosampler and the active ingredient content was determined by HPLC.
  • test results are shown in the following table.
  • the figures given are average values from 8 to 10 measurements. With ammonium sulfate and RME the penetration is significantly improved.
  • RME rapeseed oil methyl ester (use formulated as 500 EW, concentration in g

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Pretreatment Of Seeds And Plants (AREA)

Abstract

L'invention concerne des dérivés d'acide carboxylique hétérocycliques représentés par la formule (I), un procédé de fabrication de ces composés, l'utilisation des dérivés d'acide carboxylique hétérocycliques dans la lutte contre des animaux nuisibles et/ou des champignons nuisibles phytopathogènes, des procédés et des agents de lutte contre des animaux nuisibles et/ou des champignons nuisibles phytopathogènes dans et/ou sur des plantes et/ou des semences de plantes, des procédés de fabrication de tels agents et de semences traitées, ainsi que l'utilisation de ceux-ci dans la lutte contre des animaux nuisibles et/ou des champignons nuisibles phytopathogènes dans l'agriculture, le jardinage et la sylviculture, dans la santé animale, la protection des matériaux et dans les domaines du ménage et de l'hygiène.
EP08801444A 2007-06-13 2008-05-31 Dérivés d'acide hétérocyclyl-carboxylique à substitution hétérocyclique Withdrawn EP2158204A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08801444A EP2158204A2 (fr) 2007-06-13 2008-05-31 Dérivés d'acide hétérocyclyl-carboxylique à substitution hétérocyclique

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07110228A EP2014661A1 (fr) 2007-06-13 2007-06-13 Dérivés d'acides d'hétérocyclyle-carbonique substitués hétéroclites
EP08801444A EP2158204A2 (fr) 2007-06-13 2008-05-31 Dérivés d'acide hétérocyclyl-carboxylique à substitution hétérocyclique
PCT/EP2008/004352 WO2008151735A2 (fr) 2007-06-13 2008-05-31 Dérivés d'acide hétérocyclyl-carboxylique à substitution hétérocyclique

Publications (1)

Publication Number Publication Date
EP2158204A2 true EP2158204A2 (fr) 2010-03-03

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EP07110228A Ceased EP2014661A1 (fr) 2007-06-13 2007-06-13 Dérivés d'acides d'hétérocyclyle-carbonique substitués hétéroclites
EP08801444A Withdrawn EP2158204A2 (fr) 2007-06-13 2008-05-31 Dérivés d'acide hétérocyclyl-carboxylique à substitution hétérocyclique

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Country Status (9)

Country Link
US (1) US20100167931A1 (fr)
EP (2) EP2014661A1 (fr)
JP (1) JP2010532750A (fr)
CN (1) CN101679443A (fr)
AR (1) AR066945A1 (fr)
BR (1) BRPI0814251A2 (fr)
CL (1) CL2008001628A1 (fr)
TW (1) TW200911122A (fr)
WO (1) WO2008151735A2 (fr)

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TWI482771B (zh) * 2009-05-04 2015-05-01 Du Pont 磺醯胺殺線蟲劑
US9309250B2 (en) 2011-06-22 2016-04-12 Vertex Pharmaceuticals Incorporated Substituted pyrrolo[2,3-b]pyrazines as ATR kinase inhibitors
SI2941432T1 (en) 2012-12-07 2018-07-31 Vertex Pharmaceuticals Incorporated 2-AMINO-6-FLUORO-N- (5-FLUORO-4- (4- (4- (OXETHAN-3-YL) PIPERAZIN-1-CARBONYL) PIPERIDIN-1-YLIPRIDIN-3-YL) 1,5 ALFA) PYRIMIDINE-3-CARBOXAMIDE AS ATR KINAZE INHIBITOR
US8957078B2 (en) 2013-03-15 2015-02-17 Vertex Pharmaceuticals Incorporated Compounds useful as inhibitors of ATR kinase
WO2014143240A1 (fr) 2013-03-15 2014-09-18 Vertex Pharmaceuticals Incorporated Dérivés de pyrazolopyrimidine fusionnés utiles en tant qu'inhibiteurs de la kinase atr
EP2970288A1 (fr) 2013-03-15 2016-01-20 Vertex Pharmaceuticals Incorporated Composés utiles en tant qu'inhibiteurs de la kinase atr
PT3077397T (pt) 2013-12-06 2020-01-22 Vertex Pharma Composto de 2-amino-6-fluoro-n-[5-fluoro-piridin-3-il]pirazolo[1,5-a]pirimidin-3-carboxamida útil como inibidor da atr quinase, a sua preparação, diferentes formas sólidas e derivados radiomarcados do mesmo
MX373102B (es) 2014-06-05 2020-04-17 Vertex Pharma Derivados radiomarcados de un compuesto de 2-amino-6-fluoro-n-[5-fluoro-piridin-3-il]-pirazolo[1,5-a]pirimidin-3-carboxamida útil como inhibidor de ataxia telangiectasia mutada y rad3 relacionado (atr) cinasa, preparación de tal compuesto y diferentes formas sólidas del mismo.
SG11201610500WA (en) 2014-06-17 2017-01-27 Vertex Pharma Method for treating cancer using a combination of chk1 and atr inhibitors
AU2016331955B2 (en) 2015-09-30 2022-07-21 Vertex Pharmaceuticals Incorporated Method for treating cancer using a combination of DNA damaging agents and ATR inhibitors
AR121344A1 (es) 2020-02-18 2022-05-11 Pi Industries Ltd Compuestos heterocíclicos fusionados y su uso como agentes para el control de plagas
WO2023230217A1 (fr) * 2022-05-25 2023-11-30 Trustees Of Boston University Composés antileishmaniens, compositions et utilisation de ceux-ci
CN116969954B (zh) * 2023-09-21 2023-11-28 广东省农业科学院农业质量标准与监测技术研究所 一类含内酰胺的三环稠合杂环化合物及其应用

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ATE388138T1 (de) * 2003-06-27 2008-03-15 Bayer Cropscience Ag Pyrazolopyrimidine
DE102004008807A1 (de) * 2004-02-20 2005-09-08 Bayer Cropscience Ag Pyrazolopyrimidine
DE102005007534A1 (de) * 2005-02-17 2006-08-31 Bayer Cropscience Ag Pyrazolopyrimidine
WO2007023020A1 (fr) * 2005-07-13 2007-03-01 Basf Aktiengeseelschaft Composes 7-amino-6-heteroaryl-1,2,4-triazolo[1,5-a]pyrimidine et utilisation dans la lutte contre des champignons parasites

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WO2008151735A2 (fr) 2008-12-18
CL2008001628A1 (es) 2008-12-19
CN101679443A (zh) 2010-03-24
TW200911122A (en) 2009-03-16
BRPI0814251A2 (pt) 2018-08-14
WO2008151735A3 (fr) 2009-07-02
US20100167931A1 (en) 2010-07-01
EP2014661A1 (fr) 2009-01-14
AR066945A1 (es) 2009-09-23
JP2010532750A (ja) 2010-10-14

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