Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
  • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
  • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
  • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Definitions

• the invention relates to the use of heterocyclic carboxylic acid derivatives of the following formula (I)
• the present invention furthermore relates to heterocyclic carboxylic acid derivatives of the formula (I), processes for their preparation and their use for combating pests in agriculture, horticulture and forestry, in the protection of materials and in the household and hygiene sector.
• the present invention also relates to the enhancement of the effect of pesticides containing insecticidal heterocyclic carboxylic acid derivatives of the formula (I) by the addition of ammonium or phosphonium salts and optionally penetration promoters, the corresponding agents, processes for their preparation and their use in crop protection, especially as insecticides and / or acaricides.
• A is a nitrogen atom, in which case the bond in the pyrimidine ring is a single bond, or a carbon atom, in which case the bond in the pyridine ring is a double bond,
• B 1 stands for a nitrogen atom O ( ⁇ er ⁇ r ⁇ as F ra S ment
• B 2 represents a nitrogen atom 0 ( ⁇ he ⁇ * r ⁇ ra as P S ment
• Be represents a nitrogen atom ° ⁇ he ⁇ r ⁇ as fragment or a
• B 4 stands for the fragments where the dashed bonds may be single bonds, double bonds or aromatic bonds
• X is hydrogen, halogen, cyano, hydroxy, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted phenyl, optionally substituted alkylthio, optionally substituted alkylsulfinyl or optionally substituted alkylsulfonyl;
• Y is optionally substituted aryl, optionally substituted heterocyclyl, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted arylalkyl, halogen, an optionally substituted amino group, optionally substituted (C ) - Cg) alkoxy, optionally substituted (C j -Cg) -alkylthio, optionally substituted (C 5 -C 10) -acyloxy, optionally substituted (Cg-C j o) arylthio, optionally substituted hetero- cyclyloxy, optionally substituted (C6-C] Q) aryl (Ci-C4) alkoxy, optionally substituted (C6-C o j) aryl (C 1 -C 4) -alkylthio, optionally substituted heterocyclyl optionally substituted heterocycly
• Z is hydroxy, halogen or in each case optionally substituted alkoxy, alkylthio,
• G 1, G 2 and G 5 independently of one another represent hydrogen, halogen, optionally substituted alkyl or optionally substituted cycloalkyl, O- (C j-C4) alkyl or S (O) 0 .2 (C 1 -C 4) alkyl;
• L is oxygen or sulfur
• R! is hydrogen, optionally substituted alkyl, optionally substituted
• R2 is hydrogen or alkyl
• R 1 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-OR 6 , CO-SR 6 , CS-OR 6 or CS-SR 6 ;
• R ⁇ is hydrogen, in each case optionally substituted alkyl, alkenyl or alkynyl, 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 or a cation such as mono- or bivalent Metal atoms or an ammonium ion optionally substituted by alkyl or arylalkyl;
• R 5 is hydrogen, in each case optionally substituted alkyl, alkoxy, alkenyl, alkenyloxy or alkynyl, for the groups COR 7 , S (O) i_ 2 R 7 , cyano, COOR 7 ,
• Heteroatoms selected from the group consisting of N, S and / or O atoms, wherein oxygen atoms may not be adjacent; or
• R 4 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 6 is hydrogen, a cation, for example an optionally substituted by alkyl or
• Arylalkyl substituted ammonium ion in each case optionally substituted alkyl,
• R 7 is hydrogen, in each case optionally substituted alkyl, alkenyl, alkynyl is in each case optionally substituted cycloalkyl-alkyl, cycloalkyl or cycloalkenyl, in each case optionally substituted aryl, heteroaryl, arylalkyl or heteroarylalkyl;
• R 1 is hydrogen, in each case optionally substituted alkyl, alkenyl, alkynyl, alkoxy or NH-R 4 ;
• R 4 and R 7 together with the N-CO or NS (O) ] .2 group to which they are attached form a 4- to 8-membered cycle containing one or more heteroatoms from the series sulfur, oxygen and / or or nitrogen, wherein oxygen atoms may not be adjacent;
• R 7 and R. 8 together with the nitrogen atom to which they are attached, represent an optionally substituted saturated or unsaturated ring which may optionally be interrupted by further heteroatoms;
• R 1 and R 10 are each independently optionally substituted alkyl, alkenyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy,
• R 9 and R 1 0 are together with the phosphorus atom to which they are attached form an optionally substituted 5- to 7-membered cyclic group, by one or two
• Oxygen and / or sulfur atoms may be interrupted;
• R 1 and R 1 independently represent each optionally substituted alkyl, alkenyl, alkynyl, phenyl or phenylalkyl;
• Inventive heterocyclic carboxylic acid derivatives of the formula (I) and their agrochemically active salts are very suitable as pesticides, in particular for controlling animal pests such as insects, parasites of the subclass of Acari (Acarina) (such as mites, spider mites and / or ticks) and / or nematodes.
• animal pests such as insects, parasites of the subclass of Acari (Acarina) (such as mites, spider mites and / or ticks) and / or nematodes.
• the abovementioned compounds according to the invention exhibit a strong insecticidal and / or acaricidal and / or nematicidal activity and can be used both in crop protection, in the household and hygiene sector and 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.
• 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 (QC ⁇ -alkyl radicals, mono-, di- and trialkanolamines of (Q-C4) -alkanols, choline and chlorocholine.
• acids are for example mineral acids, such as Hydrochloric, sulfuric and phosphoric acid, organic acids such as acetic acid or oxalic acid, and acidic salts such as NaHSO 4 and KHSO 4.
• mineral acids such as Hydrochloric, sulfuric and phosphoric acid
• organic acids such as acetic acid or oxalic acid
• acidic salts such as NaHSO 4 and KHSO 4.
• the compounds according to the invention namely the heterocyclic carboxylic acid derivatives are generally defined by the formula (I).
• the present invention thus relates
• A represents a nitrogen atom, in which case the bond in the pyrimidine ring is a single bond, or represents a carbon atom, in which case the bond in the pyridine ring is a double bond,
• B ⁇ represents a nitrogen atom, 0 ⁇ he ⁇ "r ⁇ as fragment ° he d for a
• X is hydrogen, halogen, cyano, hydroxy, alkyl, alkoxy, phenyl, alkylthio, alkylsulfinyl or alkylsulfonyl;
• Y is aryl, heterocyclyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl,
• Z is hydroxy, halogen or alkoxy, alkylthio, alkylsulfonyl or the group
• G ⁇ , G ⁇ and G ⁇ independently represent hydrogen, halogen, alkyl or
• Cycloalkyl O- (Cj-C4) alkyl or S (O) 0 ⁇ (C i-C4>-alkyl;
• L is oxygen or sulfur
• R! for hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or heterocyclyl, hydroxy
• R ⁇ is hydrogen or alkyl
• R3 is CO-N, CO-OR 6, CO-SR 6, OR 6 or CS-CS-SR 6;
• R ⁇ is hydrogen, alkyl, alkenyl or alkynyl, in each case saturated or unsaturated cycloalkyl, which may optionally be interrupted by heteroatoms,
• R ⁇ is hydrogen, alkyl, alkoxy, alkenyl, alkenyloxy or alkynyl, for the groups COR 7 , S (O) 1 R 7 , cyano, COOR 7 ,
• R ⁇ and R-> together with the nitrogen atom to which they are attached represent a saturated, unsaturated or aromatic ring which may optionally be interrupted by further heteroatoms;
• R 6 is hydrogen, a cation, for example an ammonium ion, alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl, which may be replaced by a
• Hetero atom may be interrupted, cycloalkyl-alkyl or aryl, arylalkyl, heteroaryl or heteroaryl-alkyl;
• R 7 is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl-alkyl, cycloalkyl or cycloalkenyl, aryl, heteroaryl, arylalkyl or heteroarylalkyl;
• R 8 is hydrogen, alkyl, alkenyl, alkynyl, alkoxy or NH-R 4 ;
• R 7 and R 8 together with the nitrogen atom to which they are attached represent an optionally substituted saturated or unsaturated ring which may optionally be interrupted by further heteroatoms;
• R "and R 10 independently of one another are alkyl, alkenyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, cycloalkylalkoxy, alkylthio,
• R "and R 1" together with the phosphorus atom to which they are attached stand for an optionally substituted 5- to 7-membered cycle which may be interrupted by one or two oxygen and / or sulfur atoms;
• R1 and R1 independently represent alkyl, alkenyl, alkynyl, phenyl or phenylalkyl
• an agent for controlling animal pests in and / or on plants or in and / or on seeds of plants comprising at least one compound as defined under (1) and / or at least one of its agrochemically active compounds Salts or as under (2) mixture and agrochemically customary auxiliaries and / or additives;
• a process for producing a defined agent as defined in (3) comprising mixing at least one compound as defined under (1) and / or at least one of their agrochemically active salts or a mixture as defined under (2) with agrochemically customary auxiliaries and / or additives; and
• A preferably represents a nitrogen atom, in which case the bond in the pyrimidine ring is a single bond, or represents a carbon atom, in which case the bond in the pyridine ring is a double bond,
• - CG 1 B 1 is preferably a nitrogen atom * ⁇ __ or the fragment
• CG 2 B 2 is preferably a nitrogen atom *.-_ Or the fragment 11,
• - CG 3 B 3 is preferably a nitrogen atom u_ or the fragment
• B 4 is preferably the fragments ⁇ 3 or p3 where the dashed bonds may be single bonds, double bonds or aromatic bonds;
• X is preferably hydrogen, fluorine, chlorine, bromine, cyano, hydroxy, alkoxy of 1 to 4
• Y is preferably C 1 -C 1 O-AIlCyI, C2-C j-Q alkenyl, C2-C ⁇ Q alkynyl, C3-C8-cycloalkyl, phenyl-Cj-Cio-alkyl, wherein Y is unsubstituted or partially or completely is halogenated and / or optionally carries one to three radicals R x , or Ci-Cio-H a l ° g ena alkyl, which optionally carries one to three radicals R x , wherein the R x are the same or different selected from the group from cyano, nitro, hydroxy, Cj-Cg-alkyl,
• Y is preferably phenyl, which may optionally be monosubstituted, monosubstituted or differently monosubstituted by
• Haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;
• radicals may be monosubstituted, polysubstituted, identically or differently substituted by halogen, alkyl having 1 to 4 carbon atoms and / or haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms; or
• Y is preferably saturated or wholly or partially unsaturated or aromatic heterocyclyl having 3 to 8 ring members and 1 to 3 heteroatoms from the group nitrogen, oxygen and sulfur, where the heterocyclyl may be monosubstituted or disubstituted by halogen, alkyl having 1 to 4 carbon atoms , Alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, haloalkoxy of 1 to 4
• Z is preferably hydroxy, chlorine, bromine, in each case optionally 1 to 7
• G 1, G 2 and G * are preferably independently of one another represent hydrogen, halogen, optionally substituted by one or more halogen atoms substituted C] -C4-alkyl, optionally substituted by one or more halogen atoms substituted C3-C6-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 ;
• L is oxygen or sulfur
• R! is preferably hydrogen, alkyl of 1 to 10 carbon atoms, which is unsubstituted or monosubstituted to five times, identically or differently substituted by halogen, cyano, hydroxy, alkoxy having 1 to 4 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, mercapto, alkylthio with 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 of 1 to 4 carbon atoms, amino, mono- or dialkylamino each having 1 to 4 carbon atoms; or
• R 1 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 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! 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, wherein the
• Heterocyclyl is unsubstituted or mono- or polysubstituted by halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, cyano, nitro, cycloalkyl having 3 to 6 carbon atoms, hydroxy, alkoxy, alkenyloxy, alkynyloxy having 1 to 6 carbon atoms or mercapto ;
• 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 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 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 CO-OR 6 , CO-SR 6 , CS-OR 6 or CS-SR 6 ;
• R 4 preferably represents hydrogen, cations from the series of the alkali or alkaline earth metals or ammonium ions NH4, mono-CC j -C j oVAlkylammoniurn, di- (C j -C j o) alkyl ammonium, tri- (Ci-Cio ) -Alkylammonium, tetra (Ci-Cio) -Alkylammonium, wherein the
• Alkyl radicals of the ammonium ions may be substituted with aryl or hydroxy, or cholinium,
• R 5 is preferably hydrogen, each optionally mono- to polysubstituted by fluorine and / or chlorine-substituted C j -C jQ alkyl, C j -C jQ alkoxy, C 3 -C jQ alkenyl, C 3 -C j o Alkenyloxy or C 3 -C 10 alkynyl; for the groups CO-R 7 , S (O) j . 2 R 7, cyano,
• 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;
• R6 preferably represents hydrogen, cations from the series of the alkali or alkaline earth metals or ammonium ions NH 4, mono- (C j -C j o) -Alkylamrnonium, di- (C j -C j o) alkyl ammonium, tri- (C j -C j o) -alkylammonium, tetra- (C j -C j o) -alkylammonium, wherein the alkyl radicals of the ammonium ions may be substituted by aryl or hydroxy, or
• cholinium in each case optionally monosubstituted to polysubstituted by fluorine, chlorine, C 1 -C 4 -alkoxy, C 1 - C 4 alkylthio, cyano, CO 2 H or CO-OC r C 4 alkyl-substituted Ci-C 10 alkyl, C 3 - C-alkenyl or C 3 -C 1 O-AIkUIyI, in each case optionally mono- to polysubstituted by fluorine, chlorine, C r C 4 alkyl, C j -C 4 haloalkyl, C r C 4 alkoxy, CN , CO 2 H or CO-O-C 1 -C 4 -alkyl-substituted C 3 -C 8 cycloalkyl, C 3 -C 6 cycloalkyl-Ci-C 2 alkyl or C 5 -C 8 -
• Cycloalkenyl which may optionally be interrupted by an oxygen or sulfur atom,
• R 7 is preferably hydrogen, in each case optionally mono- to polysubstituted by fluorine, chlorine, C r C 4 alkoxy, C r C 4 alkylthio, cyano, CO 2 -H or CO-OC j -C 4 alkyl substituted C 1Q 1 -C -alkyl, C 3 -Ci0 alkenyl or C 3 -C j o-alkynyl, several times for each if necessary simply by fluorine, chlorine, C 1 -C 4 -alkyl, C j -C 4 - Haloalkyl, C 1 -
• C 4 alkoxy, CN, CO 2 H or CO-OC r C 4 -alkyl-substituted C 3 -C 8 -cycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 2 -alkyl or C 5 -C 8 -cycloalkenyl, which may optionally be interrupted by an oxygen or sulfur atom,
• R.sup.8 is preferably hydrogen, in each case optionally mono- to polysubstituted by fluorine and / or chlorine-substituted CpCg-alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl or C 1 -C 6 -alkoxy;
• R 4 and R 7 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;
• R 7 and R 8 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 9 and R 10 are preferably independently of one another represent in each case optionally monosubstituted to polysubstituted by fluorine and / or chlorine-Ci-C 8 alkyl, C 3 -C 8 alkenyl, C 8 - alkoxy, C 3 -C 8 - alkenyloxy, C 3 -C 8 alkynyloxy, C] -C 6 alkylthio, C 3 -C 6 alkenylthio, optionally mono- or disubstituted by fluorine, chlorine, Ci-C4-alkyl, Ci-C 4 haloalkyl, QC 4 -alkoxy substituted C 3 -C 8 -cycloalkoxy, C 4 -Cg -cycloalkenyloxy or C 3 -C 8 -cycloalkyl-C 1 -C 2 -alkoxy, in each case optionally mono- to trisubstituted by fluorine,
• R 9 and R 10 preferably together with the phosphorus atom to which they are bonded, represent an optionally mono- to trisubstituted by fluorine, chlorine, -C 4 alkyl, Ci-C4-alkoxy or Ci-C 4 haloalkyl substituted five- to seven membered cycle which may be interrupted by one or two oxygen and / or sulfur atoms;
• R 11 and R 12 are each, independently of one another, in each case optionally mono- to trisubstituted by fluorine or chlorine, C 1 -C 8 -alkyl, C 3 -C 8 -alkenyl or C 3 -C 8 -
• Alkynyl each optionally optionally once or twice by fluorine, chlorine, bromine, C] -C 4 -
• A is particularly preferably a nitrogen atom, in which case the bond in the
• B 4 particularly preferably represents the fragments p3 or p3
• X particularly preferably represents hydrogen, fluorine, chlorine, cyano, C r C 4 alkyl or C] -C 2 -
• Haloalkyl which may be substituted by one to five fluorine and / or chlorine atoms;
• Y particularly preferably represents in each case optionally substituted by one to five fluorine and / or chlorine atoms substituted Cj-Cg-alkyl, C2-Cg-alkenyl, C2-Cg-alkynyl or C3-Cg-cycloalkyl;
• Y is particularly preferably phenyl, which may optionally be monosubstituted to trisubstituted, identically or differently substituted by fluorine, chlorine, bromine, iodine, cyano, nitro, formyl, methyl, ethyl, n- or i-propyl, n-, i- , s- or t-butyl, vinyl, 1-propenyl, ethynyl, 1-propynyl, allyl, propargyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, Methylsulfonyl, ethylsulfonyl, allyloxy, propargyloxy, trifluoromethyl, trifluoroethyl, difluorome
• Hydroximinomethyl hydroximinoethyl, methoximinomethyl, ethoximinomethyl, methoxy iminoethyl, ethoximinoethyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or by
• Chlorine methyl, ethyl, n-propyl, i-propyl trifluoromethyl, carboxy and / or carboxymethyl; or
• Y is particularly preferably pyridyl which is linked in the 2- or 4-position and may be monosubstituted, monosubstituted or differently substituted by fluorine, chlorine, bromine, cyano, hydroxyl, mercapto, nitro, methyl, ethyl, methoxy, methylthio , Hydroxyminomethyl, hydroximinoethyl, methoximinomethyl, methoximinoethyl, trifluoromethyl,
• Thiazolyl which is linked in the 2-, 4- or 5-position and may be mono- to disubstituted by identical or different substituents by fluorine, chlorine, bromine, cyano, nitro, hydroxy, mercapto, methyl, ethyl, methoxy, methylthio, hydroximinomethyl , Hydroximinoethyl,
• Methoximinomethyl methoximinoethyl, trifluoromethyl, carboxy and / or carboxymethyl or
• Pyrimidyl which is linked in the 2- or 4-position and may be monosubstituted to trisubstituted, identically or differently, by fluorine, chlorine, bromine, cyano, nitro, hydroxyl, mercapto, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl,
• Methoximinomethyl methoximinoethyl, trifluoromethyl, carboxy and / or carboxymethyl or
• Thienyl which is linked in the 2- or 4-position and may be monosubstituted to trisubstituted by identical or different substituents by fluorine, chlorine, bromine, cyano, nitro, hydroxy, mercapto, methyl, ethyl, methoxy, methylthio, hydroximinomethyl, hydroximinoethyl,
• Methoximinomethyl methoximinoethyl, trifluoromethyl, carboxy and / or carboxymethyl
• Z is particularly preferably chlorine, bromine, in each case optionally 1 to 3
• R 2 G 1 , G 2 and G 3 are particularly preferably each independently hydrogen, halogen, optionally substituted by one or more halogen atoms (Ci-GO-alkyl optionally substituted by one or more halogen atoms cyclopropyl; SCH3, 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 ;
• L is particularly preferably oxygen or sulfur
• R 1 particularly preferably represents hydrogen, alkyl having 1 to 8 carbon atoms, which is unsubstituted or monosubstituted to trisubstituted, identically or differently, 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.1 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 with 1 up to 3 carbon atoms; or
• R! particularly preferably represents alkynyl having 3 to 8 carbon atoms, which is unsubstituted or monosubstituted to trisubstituted by identical or different substituents by fluorine, chlorine,
• Cyano alkoxy of 1 to 3 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, alkylthio of 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! particularly preferably represents saturated or unsaturated heterocyclyl of 3 to 8
• 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 may be unsubstituted or substituted up to three times by fluorine, chlorine, bromine, alkyl having 1 to 3 carbon atoms lenstoffatomen, haloalkyl having 1 to 3 carbon atoms and 1 to 5 fluorine and / or chlorine atoms, alkoxy having 1 to 3 carbon atoms, haloalkoxy having 1 to 3 carbon atoms and 1 to 5 fluorine and / or chlorine atoms, thioalkyl having 1 to 3 carbon atoms and / or haloalkylthio having 1 to 3 carbon atoms and 1 to 5 fluorine and / or chlorine atoms;
• R 3 is particularly preferably CON " R , CO-OR 6 , CO-SR 6 , CS-OR 6 or CS-SR 6 ;
• R 4 particularly preferably represents hydrogen, 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 ) /, NH 2 (C 2 Hj) 2 + , NH 3 C 2 H 5 + , NH 3 IC 3 H 7 + ,
• R 5 particularly preferably represents hydrogen, in each case optionally monosubstituted to trisubstituted by fluorine and / or chlorine, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 3 -C 8 -alkenyl, C 3 -C 8 -alkenyloxy or C C 3 -C 8 alkynyl; for the groups COR 7 , S (O) 1-2 R 7 , cyano, COOR 7 ,
• Triazine, thiazole, pyrazole, oxazole or triazole; or 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 6 particularly preferably represents hydrogen, Na + , K + , 14 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 Hj) 2 + , NH 3 C 2 H 5 + , NH 3 IC 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 7 particularly preferably represents hydrogen, represents in each case optionally mono- to pentasubstituted by fluorine, chlorine, C r C 3 alkoxy, C r C 3 alkylthio, cyano, CO 2 H or CO-OC 1 -C 3 -alkyl-substituted C -cg alkyl, C 3 -C 8 -alkenyl or C 3 -C 8 -alkynyl, in each case optionally mono- to trisubstituted by fluorine, chlorine, Ci-C 4 alkyl, C r C 2 -haloalkyl, C 2 Alkoxy, CN, CO 2 H or CO-OC r C 2 -alkyl-substituted C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl-methyl or C 5 -C 6 -cycloalkenyl, which may be replaced by an oxygen or sulfur atom can be interrupted,
• Ci-C3 alkoxy Ci-C3 haloalkoxy, nitro or cyano-substituted phenyl, pyridyl, thiazolyl, pyrimidyl, benzyl, phenethyl, pyridinylmethyl or thiazolyl methyl;
• R 8 particularly preferably represents hydrogen, in each case optionally mono- to trisubstituted by fluorine and / or chlorine, C] -C 4 alkyl, C 3 -C 4 - alkenyl, C 3 -C 4 alkynyl, or
• R 4 and R 7 form particularly preferably with the N-CO or NS (O) i -2 group to which they are attached, a 4- to 6-membered cycle containing one or more heteroatoms selected from sulfur, oxygen and or may contain nitrogen, wherein oxygen atoms may not be adjacent; or
• R 7 and R 8 are particularly preferably taken together with the nitrogen atom to which they are attached, for a saturated or unsaturated 5- or 6-membered ring optionally substituted once to twice by C 1 -C 2 -alkyl, optionally substituted by oxygen or sulfur can be interrupted;
• R 9 and R 10 are particularly preferably independently of one another in each case optionally monosubstituted to trisubstituted by fluorine and / or chlorine C r C 6 alkyl, C 3 -C 6 alkenyl, C 1 -C 6 -
• R 9 and R 10 are particularly preferably taken together with the phosphorus atom to which they are attached, for an optionally mono- to disubstituted by fluorine, chlorine, Ci-C 2 alkyl, Ci-C 2 alkoxy or C r C 2 haloalkyl substituted five to six membered cycle which may be interrupted by one or two oxygen and / or sulfur atoms; and
• R 11 and R 12 are particularly preferably independently of one another represent in each case optionally mono- to trisubstituted by fluorine or chlorine, Ci-C 6 alkyl, C 3 -C 6 alkenyl or
• R 3 and B 3 is a bond.
• X is very particularly preferably hydrogen, chlorine, methyl or trifluoromethyl
• Y very particularly preferably represents (C 1 -C 6) -alkyl, (C 3 -C 6) -alkenyl, (C 3 -C 6) -alkynyl,
• Y is very particularly preferably monosubstituted to trisubstituted phenyl having substituents selected from the group consisting of fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy or trifluoromethoxy; or
• Y very particularly preferably represents pyridyl which is linked in the 2- or 4-position and may be monosubstituted, disubstituted or differently substituted by fluorine, chlorine, bromine, cyano, methyl, ethyl, methoxy, methylthio or trifluoromethyl; or
• Pyrimidyl which is linked in the 4-position and may be monosubstituted to trisubstituted, identically or differently substituted by fluorine, chlorine, bromine, cyano, methyl, ethyl, methoxy,
• Thienyl which is linked in the 2- or 3-position and may be monosubstituted, disubstituted or differently substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy or trifluoromethyl;
• Z is very particularly preferably chlorine, methoxy, ethoxy, methylthio, ethythio or the
• G 1 , G 2 and G 3 are very particularly preferably each independently hydrogen, chlorine, bromine, methyl, ethyl, trifluoromethyl or cyclopropyl;
• L is most preferably oxygen or sulfur
• R 1 very particularly preferably represents hydrogen, alkyl having 1 to 6 carbon atoms, which is unsubstituted or monosubstituted to trisubstituted, identically or differently, by fluorine, chlorine, methoxy, ethoxy, cyclopropyl, cyclopentyl, cyclohexyl, methylthio or ethylthio; or
• R * 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 ⁇ is most preferably hydrogen, methyl or ethyl
• R 1 and R 3 together with the nitrogen atom to which they are attached are very particularly preferably a saturated or unsaturated heterocyclic ring having 3 to 6 ring members, where the heterocycle optionally contains a further nitrogen, oxygen or sulfur atom as ring member and wherein the heterocycle unsubstituted or substituted up to two times by fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy or ethoxy;
• R 3 is very particularly preferably CO-N ⁇ or CO-OR 6 ;
• R 4 very particularly preferably represents hydrogen, 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 Hs) 3 + , NH 2 (C 2 Hj) 2 + , NH 3 C 2 H 5 + , NH 3 IC 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 + ,
• C 3 -C 6 alkenyl or C 3 -C 6 alkynyl each optionally optionally mono- to trisubstituted by fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, cyano, CO-O-methyl or CO-O-ethyl substituted C 3 -C 6 cycloalkyl;
• R.5 very particularly preferably represents hydrogen, represents in each case optionally mono- to trisubstituted by fluorine and / or chlorine-C] -C6 alkyl, C r C 6 alkoxy, C 3 -C 6 -
• R 4 and R 5 are most preferably taken together with the nitrogen atom to which they are attached, for saturated 5- or 6-membered ring, which may optionally be interrupted by oxygen or sulfur;
• R 6 very particularly preferably represents hydrogen, 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 ) /, NH 3 C 2 H 5 + , NH 3 IC 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 7 very particularly preferably represents hydrogen, in each case optionally monosubstituted to trisubstituted by fluorine, chlorine, methoxy, ethoxy, methylthio, ethylthio, cyano, CO-O-
• Methyl or ethyl-substituted CO-O-C r C 6 alkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl represents in each case optionally monosubstituted by fluorine, chlorine, methyl, ethyl, methoxy, trifluoromethyl, cyano CO 2 H, CO-O-methyl or CO-O-ethyl-substituted C 3 -C 6 - cycloalkyl, C 3 -C 6 -cycloalkyl-methyl, or C5-C6 cycloalkenyl, which is optionally may be interrupted by an oxygen or sulfur atom, each optionally optionally mono- to disubstituted by fluorine, chlorine, bromine methyl, trifluoromethyl, methoxy-substituted phenyl, pyridyl, thiazolyl, pyrimidyl, benzyl, phene
• R 8 most preferably represents hydrogen, methyl, ethyl, propyl, iso-propyl, AHyI, propargyl, C 3 -C 4 alkenyl, methoxy or ethoxy; or
• R 7 and R 8 are most preferably taken together with the nitrogen atom to which they are attached, for a saturated 5- or 6-membered ring, which may optionally be interrupted by oxygen or sulfur;
• R 9 and R 10 are very particularly preferably each independently of the other preferably optionally mono- to trisubstituted by fluorine and / or chlorine methyl, ethyl, methoxy, ethoxy, propoxy, i-propoxy, butoxy, alkoxy, methylthio, ethylthio, propylthio, butylthio, i-Propylthio, sec-butylthio, allylthio.
• 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 particularly particularly preferred embodiment of the present invention; especially particularly preferred are the compounds of the formulas (1-3) which correspond to the formula (I), where the symbols A, B 1 , B 2 , B 3 and B 4 have the following particularly particularly particularly preferred meanings:
• X is particularly particularly preferably hydrogen, chlorine, methyl or trifluoromethyl
• Y is particularly particularly preferably (C 1 -C 8) -alkyl, (C 3 -G) -alkenyl, (C 3 -C 6) -alkynyl, (C 3 -C 9) -cycloalkyl, where Y is unsubstituted or substituted by one to three fluoro or chlorine atoms is substituted; or Y is especially particularly preferably monosubstituted to trisubstituted phenyl having substituents selected from the group consisting of fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy or trifluoromethoxy; or
• Y is particularly particularly preferably pyridyl which is linked in the 2- or 4-position and may be monosubstituted, disubstituted or differently substituted by fluorine, chlorine, bromine, cyano, methyl, ethyl, methoxy, methylthio or trifluoromethyl; or
• Pyrimidyl which is linked in the 4-position and may be monosubstituted to trisubstituted, identically or differently substituted by fluorine, chlorine, bromine, cyano, methyl, ethyl, methoxy, methylthio or trifluoromethyl; or
• Thienyl which is linked in the 2- or 3-position and may be monosubstituted, disubstituted or differently substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy or trifluoromethyl;
• Z is particularly particularly preferably chlorine, methoxy, ethoxy, methylthio,
• G 1 , G 2 and G 3 are very particularly preferably, independently of one another, hydrogen, chlorine, bromine, methyl, ethyl, trifluoromethyl or cyclopropyl;
• L is very particularly preferably oxygen or sulfur
• R 1 very particularly preferably represents hydrogen, alkyl having 1 to 6 carbon atoms, which is unsubstituted or monosubstituted to trisubstituted, identically or differently, by fluorine, chlorine, methoxy, ethoxy, cyclopropyl, cyclopentyl, cyclohexyl, methylthio or ethylthio; or
• R.1 is particularly particularly preferably alkenyl having 3 to 6 carbon atoms, which is unsubstituted or monosubstituted to trisubstituted by identical or different substituents by fluorine, chlorine, methoxy, ethoxy, methylthio or ethylthio; or
• R! is particularly particularly preferred for alkynyl having 3 to 6 carbon atoms, which is unsubstituted or monosubstituted to trisubstituted by identical or different substituents by fluorine, chlorine, methoxy, ethoxy, methylthio or ethylthio; or
• R 1 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.2 is particularly particularly preferably hydrogen, methyl or ethyl
• R1 and R2 together with the nitrogen atom to which they are attached, represent a saturated or unsaturated heterocyclic ring having from 3 to 6 ring members, where the heterocycle optionally represents another nitrogen, oxygen or sulfur atom as ring member and wherein the heterocycle may be unsubstituted or substituted up to twice by fluorine, chlorine, methyl,
• R is particularly particularly preferably hydrogen
• C 3 -C 6 alkenyl or C 3 -C 6 alkynyl each optionally optionally mono- to trisubstituted by fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, cyano, CO-O-methyl or CO-O-ethyl substituted C 3 -C 6 cycloalkyl;
• R-> is especially particularly preferably hydrogen, in each case optionally monosubstituted to trisubstituted by fluorine and / or chlorine, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy,
• R 4 and R 5 are particularly particularly preferred together with the nitrogen atom to which they are attached, for saturated 5- or 6-membered ring, which may optionally be interrupted by oxygen or sulfur;
• R 6 is particularly particularly preferably hydrogen
• R 7 particularly particularly preferably represents hydrogen, in each case optionally monosubstituted to trisubstituted by fluorine, chlorine, methoxy, ethoxy, methylthio, ethylthio, cyano, CO-O-methyl or CO-O-ethyl, C r C 6 -alkyl, C 3 -C 6 alkenyl or C 3 -C 6 -
• Alkynyl each optionally optionally substituted by fluorine, chlorine, methyl, ethyl, methoxy, trifluoromethyl, cyano, CO 2 H, CO-O-methyl or CO-O-ethyl substituted C 3 -C 6 - cycloalkyl, C 3 -C 6 cycloalkyl-methyl, or C5-C6 cycloalkenyl, which may be optionally interrupted by an oxygen or sulfur atom, in each case optionally mono- to disubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl,
• R 8 very particularly preferably represents hydrogen, methyl, ethyl, propyl, isopropyl, allyl, propargyl, C 3 -C 4 -alkenyl, methoxy or ethoxy; or
• R 7 and R 8 together with the nitrogen atom to which they are attached represent a saturated 5- or 6-membered ring which may optionally be interrupted by oxygen or sulfur;
• R 9 and R 10 are particularly particularly preferably each independently of one another in each case optionally mono- to trisubstituted by fluorine and / or chlorine, methyl, ethyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, alkyloxy, methylthio, ethylthio,
• Especially preferred compounds according to the invention are the compounds of the formula (I) which contain a combination of the meanings given above as being particularly particularly preferred.
• 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.
• salts of sulfonic acids in which the acids themselves paralyze acting on insects (US 2,842,476).
• An increase in activity, for example, by ammonium sulfate is described, for example, for the herbicides glyphosate and phosphinothricin (US Pat. No. 6,645,914, EP-A2 0 036 106).
• a corresponding effect on insecticides is neither disclosed nor suggested by this prior art.
• the use of 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 increase the activity of crop protection agents containing heterocyclic carboxylic acid derivatives (I) are defined by formula (II)
• Q is nitrogen or phosphorus
• Q is preferably nitrogen
• R 26 , R 27 , R 28 and R 29 independently of one another represent hydrogen or in each case optionally substituted CpCg-alkyl or mono- or polyunsaturated, optionally substituted C 1 -C 8 -alkylene, where the substituents can be selected from halogen, nitro and cyano,
• R 26 , R 27 5 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 hydrogen carbonate, tetraborate, fluoride, bromide, iodide, chloride, monohydrogen phosphate, dihydrogen phosphate, hydrogen sulfate, tartrate, sulfate, nitrate,
• 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 (II) can be used in a wide concentration range for increasing the effect of crop protection agents containing heterocyclic carboxylic acid derivatives (1).
• the ammonium or phosphonium salts in the ready-to-use crop protection agent are used 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 / l.
• the concentration of ammonium and / or phosphonium salt in the formulation is chosen so that, after dilution of the formulation to the desired active ingredient concentration, it is expressed in this general, preferred or particularly preferred ranges.
• the concentration of the salt in the formulation is usually 1-50 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
• R ' has the meaning given above, EO is -CH 2 -CH 2 -O- and n is a number from 2 to 20.
• Another preferred group of penetration promoters are alkanol alkoxylates of the formula RO - (- EO-) p - (- PO-) q -R '(III-b) in which
• R has the abovementioned meaning
• R ' has the abovementioned meaning
• EO is -CH 2 -CH 2 -O-
• PO is C o H ⁇ 2r-C y H p - Ou
• p stands for numbers from 1 to 10 and q stands for numbers from 1 to 10.
• Another preferred group of penetration promoters are alkanol alkoxylates of the formula
• R has the meaning given above, R 'has the meaning given above, EO is -CH 2 -CH 2 -O-,
• PO is CH-CH-0 ;
• r is a number from 1 to 10 and s is a number from 1 to 10.
• Another preferred group of penetration enhancers are alkanol alkoxylates of the formula
• R and R ' have the meanings given above, EO is CH 2 -CH 2 -O-, BO is --CH r CH r CH-O,
• p stands for numbers from 1 to 10 and q stands for numbers from 1 to 10.
• Another preferred group of penetration enhancers are alkanol alkoxylates of the formula
• BO represents - CH r CH r CH-O
• EO is CH 2 -CH 2 -O-, r is a number from 1 to 10 and s is a number 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 Dodecyl, i-dodecyl, lauryl, myristyl, i-tridecyl, trimethyl-nonyl, palmityl, stearyl or eicosyl.
• alkanol alkoxylate of the formula (III-c) is 2-ethyl-hexyl alkoxylate of the formula
• EO stands for -CH 2 -CH 2 -O-
• the numbers 8 and 6 represent average values called.
• EO is CH 2 -CH 2 -O-
• BO stands for - CH ⁇ -CH j -CH-O
• the numbers 10, 6 and 2 represent average values called.
• Particularly preferred alkanol alkoxylates of the formula (ITI-f) are compounds of this formula in which
• 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 partly available commercially or can be prepared by known methods (compare WO 98/35 553, WO 00/35 278 and EP-A 0 681 865).
• Suitable penetration promoters are substances which promote the availability of the compounds of the formula (I) in the spray coating. 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 In the case of 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 In the ready-to-use agents (spray liquors), 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.
• Suitable additives which may be present in the formulations according to the invention are emulsifiers, foam-inhibiting agents, preservatives, antioxidants, dyes and inert fillers.
• 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 molluscs which are found in agriculture, horticulture, livestock, forests, gardens and recreational facilities, in the protection of materials and materials and in the hygiene sector. They can preferably be used as crop protection agents. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
• the above mentioned pests include:
• 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.
• helminths e.g. 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 flaria, Diphyllobothrium latum , Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa
• protozoa such as Eimeria
• Eimeria protozoa
• Laodelphax striatellus Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva fimbriolata, Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phy
• Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp., Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana, Trichoplusia spp ..
• Orthoptera for example, Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.
• Siphonaptera eg Ceratophyllus spp.
• Xenopsylla cheopis From the order of Symphyla eg Scutigerella immaculata.
• Thysanoptera eg Basothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp ..
• Thysanura eg 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 distinguished, in particular, by potent activity against insects, parasites of the subclass of Acari (Acarina ) (such as mites, spider mites and / or ticks) and / or nematodes.
• Acarina the subclass of Acari
• nematodes such as mites, spider mites and / or ticks
• 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, antimycotics, bactericides, viricides (including anti-viral agents) or as anti-MLO agents ( 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.
• Suitable extenders are, for example, water, polar and non-polar organic chemical liquids, for example 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, the simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, the sulfones and sulfoxides (such as dimethylsulfoxide).
• aromatic and non-aromatic hydrocarbons such as paraffins, Alkylbenzenes, alkylnaphthalenes, chlorobenzenes
• alcohols and polyols which may also be substituted, etherified and
• organic solvents can also be used as auxiliary solvents.
• Suitable liquid solvents are essentially: 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, for example petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethyl sulfoxide, and water.
• Suitable solid carriers are: for example, ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates, as solid carriers for granules: eg broken 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: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfon
• oligo- or polymers for example starting from vinylic monomers, from acrylic acid, from EO and / or PO alone or in combination with, for example, (poly) alcohols or (poly) amines.
• lignin and its sulfonic acid derivatives simple and modified celluloses, aromatic and / or aliphatic sulfonic acids and their adducts with formaldehyde.
• 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 such as iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
• Other 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 can be used in its commercial formulations as well as in the formulations prepared from these formulations in admixture with other active ingredients such as
• Insecticides Insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, safeners, fertilizers or semiochemicals.
• Particularly favorable mixing partners are e.g. the following: Fungicides:
• Azoxystrobin Cyazofamide, Dimoxystrobin, Enestrobin, Famoxadone, Fenamidon, Fluoxastrobin, Kresoximmethyl, Metominostrobin, Orysastrobin, Pyraclostrobin, Picoxystrobin, Trifloxystrobin
• copper salts such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and bordeaux mixture, dichlofluanid, dithianon, dodine, dodine free base, ferbam, folpet, fluorofolpet, guazatine, guazatin acetate, iminoctad
• Mancozeb Maneb, Metiram, Metiram Zinc, propineb, sulfur and sulfur preparations containing calcium polysulphide, thiram, tolylfluanid, zineb, ziram
• Pentachlorophenol and salts 2-phenylphenol and salts, piperine, propanosine sodium, proquinazide, pyribencarb, pyrrolnitrin, quintozene, tecloftalam, tecnazene, triazoxide, trichlamide, valiphenal, zarilamide,
• Insecticides / acaricides / nematicides acetylcholinesterase (AChE) inhibitors carbamates, for example alanycarb, aldicarb, aldoxycarb, allyxycarb, aminocarb, bendiocarb, benfuracarb, bufencarb, butacarb, butocarboxime, butoxycarboxime, carbaryl, carbofuran,
• AChE acetylcholinesterase
• Carbosulfan Cloethocarb, Dimetilan, Ethiofencarb, Fenobucarb, Fenothiocarb, Formetanate, Furathiocarb, Isoprocarb, Metam-sodium, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Promecarb, Propoxur, Thiodicarb, Thiofanox, Trimethacarb, XMC, Xylylcarb, Triazamate Organophosphate, to Example Acephate, Azamethiphos, Azinphos (-methyl, -ethyl), Bromophos-ethyl, Bromfenvinfos (-methyl), Butathiofos, Cadusafos, Carbophenothione, Chloroethoxyfos, Chlorfenvinphos, Chlormephos, Chlo ⁇ yrifos
• Pirimiphos (-methylAethyl), Profenofos, Propaphos, Propetamphos, Prothiofos, Prothoates, Pyraclofos, Pyridaphenthion, Pyridathion, Quinalphos, Sebufos, Sulfotep, Sulprofos, Tebupirimfos, Temephos, Terbufos, Tetrachlorvinphos, Thiometone, Triazophos, Triclorfone, Vamidothion Sodium Channel Modulators / Voltage-Dependent Sodium Channel Blocker Pyrethroids, for example, acrinathrin, allethrin (d-cis-trans, d-trans), beta-cyfluthrin, bifenthrin, bioallethrin, bioallethrin-S-cyclopentyl isomer, bioethanomethrin, biopermethrin, bioresmethrin, chl
• acetylcholine receptor agonists / antagonists chloronicotinyls for example acetamipride, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazines, thiacloprid, thiamethoxam nicotine, bensultap, cartap
• chloronicotinyls for example acetamipride, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazines, thiacloprid, thiamethoxam nicotine, bensultap, cartap
• Spinosyne for example spinosad
• GABA-controlled chloride channel antagonists Organochlorines, for example, Camphechlor, Chlordane, Endosulfan, Gamma-HCH, HCH, Heptachlor, Lindane, Methoxychlor Fiprole, for example, acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole, vanilliprole chloride channel activators Mectins , for example, abamectin, emamectin, emamectin benzoate, ivermectin, lepimectin, milbemycin
• Juvenile hormone mimetics for example, diofenolan, epofenonans, fenoxycarb, hydroprene, kinoprenes,
• Organotin compounds for example azocyclotin, cyhexatin, fenbutatin oxides
• METI Site I electron transport inhibitors METI's, for example Fenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebufenpyrad, Tolfenpyrad, Hydramethylnon Dicofol
• Bacillus thuringiensis strains inhibitors of fatty synthesis tetronic acids for example spirodiclofen, spiromesifen,
• Tetramic acids for example spirotetramat, cis-3- (2,5-dimethylphenyl) -4-hydroxy-8-methoxy-1-azaspiro [4.5] dec-3-en-2-one
• Carboxamides for example flonicamide
• Octopaminergic agonists for example, amitraz
• Nereistoxin analogs for example thiocyclam hydrogen oxalate, thiosultap-sodium
• Agonists of the ryanodine receptor benzoic acid dicarboxamides, for example flubendiamide
• anthranilamides for example, rynaxypyr (3-bromo-N- ⁇ 4-chloro-2-methyl-6- [(methylamino) arbonyl) -phenyl] -1-chloro-pyridine ⁇ -yO-1H-pyrazole-S-carboxamide)
• Active substances with unknown or nonspecific action mechanisms fumigants, for example aluminum phosphides, methyl bromides, sulfuryl fluoride feed inhibitors, for example cryolites, flonicamide, pymetrozine mite growth inhibitors, for example clofentezine, etoxazole, hexythiazox
• Cyflumetofen Dicyclanil, Fenoxacrim, Fentrifanil, Flubenzimine, Flufenerim, Flutenzine, Gossyplure, Hydramethylnone, Japonilure, Metoxadiazone, Petroleum, Piperonylbutoxide, Potassium oleate, Pyralidyl, Sulfluramid, Tetradifon, Tetrasul, Tri- arathene, Verbutin.
• 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 when used as insecticides in their commercial formulations as well as in the formulations prepared from these formulations in admixture with synergists.
• 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 furthermore, when used as insecticides in their commercial formulations and in the forms of use prepared from these formulations, be present in mixtures with inhibitors which reduce degradation of the active ingredient after application in the environment of the plant, on the surface of plant parts or in plant tissues ,
• 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.
• all plants and parts of plants can be treated.
• plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
• Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or can not be protected by plant breeders' rights.
• 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 takes place directly or by acting on their environment, habitat or storage space according to the usual treatment methods, for example by dipping, pouring, spraying, evaporating, atomizing, spreading, brushing, injecting and in propagation material, in particular at Seeds, still by single or multi-layer coating.
• 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 as meaning plants having new traits which have been bred by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, biotypes and genotypes.
• the treatment according to the invention may also give rise to superadditive ("synergistic") effects.
• superadditive for example, reduced application rates and / or extensions of the activity spectrum and / or enhancement of the action of the substances and agents which can be used according to the invention, 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 Harvest products possible that go beyond the expected effects.
• the preferred plants or plant varieties to be treated according to the invention to be treated include all plants which, as a result of the genetic engineering modification, obtained genetic material which gives these plants particularly advantageous valuable properties ("traits").
• traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to bottoms salt, increased flowering, easier harvesting, 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.
• Further and particularly emphasized examples of such properties are an increased defense of the plants against animal and microbial pests, as against insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance of the plants to certain herbicidal active substances.
• 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.
• Traits that are particularly emphasized 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, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF and combinations thereof) in the plants (hereinafter "Bt plants”). Traits also highlight the increased resistance of plants to 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
• Traits which are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (eg "PAT" gene).
• the genes which confer the desired properties (“traits") can also occur in combinations with one another in the transgenic plants.
• “Bt plants” are maize varieties, cotton varieties, soybean varieties and potato varieties which are sold under the trade names YIELD GARD® (eg corn, cotton, soya), KnockOut® (eg maize), StarLink® (eg maize), Bollgard® ( Cotton), Nucotn® (cotton) and NewLeaf® (Potato) are sold.
• 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, soy), Liberty Link® (tolerance to phosphinotricin, eg rapeseed), IMI® (tolerance against imidazolinone) and STS® (tolerance to sulfonylureas eg corn).
• Roundup Ready® tolerance to glyphosate eg corn, cotton, soy
• Liberty Link® tolerance to phosphinotricin, eg rapeseed
• IMI® tolerance against imidazolinone
• STS® tolerance to sulfonylureas eg corn
• Clearf ⁇ eld® 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 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.
• These parasites include: From the order of Anoplurida eg Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
• siphonaptrida e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
• Heteropterida e.g. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
• Actinedida Prostigmata
• Acaridida Acaridida
• eg 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.
• the active compounds of the formula (I) are also suitable for controlling arthropods, the livestock, such as cattle, sheep , Goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, put en, ducks, geese, bees, other pets such as dogs, cats, caged birds, aquarium fish and so-called experimental animals, such as hamsters, guinea pigs, rats and mice infested.
• livestock such as cattle, sheep , Goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, put en, ducks, geese, bees, other pets such as dogs, cats, caged birds, aquarium fish and so-called experimental animals, such as hamsters, guinea pigs, rats and mice infested.
• enteral administration in the form of, for example, tablets, capsules, infusions, drenches, granules, pastes, BoIi, the feed-through process, suppositories
• parenteral Administration for example by injections (
• 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 such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec. Tryptodendron spec.
• 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 antifouling 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 are used in closed rooms, such as apartments, factory buildings, offices, vehicle cabins u.a. occurrence. They can be used to control 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.
• isopods e.g. Oniscus asellus, Porcellio scaber.
• Anopheles spp. Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp.
• 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.
• Pemphigus spp. Phylloera vastatrix, Phthirus pubis. From the order of Heteroptera, e.g. Cimex hemipterus, Cimex lectularius, Rhodinus prolixus,
• Moth papers, moth sacs and moth gels, as granules or dusts, in straw baits or bait stations are known from WO 05/056556, WO 05/082907 and the international patent application with the application number PCT / EP 2006/001064 or can be prepared by the processes described therein.
• 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 a preparation of active compound 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, 1-3-3, 1-3-4, 1-3-5, 1 -3-6, 1-3-7, 1-3-9, 1-3-10, 1-3-11, 1-3-12, 1-3-13, 1-3-14, 1-3 -15, 1-3-16, 1-3-17, 1-3-19, 1-3-21, 1-3-22, 1-3-25, 1-3-26, 1-3-27 , 1-3-28, 1-3-29, 1-3-30, 1-3-31, 1-3-32, 1-3-35, 1-3-37, 1-3-38, 1 -3-39, 1-3-42, 1-3-47, 1-3-48, 1-3-49, 1-3-50, 1-3-52, 1-3-53, 1-3 -54, 1-3-55, 1-3-56, 1-3-57, 1-3-58, 1-3-59, 1-3-60, 1-3-61, 1-3-62 , 1-3-63, 1-3
• 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) infested with 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.
• 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.
• Corn leaf discs ⁇ Zea mays) are sprayed with an active compound preparation of the desired concentration and, after drying, are infested with caterpillars of the armyworm (Spodoptera frugiperda).
• the effect is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillar has 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, 1-3-5, 1-3-6, 1-3-8, 1 -3-9, 1-3- 10, 1-3-1 1, 1-3-12, 1-3-13, 1-3-14, 1-3-15, 1-3-16, 1- 3-17, 1-3-21, 1-3-23, 1-3-24, 1-3-25, 1-3-27, 1-3-28, 1-3-30, 1-3- 31, 1-3-32, 1-3-33, 1-3-35, 1-3-36, 1-3-37, 1-3-38, 1-3-45, 1-3-46, 1-3-47, 1-3-48, 1-3- 49, 1-3-50, 1-3-51, 1-3-58, 1-3-59, 1-3-60, 1- 3-61, 1-3-62, 1-3-64, 1-3-66, 1-3-67, 1-3-68, 1-3-71, 1-3-72, 1-3- 76, 1-3-79, 1-3-81,
• 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 have an activity of> 80% at an application rate of 100 g / ha: 1-3-58, 1-3-76, 1-3-315, 1-3-316, 1-3-318, 1-3-329, 1-3-330, 1-3-346, 1-3-348.
• the following compounds of the preparation examples show an activity of> 80% at an application rate of 500 g / ha: 1-3-6, 1-3-1 1, 1-3-14, 1-3-17 , 1-3-27, 1-3-38, 1-3-68, 1-3-79, 1-3-81, 1-3-92, 1-3-125, 1-3-246, 1 -3-248, 1-3-251, 1-3-260, 1-3-262, 1-3-283, 1-3-301, 1-3-302, 1-3-309, 1-3 -388, 1-3-389, 1-3-320, 1-3-334, 1-3-337, 1-3-340, 1-3-348, 1-3-359, 1-3-362 , 1-3-365, 1-3-382 "I-3-401, 1-3-407, 1-3-410.
• Solvent dimethyl sulfoxide To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of water and the concentrate is diluted with water to the desired concentration.
• Vessels containing horsemeat treated with the preparation of active compound of the desired concentration are mated 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 following compounds of the preparation examples with a test concentration of 100 ppm have an efficacy of> 80%: 1-3-1, 1-3-6,, 1-3-7, 1-3-8, 1-3-9, I 3-10, 1-3-11, 1-3-12, 1-3-13, 1-3-14, 1-3-15, 1-3-16, 1-3-17, 1-3 -18, 1-3-19, 1-3-21, 1-3-22, 1-3-23, 1-3-24, 1-3-25, 1-3-26, 1-3-27 , 1-3-28, 1-3-30, 1-3-31, 1-3-32, 1-3-33, 1-3-35, 1-3-36, 1-3-37, 1 -3-38, 1-3- 63, 1-3-67, 1-3-76, 1-3-127, 1-3-129, 1-3-149, 1-3-188, 1-3 -205, 1-3-214, 1-3-225, 1-3-246, 1-3-248, 1-3251, 1-3-260, 1-3-323, 1-3-339 ,
• the drug solution is injected into the abdomen ⁇ Boophilus mircoplus), the animals are transferred into trays and kept in an air-conditioned room.
• the effect is determined in%. 100% means that no ticks have laid fertile eggs.
• the following compounds show an efficacy of> 80% for the test concentration of 20 ⁇ g / animal: 1-3-1, 1-3-4, 1-3-11, 1-3-12, 1-3- 17, 1-3-18, 1-3-27, 1-3-28, 1-3-31, I-3-33, 1-3-35, 1-3-36, 1-3-37, 1-3-38, 1-3-46, 1-3-58, 1-3-67, 1-3-74, 1-3-76, 1-3-88, 1-3-92, 1- 3-114, I-3-119, 1-3-122, 1-3-123, 1-3-127, 1-3-128, 1-3-129, 1-3-147, 1-3- 149, 1-3-159, 1-3-172, 1-3-176, 1-3-185, 1-3-187, 1-3-188, 1-3-202, 1-3-205, 1-3-214, 1-3-225, 1-3-227, 1-3-228, 1-3-229, 1-3-231, 1-3- 246, 1-3-248, 1-3-251, 1-
• Vessels containing a sponge treated with the preparation of active compound of the desired concentration are occupied by (Musca domestic) adults.
• the kill is determined in%. 100% means that all flies have been killed; 0% means that no flies have been killed.
• 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 show an activity of> 80% at an application rate of 20 ppm: 1-3-7, 1-3-41, 1-3-42, 1-3-46, 1-3 - 59, 1-3-61, 1-3-64, 1-3-65, 1-3-66, 1-3-70, 1-3-71, 1-3-78, 1-3-80 , 1-3-82, 1-3-96, 1-3-101, 1-3-1 15, I-3-1 16, 1-3-117, 1-3-118, 1-3-120 , 1-3-127, 1-3-131, 1-3-133, 1-3-135, 1-3-136, 1-3-137, 1-3-138, 1-3-163, 1 -3-164, 1-3-166, 1-3-198, 1-3-200
• the following compounds of the preparation examples have an activity of> 80% at an application rate of 4 ppm: 1-3-1, 1-3-29, 1-3-30, 1-3-99, 1-3-193, 1- 3-194, 1-3-227, 1-3-230, 1-3-275.
• Nilaparvata lugens test (NILALU hydroponic treatment)
• 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.
• the preparation of the active compound is pipetted in water.
• the effect is determined in%. 100% means that all rice cicadas have been killed, 0% means that no rice cicadas have been killed.
• 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.
• Soybean leaves ⁇ Glycine max.) Are sprayed with an active compound preparation of the desired concentration and, after drying, are populated with eggs of the cotton bollworm ⁇ Heliotis virescens).
• the effect is determined in%. 100% means that all eggs have been killed; 0% means that no eggs were killed.
• Example 11 Increasing the Effectiveness of Ammonium / Phosphonium Salts in Combination with Penetration Promoters
• 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, penetration enhancers or ammonium salts and penetration promoters these are pipetted in each case to the finished preparation solution in a concentration of 1000 ppm after dilution.
• Paprika plants (Capsicum annuur ⁇ ) which are heavily infested with the green peach aphid ⁇ Myzus persicae) are treated by drip-whisking with the preparation of active compound in the desired concentration. After the desired time the kill is determined in%. 100% means that all animals have been killed; O% means that no animals have been killed.
• 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, penetration enhancers or ammonium salts and penetration promoters these are pipetted in each case to the finished preparation solution in a concentration of 1000 ppm after dilution.
• Cotton plants (Gossypium hirsutum) heavily infested with the cotton aphid ⁇ Aphis gossypii) are treated by drip-wet spraying with the preparation of active compound in the desired concentration.
• the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.

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• 2006
  • 2006-08-22 DE DE102006039255A patent/DE102006039255A1/de not_active Withdrawn
• 2007
  • 2007-06-14 EP EP07726015A patent/EP2061319A1/de not_active Withdrawn
  • 2007-06-14 KR KR1020097005231A patent/KR20090040468A/ko not_active Application Discontinuation
  • 2007-06-14 JP JP2009524083A patent/JP2010500979A/ja not_active Withdrawn
  • 2007-06-14 WO PCT/EP2007/005251 patent/WO2008019723A1/de active Application Filing
  • 2007-06-14 US US12/377,566 patent/US20100222218A1/en not_active Abandoned
  • 2007-06-14 BR BRPI0715792-4A patent/BRPI0715792A2/pt not_active Application Discontinuation

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