Selective insecticides based on substituted cyclic ketoenols and safeners

The present invention relates to the use of selective insecticidal compositions, characterized in that they comprise an effective amount of an active compound combination comprising

This application is a National Stage of International Application No. PCT/EP2005/007794, filed Jul. 18, 2005, which claims the benefit of German Patent Application No. 10 2004 035 133.3, filed Jul. 20, 2004. The entirety of each of these applications is incorporated by reference herein.

The invention relates to the use of selective insecticidally and/or acaricidally active compound combinations which comprise substituted cyclic ketoenols, on the one hand, and at least one compound which improves crop plant compatibility, on the other, for the selective control of insects and/or spider mites in various crops of useful plants.

Moreover, selective herbicides based on substituted cyclic ketoenols and safeners have been described (WO 03/013249).

However, the compatibility of these compounds in particular with monocotyledonous crop plants is not under all conditions entirely satisfactory.

Surprisingly, it has now been found that certain substituted cyclic ketoenols, when used together with the crop plant compatibility-improving compounds (safeners/antidotes) described below, prevent damage to the crop plants extremely efficiently and can be used particularly advantageously as broadband combination preparations for the selective control of insects even in crops of monocotyledonous useful plants, such as, for example, in cereals, but also in maize, millet and rice.

The invention provides the use of selective insecticidal and/or acaricidal compositions comprising an effective amount of an active compound combination comprising, as components,(a) at least one substituted cyclic ketoenol of the formula (I)

in whichA represents hydrogen, in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, saturated or unsaturated, optionally substituted cycloalkyl, in which optionally at least one ring atom is replaced by a heteroatom, or in each case optionally halogen-, alkyl-, haloalkyl-, alkoxy-, haloalkoxy-, cyano- or nitro-substituted aryl, arylalkyl or hetaryl,B represents hydrogen, alkyl or alkoxyalkyl, orA and B together with the carbon atom to which they are attached represent a saturated or unsaturated, unsubstituted or substituted cycle which optionally contains at least one heteroatom,D represents hydrogen or an optionally substituted radical from the group consisting of alkyl, alkenyl, alkynyl, alkoxyalkyl, saturated or unsaturated cycloalkyl, in which optionally one or more ring members are replaced by heteroatoms, arylalkyl, aryl, hetarylalkyl or hetaryl, orA and D together with the atoms to which they are attached represent a saturated or unsaturated cycle which is unsubstituted or substituted in the A,D moiety and optionally contains at least one heteroatom, orA and Q1together represent alkanediyl or alkenediyl which are in each case optionally substituted by hydroxyl or by in each case optionally substituted alkyl, alkoxy, alkylthio, cycloalkyl, benzyloxy or aryl, orQ1represents hydrogen or alkyl,Q2, Q4, Q5and Q6independently of one another represent hydrogen or alkyl,Q3represents hydrogen, alkyl, alkoxyalkyl, alkylthioalkyl, optionally substituted cycloalkyl (in which optionally one methylene group is replaced by oxygen or sulphur) or optionally substituted phenyl, orQ3and Q4together with the carbon atom to which they are attached, represent a saturated or unsaturated, unsubstituted or substituted cycle which optionally contains a heteroatom,G represents hydrogen (a) or represents one of the groups

or of the general formula (IIb)

or the formula (IIc)

wherem represents a number 0, 1, 2, 3, 4 or 5,A1represents one of the divalent heterocyclic groupings shown below

or of the general formula (IIe)

In the definitions, the hydrocarbon chains, such as in alkyl or alkanediyl, are in each case straight-chain or branched—including in combination with heteroatoms, such as in alkoxy.

Depending inter alia on the nature of the substituents, the compounds of the formula (I) can be present as geometrical and/or optical isomers or isomer mixtures of varying composition which, if appropriate, can be separated in a customary manner. The present invention provides both the pure isomers and the isomer mixtures, and their use and the compositions comprising them. However, for the sake of simplicity, hereinbelow only compounds of the formula (I) are referred to, although what is meant are both the pure compounds and, if appropriate, also mixtures having various proportions of isomeric compounds.

Including the meanings (1) to (6) of the group CKE, the following principal structures (I-1) to (I-6) result:

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following principal structures (I-1-a) to (I-1-g) result if CKE represents the group (1),

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following principal structures (I-2-a) to (I-2-g) result if CKE represents the group (2)

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following principal structures (I-3-a) to (I-3-g) result if CKE represents the group (3)

Depending on the position of the substituent G, the compounds of the formula (I-4) can be present in the two isomeric forms of the formulae (I-4-A) and (I-4-B)

which is meant to be indicated by the broken line in formula (I-4).

The compounds of the formulae (I-4-A) and (I-4-B) can be present both as mixtures and in the form of their pure isomers. Mixtures of the compounds of the formulae (I-4-A) and (I-4-B) can, if appropriate, be separated in a manner known per se by physical methods, for example by chromatographic methods.

For reasons of clarity, hereinbelow only one of the possible isomers is shown in each case. This does not exclude that the compounds may, if appropriate, be present in the form of the isomer mixtures or in the respective other isomeric form.

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following principal structures (I-4-a) to (I-4-g) result if CKE represents the group (4)

Depending on the position of the substituent G, the compounds of the formula (I-5) can be present in the two isomeric forms of the formulae (I-5-A) and (I-5-B)

which is meant to be indicated by the broken line in the formula (I-5).

The compounds of the formulae (I-5-A) and (I-5-B) can be present both as mixtures and in the form of their pure isomers. Mixtures of the compounds of the formulae (I-5-A) and (I-5-B) can, if appropriate, be separated by physical methods, for example by chromatographic methods.

For reasons of clarity, hereinbelow only one of the possible isomers is shown in each case. This does not exclude that the compounds may, if appropriate, be present in the form of the isomer mixtures or in the respective other isomeric form.

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following principal structures (I-5-a) to (I-5-g) result:

Depending on the position of the substituent G, the compounds of the formula (I-6) can be present in the two isomeric forms of the formulae (I-6-A) and (I-6-B) which is meant to be indicated by the broken line in the formula (I-6):

The compounds of the formulae (I-6-A) and (I-6-B) can be present both as mixtures and in the form of their pure isomers. Mixtures of the compounds of the formulae (I-6-A) and (I-6-B) may, if appropriate, be separated by physical methods, for example by chromatographic methods.

For reasons of clarity, hereinbelow only one of the possible isomers is shown in each case. This includes that the compound in question may, if appropriate, be present as an isomer mixture or in the respective other isomeric form.

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following principal structures (I-6-a) to (I-6-g) result:

The formula (I) provides a general definition of the substituted cyclic ketoenols according to the invention of the acaricidal and insecticidal compositions. Preferred substituents and ranges of the radicals given in the formulae mentioned above and below are illustrated below:X preferably represents halogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C1-C6-alkoxy, C3-C6-alkenyloxy, C1-C6-haloalkoxy, C3-C6-haloalkenyloxy, nitro or cyano,Z preferably represents hydrogen, halogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or represents one of the radicals

A particularly preferably represents hydrogen, in each case optionally fluorine- or chlorine-substituted C1-C6-alkyl, C1-C4-alkoxy-C1-C4-alkyl or optionally fluorine-, chlorine-, C1-C4-alkyl- or C1-C4-alkoxy-substituted C3-C7-cycloalkyl,B particularly preferably represents hydrogen or C1-C6-alkyl, orA, B and the carbon atom to which they are attached particularly preferably represent saturated C3-C7-cycloalkyl or unsaturated C5-C7-cycloalkyl in which optionally one ring member is replaced by oxygen or sulphur and which is optionally monosubstituted by C1-C6-alkyl, C1-C3-haloalkyl or C1-C6-alkoxy, orA, B and the carbon atom to which they are attached particularly preferably represent C5-C6-cycloalkyl which is substituted by an alkylenediyl or by an alkylenedioxy or by an alkylenedithiol group which, together with the carbon atom to which it is attached, forms a further five- or six-membered ring and which is optionally substituted by methyl or ethyl and optionally contains one or two not directly adjacent oxygen or sulphur atoms,D particularly preferably represents hydrogen, represents in each case optionally fluorine- or chlorine-substituted C1-C6-alkyl, C3-C6-alkenyl, C1-C4-alkoxy-C2-C3-alkyl, represents optionally C1-C4-alkyl-, C1-C4-alkoxy- or C1-C2-haloalkyl-substituted C3-C7-cycloalkyl, orA and D together particularly preferably represent optionally substituted C3-C5-alkanediyl in which one methylene group may be replaced by oxygen or sulphur, possible substituents being C1-C4-alkyl, orA and D (in the case of the compounds of the formula (I-1)) together with the atoms to which they are attached represent one of the groups AD-1 to AD-10:

A and Q1together particularly preferably represent C3-C4-alkanediyl or C3-C4-alkenediyl, each of which is optionally mono- or disubstituted by identical or different substituents from the group consisting of C1-C4-alkyl and C1-C4-alkoxy, orQ1particularly preferably represents hydrogen,Q2particularly preferably represents hydrogen,Q4, Q5and Q6independently of one another particularly preferably represent hydrogen or C1-C2-alkyl,Q3particularly preferably represents hydrogen, C1-C4-alkyl, C1-C4-alkoxy-C1-C2-alkyl, C1-C4-alkylthio-C1-C2-alkyl or optionally methyl- or methoxy-substituted C3-C6-cycloalkyl in which optionally one methylene group is replaced by oxygen or sulphur, orQ3and Q4together with the carbon to which they are attached particularly preferably represent an optionally C1-C4-alkyl- or C1-C4-alkoxy-substituted saturated C5-C6-ring in which optionally one ring member is replaced by oxygen or sulphur,G particularly preferably represents hydrogen (a) or represents one of the groups

In the radical definitions mentioned as being particularly preferred, halogen represents fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine.W very particularly preferably represents hydrogen, chlorine, bromine, methyl, ethyl or methoxy,X very particularly preferably represents chlorine, bromine, methyl, ethyl, methoxy, ethoxy or trifluoromethyl,Y very particularly preferably represents hydrogen, chlorine, bromine, methyl, ethyl, propyl or trifluoromethyl,Z very particularly preferably represents hydrogen, chlorine, bromine, methyl or represents the radical

V1very particularly preferably represents hydrogen, fluorine, chlorine, methyl, ethyl, methoxy, trifluoromethyl or trifluoromethoxy,V2very particularly preferably represents hydrogen, fluorine, chlorine or methyl,CKE very particularly preferably represents one of the groups

A very particularly preferably represents hydrogen, in each case optionally fluorine-substituted C1-C4-alkyl, C1-C2-alkoxy-C1-C2-alkyl or C3-C6-cycloalkyl,B very particularly preferably represents hydrogen or methyl, orA, B and the carbon atom to which they are attached very particularly preferably represent saturated C5-C6-cycloalkyl in which optionally one ring member is replaced by oxygen or sulphur and which is optionally monosubstituted by methyl, ethyl, propyl, trifluoromethyl, methoxy, ethoxy, propoxy, butoxy or isobutoxy, orA, B and the carbon atom to which they are attached very particularly preferably represent C5-C6-cycloalkyl which is substituted by an alkylenedioxyl group which contains two not directly adjacent oxygen atoms and which, together with the carbon to which they are attached, form a further five- or six-membered ring,D very particularly preferably represents hydrogen, C1-C4-alkyl, C3-C4-alkenyl, C1-C2-alkoxy-C2-C3-alkyl or C3-C6-cycloalkyl,orA and D together very particularly preferably represent optionally substituted C3-C5-alkanediyl in which optionally one carbon atom is replaced by oxygen or sulphur,A and D (in the case of the compounds of the formula (I-1)) together with the atoms to which they are attached represent the group:

A and Q1together very particularly preferably represent C3-C4-alkanediyl which is optionally mono- or disubstituted by methyl or methoxy, orQ1very particularly preferably represents hydrogen,Q2very particularly preferably represents hydrogen,Q4, Q5and Q6independently of one another very particularly preferably represent hydrogen or methyl,Q3very particularly preferably represents hydrogen, methyl, ethyl or C3-C6-cycloalkyl, orQ3and Q4together with the carbon to which they are attached very particularly preferably represent a saturated C5-C6-ring which is optionally substituted by methyl or methoxy and in which optionally one ring member is replaced by oxygen,G very particularly preferably represents hydrogen (a) or represents one of the groups

which is located in the para-position to the substituent X,V1especially preferably represents fluorine, chlorine, or trifluoromethyl,V2especially preferably represents hydrogen, fluorine or chlorine,CKE especially preferably represents one of the groups

A, B and the carbon atom to which they are attached especially preferably represent unsaturated C5-C6-cycloalkyl in which optionally one ring member is replaced by oxygen and which is optionally monosubstituted by methyl, methoxy, ethoxy, propoxy or trifluoromethyl,D especially preferably represents hydrogen,G especially preferably represents hydrogen (a) or represents one of the groups

in whichL represents oxygen andM represents oxygen or sulphur,R1especially preferably represents C1-C6-alkyl, C2-C6-alkenyl, C1-C2-alkoxy-C1-alkyl, C1-C2-alkylthio-C1-alkyl or represents cyclopropyl or cyclohexyl, each of which is optionally monosubstituted by fluorine, chlorine, methyl or methoxy,represents phenyl which is optionally monosubstituted by fluorine, chlorine, bromine, cyano, nitro, methyl, methoxy, trifluoromethyl or trifluoromethoxy,R2especially preferably represents phenyl or benzyl, C1-C8-alkyl, C2-C6-alkenyl or C1-C4-alkoxy-C2-C3-alkyl, each of which is optionally mono- to trisubstituted by fluorine.

Emphasis is given to compounds of the formula (I) mentioned above in which the radicals are as defined below:W especially represents hydrogen or methyl,X especially represents chlorine, bromine, methyl or ethyl,Y especially represents hydrogen, chlorine, bromine or methyl,Z especially represents hydrogen, chlorine, bromine or methyl,CKE especially represents the group

A, B and the carbon atom to which they are attached especially represent saturated C6-cycloalkyl in which optionally one ring member is replaced by oxygen and which is optionally monosubstituted by methyl, trifluoromethyl, methoxy, ethoxy or propoxy,G especially represents hydrogen (a) or represents one of the groups

Particular emphasis, as examples, is given to compounds of the formula (I-1′), in which the radicals are as defined below:

The general or preferred radical definitions or illustrations given above can be combined with one another as desired, i.e. including combinations between the respective ranges and preferred ranges.

Preference according to the invention is given to the use of the compounds of the formula (I) which contain a combination of the meanings given above as being preferred (preferable).

Particular preference according to the invention is given to the use of the compounds of the formula (I) which contain a combination of the meanings given above as being particularly preferred.

Very particular preference according to the invention is given to the use of the compounds of the formula (I) which contain a combination of the meanings given above as being very particularly preferred.

Especial preference according to the invention is given to the use of the compounds of the formula (I) which contain a combination of the meanings given above as being especially preferred.

Emphasis is given, according to the invention, to the use of the compounds of the formula (I) which contain a combination of the meanings given above as being especial.

Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl can, as far as this is possible, in each case be straight-chain or branched, including in combination with heteroatoms, such as, for example, in alkoxy.

Unless indicated otherwise, optionally substituted radicals can be mono- or polysubstituted, where in the case of polysubstitution, the substituents can be identical or different.

In addition to the compounds mentioned in the examples, the following compounds of the formula (I-1-a) may be specifically mentioned:

TABLE 1W = CH3, X = CH3, Y = 4-CH3, Z = H.ABDCH3CH3HC2H5CH3HC3H7CH3Hi-C3H7CH3HCH3H—(CH2)4H—(CH2)5—H—(CH2)2—O—(CH2)2—H—CH2—O—(CH2)3—H—CH2—CHCH3—(CH2)3—H—(CH2)2—CHCH3—(CH2)2—H—(CH2)2—CHOCH3—(CH2)2—H—(CH2)2—CHOC2H5—(CH2)2—H—(CH2)2—C(CH3)2—(CH2)2—HTable 2: A, B and D are as indicated in Table 1W═CH3; X═CH3; Y=4-Cl; Z═H.Table 3: A, B and D are as indicated in Table 1W═CH3; X═CH3; Y=4-Br; Z═H.Table 4: A, B and D are as indicated in Table 1W═C2H5; X═CH3; Y=4-Cl; Z═H.Table 5: A, B and D are as indicated in Table 1W═C2H5; X═CH3; Y=4-Br; Z═H.Table 6: A, B and D are as indicated in Table 1W═C2H5; X═C2H5; Y=4-Cl; Z═H.Table 7: A, B and D are as indicated in Table 1W═C2H5; X═C2H5; Y=4-Br; Z═H.Table 8: A, B and D are as indicated in Table 1W═CH3; X═Cl; Y=4-Cl; Z═H.Table 9: A, B and D are as indicated in Table 1W═CH3; X═Br; Y═4-Br; Z═H.Table 10: A, B and D are as indicated in Table 1W═C1H3; X═Cl; Y═4-Br; Z═HTable 11: A, B and D are as indicated in Table 1W═CH3; X═Br; Y=4-Cl; Z═H.Table 12: A, B and D are as indicated in Table 1W═C2H5; X═Cl; Y═4-Cl; Z═H.Table 13: A, B and D are as indicated in Table 1W═C2H5; X═Br; Y=4-Br; Z═H.Table 14: A, B and D are as indicated in Table 1W═C2H5; X═Cl; Y═4-Br; Z═H.Table 15: A, B and D are as indicated in Table 1W═C2H5; X═Br; Y═4-Cl; Z═H.Table 16: A, B and D are as indicated in Table 1W═H; X═Cl; Y═H; Z═H.Table 17: A, B and D are as indicated in Table 1W═H; X═Br; Y═H; Z═H.Table 18: A, B and D are as indicated in Table 1W═H; X═CH3; Y═H; Z═H.Table 19: A, B and D are as indicated in Table 1W═H; X═CF3; Y═H; Z═H.Table 20: A, B and D are as indicated in Table 1W═H; X═CH3; Y=4-Cl; Z═H.Table 21: A, B and D are as indicated in Table 1W═H; X═Cl; Y=4-CH3; Z═H.Table 22: A, B and D are as indicated in Table 1W═H; X═CH3; Y=4-Br; Z═H.Table 23: A, B and D are as indicated in Table 1W═H; X═Br; Y=4-CH3; Z═H.Table 24: A, B and D are as indicated in Table 1W═H; X═Cl; Y=4-Cl; Z═H.Table 25: A, B and D are as indicated in Table 1W═H; X═Cl; Y=4-Br; Z═H.Table 26: A, B and D are as indicated in Table 1W═H; X═Br; Y=4-Cl; Z═H.Table 27: A, B and D are as indicated in Table 1W═CH3; X═Cl; Y=4-CH3; Z═H.Table 28: A, B and D are as indicated in Table 1W═CH3; X═Br; Y=4-CH3; Z═H.Table 29: A, B and D are as indicated in Table 1W═C2H5; X═Cl; Y=4-CH3; Z═H.Table 30: A, B and D are as indicated in Table 1W═C2H5; X═Br; Y=4-CH3; Z═H.Table 31: A, B and D are as indicated in Table 1W═C2H5; X═CH3; Y=4-CH3; Z═H.Table 32: A, B and D are as indicated in Table 1W═C2H5; X═C2H5; Y=4-CH3; Z═H.Table 33: A, B and D are as indicated in Table 1W═C2H5; X═C2H5; Y=4-C2H5; Z═H.Table 34: A, B and D are as indicated in Table 1W═H; X═CH3; Y=4-CH3; Z=5-CH3.Table 35: A, B and D are as indicated in Table 1W═H; X═CH3; Y=4-Cl; Z=5-CH3.Table 36: A, B and D are as indicated in Table 1W═H; X═Br; Y=4-CH3; Z=5-CH3.Table 37: A, B and D are as indicated in Table 1W═H; X═Cl; Y=4-Cl; Z=5-CH3.Table 38: A, B and D are as indicated in Table 1W═H; X═CH3; Y=4-Br; Z=5-CH3.Table 39: A, B and D are as indicated in Table 1W═H; X═Cl; Y=4-CH3; Z=5-Cl.Table 40: A, B and D are as indicated in Table 1W═H; X═CH3; Y═H; Z=5-CH3.Table 41: A, B and D are as indicated in Table 1W═H; X═Cl; Y═H; Z=5-CH3.Table 42: A, B and D are as indicated in Table 1W═H; X═Br; Y═H; Z=5-CH3.Table 43: A, B and D are as indicated in Table 1W═CH3; X═CH3; Y=4-CH3; Z=3-CH3.Table 44: A, B and D are as indicated in Table 1W═CH3; X═CH3; Y═H; Z=3-Br.Table 45: A, B and D are as indicated in Table 1W═CH3; X═CH3; Y=4-CH3; Z=3-Cl.Table 46: A, B and D are as indicated in Table 1W═CH3; X═CH3; Y=4-CH3; Z=3-Br.Table 47: A, B and D are as indicated in Table 1W═CH3; X═CH3; Y═H; Z=3-Cl.

The compounds of the formula (I) are known in principle from the patent specifications mentioned at the outset, or they may be prepared according to the methods described therein.

Preferred meanings of the groups listed above in connection with the crop plant compatibility-improving compounds (“insecticide and acaricide safeners”) of the formulae (IIa), (IIb), (IIc), (IId) and (IIe) are defined below.m preferably represents the number 0, 1, 2, 3 or 4,A1preferably represents one of the divalent heterocyclic groupings shown below

Examples of compounds of the formula (IIa) which are very particularly preferred as insecticide and acaricide safeners according to the invention are listed in the table below.

Table Examples of the compounds of the formula (IIa)

Examples of compounds of the formula (IIb) which are very particularly preferred as insecticide and acaricide safeners according to the invention are listed in the table below.

Examples of the compounds of the formula (IIc) which are very particularly preferred as insecticide and acaricide safeners according to the invention are listed in the table below.

TABLE(IIc)Examples of the compounds of the formula (IIc)ExampleNo.R10N(R11, R12)IIc-1CHCl2N(CH2CH═CH2)2IIc-2CHCl2IIc-3CHCl2IIc-4CHCl2IIc-5CHCl2IIc-6CHCl2IIc-7CHCl2

Examples of the compounds of the formula (IId) which are very particularly preferred as insecticide and acaricide safeners according to the invention are listed in the table below.

Examples of the compounds of the formula (IIe) which are very particularly preferred as insecticide and acaricide safeners according to the invention are listed in the table below.

Examples of the selectively insecticidal and/or acaricidal 1 combinations according to the invention of in each case one active compound of the formula (I) and in each case one of the safeners defined above are listed in the table below.

Table Examples of the combinations according to the invention

Active compound of theformula (I)SafenerI-1cloquintocet-mexylI-1fenchlorazole-ethylI-1isoxadifen-ethylI-1mefenpyr-diethylI-1furilazoleI-1fenclorimI-1cumyluronI-1daimuron/dymronI-1dimepiperateI-1IIe-11I-1IIe-5I-1dichlormidI-2cloquintocet-mexylI-2fenchlorazole-ethylI-2isoxadifen-ethylI-2mefenpyr-diethylI-2furilazoleI-2fenclorimI-2cumyluronI-2daimuron/dymronI-2dimepiperateI-2IIe-11I-2IIe-5I-2dichlormidI-3cloquintocet-mexylI-3fenchlorazole-ethylI-3isoxadifen-ethylI-3mefenpyr-diethylI-3furilazoleI-3fenclorimI-3cumyluronI-3daimuron/dymronI-3dimepiperateI-3IIe-5I-3IIe-11I-3dichlormidI-4cloquintocet-mexylI-4fenchlorazole-ethylI-4isoxadifen-ethylI-4mefenpyr-diethylI-4furilazoleI-4fenclorimI-4cumyluronI-4daimuron/dymronI-4dimepiperateI-4IIe-11I-4IIe-5I-4dichlormidI-5cloquintocet-mexylI-5fenchlorazole-ethylI-5isoxadifen-ethylI-5mefenpyr-diethylI-5furilazoleI-5fenclorimI-5cumyluronI-5daimuron/dymronI-5dimepiperateI-5IIe-5I-5IIe-11I-5dichlormidI-6cloquintocet-mexylI-6fenchlorazole-ethylI-6isoxadifen-ethylI-6mefenpyr-diethylI-6furilazoleI-6fenclorimI-6cumyluronI-6daimuron/dymronI-6dimepiperateI-6IIe-5I-6IIe-11I-6dichlormid

The compounds of the general formula (IIa) to be used as safeners are known and/or can be prepared by processes known per se (cf. WO-A-91/07874, WO-A-95/07897).

The compounds of the general formula (IIb) to be used as safeners are known and/or can be prepared by processes known per se (cf. EP-A-191736).

The compounds of the general formula (IIc) to be used as safeners are known and/or can be prepared by processes known per se (cf. DE-A-2218097, DE-A-2350547).

The compounds of the general formula (IId) to be used as safeners are known and/or can be prepared by processes known per se (cf. DE-A-19621522/U.S. Pat. No. 6,235,680).

The compounds of the general formula (IIe) to be used as safeners are known and/or can be prepared by processes known per se (cf. WO-A-99/66795/U.S. Pat. No. 6,251,827).

Surprisingly, it has now been found that the above-defined active compound combinations of substituted ketoenols of the general formula (I) and safeners (antidotes) of group (b) listed above, whilst being tolerated very well by useful plants, have good insecticidal and/or acaricidal activity and can be used in various crops, in particular in cereals (especially wheat and barley), but also in millet, maize and rice, for the selective control of insects.

Here, it has to be considered to be surprising that, from a large number of known safeners or antidotes which are capable of antagonizing the damaging effect of a herbicide on the crop plants, it is in particular the abovementioned compounds of group (b) which are suitable for neutralizing the damaging effect of substituted cyclic ketoenols of the formula (I) on the crop plants virtually completely without negatively affecting the insecticidal and/or acaricidal activity.

Furthermore, it has to be considered to be completely surprising that compounds from group (b) listed above are not only capable of virtually completely neutralizing the damaging effect of substituted cyclic ketoenols of the formula (I) on the crop plants but in some cases even enhance the insecticidal and/or acaricidal activity of the substituted cyclic ketoenols of the formula (I), so that a synergistic effect can be observed.

Emphasis is given here to the particularly advantageous effect of the particularly and most preferred combination partners from group (b), in particular in respect of sparing cereal plants, such as, for example, wheat, barley and rye, but also millet, maize and rice, as crop plants.

The combinations of active compounds can be used, for example, for the following plants:

However, the use of the combinations of active compounds is by no means limited to these genera but equally also extends to other plants.

The advantageous effect of the combinations of active compounds is particularly strongly pronounced at certain concentration ratios. However, the weight ratios of the active compounds in the combinations of active compounds can be varied within relatively wide ranges. In general, 0.001 to 1000 parts by weight, preferably 0.01 to 100 parts by weight, particularly preferably 0.05 to 10 parts by weight and most preferably 0.07 to 1.5 parts by weight of one of the crop plant compatibility-improving compounds (antidotes/safeners) mentioned above under (b) are present per part by weight of active compound of the formula (I) or salts thereof.

The active compounds or active compound combinations can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspoemulsion concentrates, natural and synthetic materials impregnated with active compound and microencapsulations in polymeric materials.

These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is, emulsifiers and/or dispersants and/or foam formers.

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; suitable as solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable as 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, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable as dispersants are: for example lignosulphite waste liquors and methylcellulose.

The formulations in general comprise between 0.1 and 95% by weight of active compounds, including the active compounds with a safening effect, preferably between 0.5 and 90%.

The combinations of active compounds are generally applied in the form of ready-to-use formulations. However, the active compounds contained in the combinations of active compounds may also be applied in the form of individual formulations which are mixed upon use, that is, in the form of tank mixes.

The combinations of active compounds, as such or in their formulations, may furthermore also be used as a mixture with other known herbicides, again with ready-to-use formulations or tank mixes being possible. A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, attractants, sterilants, bactericides, bird repellents, growth substances, plant nutrients and soil conditioners is also possible. It may furthermore be advantageous for specific applications, in particular for the post-emergence method, to incorporate into the formulations plant-compatible mineral or vegetable oils (for example the commercial product “Rako Binol”) or ammonium salts, such as, for example, ammonium sulphate or ammonium thiocyanate, as further additives.

The combinations of active compounds can be used as such, in the form of their formulations or the use forms which are prepared from these formulations by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. Application is effected in the customary manner, for example by watering, spraying, atomizing, dusting or broadcasting.

The application rates of the combinations of active compound can be varied within a certain range; they depend inter alia on the weather and on the soil factors. In general, the application rates are between 0.005 and 5 kg per ha, preferably between 0.01 and 2 kg per ha, particularly preferably between 0.05 and 1.0 kg per ha.

The combinations of active compounds can be applied before and after emergence of the plants, i.e. by the pre-emergence and the post-emergence method.

Depending on their properties, the safeners to be used can be employed for pretreating the seed of the crop plant (seed dressing) or be incorporated into the seed furrows before sowing or, together with the herbicide, be applied before or after emergence of the plants.

The combinations of active compounds are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids, encountered in agriculture, in animal healthcare, in forests, in the protection of stored products and in the protection of materials, and also in the hygiene sector. They are effective against normally sensitive and resistant species and against all or individual stages of development. The abovementioned pests include:

From the order of the Diplopoda, for example,Blaniulus guttulatus.

From the order of the Chilopoda, for example,Geophilus carpophagus, Scutigeraspp.

From the order of the Symphyla, for example,Scutigerella immaculata.

From the order of the Thysanura, for example,Lepisma saccharina.

From the order of the Collembola, for example,Onychiurus armatus.

From the order of the Orthoptera, for example,Acheta domesticus, Gryllotalpaspp.,Locusta migratoria migratorioides, Melanoplusspp.,Schistocerca gregaria.

From the order of the Dermaptera, for example,Forficula auricularia.

From the order of the Isoptera, for example,Reticulitermesspp.

From the order of the Thysanoptera, for example,Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis.

From the order of the Siphonaptera, for example,Xenopsylla cheopis, Ceratophyllusspp.

When used as insecticides, the combinations of active compounds can furthermore be present, in their commercial formulations and in the use forms prepared from these formulations, as a mixture with synergists. Synergists are compounds which enhance the activity of the active compounds, without it being necessary for the added synergist to be active for its part.

The content of active compounds of the use forms prepared from the commercial formulations may vary within wide ranges. The concentration of active compounds of the use forms may be from 0.0000001 to 95% by weight of active compound and is preferably from 0.0001 to 1% by weight.

Application is carried out in a customary manner adapted to the use forms.

According to the invention, it is possible to treat all plants and parts of plants. Plants are to be understood here 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 cultivars which can or cannot be protected by plant breeder's certificates. Parts of plants are to be understood as meaning all above-ground and below-ground parts and organs of plants, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stems, trunks, flowers, fruit bodies, fruits and seeds and also roots, tubers and rhizomes. Parts of plants also include harvested plants and vegetative and generative propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds.

The treatment of the plants and parts of plants according to the invention with the active compounds is carried out directly or by action on their environment, habitat or storage area according to customary treatment methods, for example by dipping, spraying, evaporating, atomizing, broadcasting, brushing-on and, in the case of propagation material, in particular in the case of seeds, furthermore by one- or multi-layer coating.

As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant varieties, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant varieties obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The term “parts” or “parts of plants” or “plant parts” has been explained above.

Particularly preferably, plants of the plant varieties which are in each case commercially available or in use are treated according to the invention.

Depending on the plant species or plant varieties, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive (“synergistic”) effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible which exceed the effects which were actually to be expected.

The transgenic plants or plant varieties (i.e. those obtained by genetic engineering) which are preferred and to be treated according to the invention include all plants which, in the genetic modification, received genetic material which imparts particularly advantageous useful traits to these plants. Examples of such traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products. Further and particularly emphasized examples of such properties are a better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soya beans, potatoes, cotton, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to maize, soya beans, potatoes, cotton and oilseed rape. Traits that are particularly emphasized are the increased defence of the plants against insects by toxins formed in the plants, in particular those formed by the genetic material fromBacillus thuringiensis(for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and also combinations thereof) (hereinbelow referred to as “Bt plants”). Traits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (for example the “PAT” gene). The genes which impart the desired traits in question can also be present in combinations with one another in the transgenic plants. Examples of “Bt plants” which may be mentioned are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD® (for example maize, cotton, soya bean), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfield® (for example maize). Of course, these statements also apply to plant varieties having these or still-to-be-developed genetic traits, which plant varieties will be developed and/or marketed in the future.

The plants listed can be treated according to the invention in a particularly advantageous manner with the active compound mixtures. The preferred ranges stated above for the mixtures also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the mixtures specifically mentioned in the present text.

USE EXAMPLES

Solvent: 7 parts by weight of DMF

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with tap water to the desired concentration. The desired amount of safener (in the case of mefenpyr-diethyl as WP 20) is mixed into the water used for dilution. Furthermore, 2 g of a.i./l of rapeseed oil methyl ester 500 EW are added. Leaves of winter barley at the 2-leaf stage which are infested by the bird cherry-oat aphid (Rhopalosiphum padi) are treated with the desired active compound and safener concentrations using a spray boom, the water application rate being 3001/ha. Per variant, the test is carried out at least twice. Evaluation is carried out after 7 d and/or 14 d by assessing the plant damage in % and the kill of the grain aphids in % compared to the untreated control. 100% damage means that the plant has died, and 0% means no damage. 100% effect on the grain aphids means that all aphids have been killed; 0% means that none of the aphids have been killed.

Results for greenhouse trials with safener after spraying againstRhopalosiphum padion summer barley/winter barley

The expected activity of a given combination of two active compounds can be calculated as follows (cf. Colby, S. R., “Calculating Synergistic and Antagonistic Responses of Herbicide Combinations”, Weeds 15, pages 20-22, 1967):

X is the kill rate expressed in % of the untreated control when employing active compound A at an application rate of m ppm,Y is the kill rate expressed in % of the untreated control when employing active compound B at an application rate of n ppm,E is the kill rate expressed in % of the untreated control when using the active compounds A and B at application rates of m and n ppm,

If the actual insecticidal kill rate exceeds the calculated value, the kill of the combination is superadditive, i.e. a synergistic effect is present. In this case, the actually observed kill rate must exceed the value calculated using the above formula for the expected kill rate (E).

Examples of Spray Application

To prepare a suitable application solution, 1 part by weight of formulation is mixed with the appropriate amount of water and the adjuvant and the concentrate is diluted with water to the desired concentration.

Example A

Cotton plants (Gossypium herbaceum) which are heavily infested by the cotton aphid (Aphis gossypii) are sprayed to runoff point with the desired concentration of the application solution.

Example B

Barley plants (Hordeum vulgare) which are heavily infested by a grain aphid (Metopolophium dirhodum) are sprayed to runoff point with the desired concentration of the application solution.

Example C

Bell pepper plants (Capsicum sativum) which are heavily infested by the green peach aphid (Myzus persicae) are sprayed to runoff point with the desired concentration of the application solution.

After the desired period of time, the kill in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed. The determined kill rates are entered in Colby's formula.

In this test, for example, the following active compound combination in accordance with the present application shows a synergistically enhanced activity compared to the active compounds applied individually: