The invention relates to novel compounds of the formula (I)in which    The invention relates furthermore to increasing the activity of crop protection compositions comprising compounds of the formula (I) by adding ammonium or phosphonium salts and, if appropriate, penetrants.

The present invention relates to novel cis-alkoxyspirocyclic biphenyl-substituted tetramic acid derivatives, to a plurality of processes for their preparation and to their use as pesticides and/or herbicides. The invention also provides selective herbicidal compositions comprising, firstly, the cis-alkoxy-spirocyclic biphenyl-substituted tetramic acid derivatives and, secondly, a crop plant compatibility-improving compound.

The present invention further relates to the boosting of the action of crop protection compositions comprising, in particular, cis-alkoxyspirocyclic biphenyl-substituted tetramic acid derivatives, through the addition of ammonium salts or phosphonium salts and optionally penetrants, to the corresponding compositions, to processes for producing them and to their application in crop protection as insecticides and/or acaricides and/or for preventing unwanted plant growth.

Also known are biphenyl-substituted 1H-pyrrolidinedione derivatives having fungicidal action (WO 03/059065).

However, in particular at low application rates and concentrations, the activity and activity spectrum of these compounds is not always satisfactory. Furthermore, the compatibility of these compounds with some crop plants is not always sufficient. Moreover, the toxicological properties and/or environmental properties of these compounds are not always entirely satisfactory.

This invention now provides novel compounds of the formula (I)

in whichX represents halogen, alkyl, alkoxy, haloalkyl or haloalkoxy,Z represents optionally mono- or polysubstituted fluorophenyl,W and Y independently of one another represent hydrogen, halogen, alkyl, alkoxy, haloalkyl or haloalkoxy,A represents alkyl,G represents hydrogen (a) or represents one of the groups

in whichE represents a metal ion or an ammonium ion,L represents oxygen or sulphur,M represents oxygen or sulphur,R1represents in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or optionally halogen-, alkyl- or alkoxy-substituted cycloalkyl which may be interrupted by at least one heteroatom, in each case optionally substituted phenyl, phenylalkyl, hetaryl phenoxyalkyl or hetaryloxyalkyl,R2represents in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or represents in each case optionally substituted cycloalkyl, phenyl or benzyl,R3, R4and R5independently of one another represent in each case optionally halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, cycloalkylthio or represent in each case optionally substituted phenyl, benzyl, phenoxy or phenylthio andR6and R7independently of one another represent hydrogen, in each case optionally halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, represent optionally substituted phenyl, represent optionally substituted benzyl or together with the nitrogen atom to which they are attached represent a ring which is optionally interrupted by oxygen or sulphur.

Depending inter alia on the nature of the substituents, the compounds of the formula (I) may be present as geometrical and/or optical isomers or isomer mixtures of varying composition which, if appropriate, may be separated in a customary manner. The present invention provides for the pure isomers and the isomer mixtures, their preparation and use and 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, mixtures having various proportions of isomeric compounds.

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

Furthermore, it has been found that the novel compounds of the formula (I) are obtained by one of the processes described below:(A) Compounds of the formula (I-a),

in whichA, W, X, Y and Z have the meanings given above,are obtained whencompounds of the formula (II),

in whichA, W, X, Y and Z have the meanings given above,andR8represents alkyl (preferably C1-C6-alkyl),are condensed intramolecularly in the presence of diluent and in the presence of a base.(B) Furthermore, it has been found that compounds of the formulae (I-a) to (I-g) shown above, in which A, G, W, X, Y and Z have the meaning given above, are obtained when compounds of the formulae (I-a′) to (I-g′),

in whichW, X and Y have the meaning given above andZ′ represents chlorine, bromine, iodine, preferably bromine,are reacted with boronic acids or boronic acid derivatives of the formula (III)

in whichR9represents hydrogen, C1-C6-alkyl or C2-C6-alkanediylandZ has the meaning given above,in the presence of a solvent, a base and a catalyst, suitable catalysts being in particular palladium salts or palladium complexes.Moreover, it has been found(C) that the compounds of the formula (I-b) shown above, in which A, R1, W, X, Y and Z have the meanings given above, are obtained when compounds of the formula (I-a) shown above, in which A, W, X, Y and Z have the meanings given above, are in each case(α) reacted with acid halides of the formula (IV)

in whichR1has the meaning given above andHal represents halogen (in particular chlorine or bromine)or(β) reacted with carboxylic anhydrides of the formula (V)
R1—CO—O—CO—R1(V)in whichR1has the meaning given above,if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;(D) that the compounds of the formula (I-c) shown above, in which A, R2, M, W, X, Y and Z have the meanings given above and L represents oxygen, are obtained when compounds of the formula (I-a) shown above, in which A, W, X, Y and Z have the meanings given above, are in each casereacted with chloroformic esters or chloroformic thioesters of the formula (VI)
R2-M-CO—Cl  (VI)in whichR2and M have the meanings given above,if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;(E) that compounds of the formula (I-c) shown above, in which A, R2, M, W, X, Y and Z have the meanings given above and L represents sulphur, are obtained when compounds of the formula (I-a) shown above, in which A, W, X, Y and Z have the meanings given above, are in each casereacted with chloromonothioformic esters or chlorodithioformic esters of the formula (VII)

in whichM and R2have the meanings given above,if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,and(F) that compounds of the formula (I-d) shown above, in which A, R3, W, X, Y and Z have the meanings given above, are obtained when compounds of the formula (I-a) shown above, in which A, W, X, Y and Z have the meanings given above, are in each casereacted with sulphonyl chlorides of the formula (VIII)
R3—SO2—Cl  (VIII)in whichR3has the meaning given above,if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,(G) that compounds of the formula (I-e) shown above, in which A, L, R4, R5, W, X, Y and Z have the meanings given above, are obtained when compounds of the formula (I-a) shown above, in which A, W, X, Y and Z have the meanings given above are in each casereacted with phosphorus compounds of the formula (IX)

in whichL, R4and R5have the meanings given above andHal represents halogen (in particular chlorine or bromine),if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,(H) that compounds of the formula (I-f) shown above, in which A, E, W, X, Y and Z have the meanings given above, are obtained when compounds of the formula (I-a) shown above, in which A, W, X, Y and Z have the meanings given above, are in each casereacted with metal compounds or amines of the formulae (X) or (XI), respectively,

in whichMe represents a mono- or divalent metal (preferably an alkali metal or alkaline earth metal, such as lithium, sodium, potassium, magnesium or calcium),t represents the number 1 or 2 andR10, R11, R12independently of one another represent hydrogen or alkyl (preferably C1-C8-alkyl),if appropriate in the presence of a diluent,(I) that compounds of the formula (I-g) shown above, in which A, L, R6, R7, W, X, Y and Z have the meanings given above, are obtained when compounds of the formula (I-a) shown above, in which A, W, X, Y and Z have the meanings given above, are in each case(α) reacted with isocyanates or isothiocyanates of the formula (XII)
R6—N═C=L  (XII)in whichR6and L have the meanings given above,if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst, or(β) reacted with carbamoyl chlorides or thiocarbamoyl chlorides of the formula (XIII)

in whichL, R6and R7have the meanings given above,if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

Furthermore, it has been found that the novel compounds of the formula (I) are very effective as pesticides, preferably as insecticides and/or acaricides and/or herbicides, are additionally frequently highly compatible with plants, in particular with crop plants, and/or have favourable toxicological and/or environmentally relevant properties.

Surprisingly, it has now also been found that certain cis-alkoxyspirocyclic biphenyl-substituted tetramic acid derivatives, when used together with the crop plant compatibility-improving compounds (safeners/antidotes) described below, efficiently prevent damage to the crop plants and can be used in a particularly advantageous manner as broad-spectrum combination preparations for the selective control of unwanted plants in crops of useful plants, such as, for example, in cereals, but also in maize, soya beans and rice.

or of the general formula (IIb)

or of 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)

The formula (I) provides a general definition of the compounds according to the invention. Preferred substituents or ranges of the radicals listed in the formulae mentioned above and below are illustrated below:X preferably represents halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy,Z preferably represents the radicals

V1, V2independently of one another preferably represent hydrogen, halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-haloalkyl or C1-C4-haloalkoxy,V3preferably represents hydrogen, chlorine, bromine, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-haloalkyl or C1-C4-haloalkoxy,W and Y independently of one another preferably represent hydrogen, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy or C1-C6-haloalkoxy,A preferably represents C1-C6-alkyl,G preferably represents hydrogen (a) or represents one of the groups

In the radical definitions mentioned as being preferred, halogen represents fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine.W particularly preferably represents hydrogen, methyl or chlorine,X particularly preferably represents fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl or C1-C4-haloalkoxy,Y particularly preferably represents hydrogen, C1-C4-alkyl, fluorine, chlorine, bromine, methoxy or trifluoromethyl,Z particularly preferably represents the radicals

V1, V2independently of one another particularly preferably represent hydrogen, fluorine, chlorine, bromine, C1-C6-alkyl, C1-C4-alkoxy, C1-C2-haloalkyl or C1-C2-haloalkoxy,V3particularly preferably represents hydrogen, chlorine, bromine, C1-C4-alkyl or C1-C4-alkoxy, C1-C2-haloalkyl or C1-C2-haloalkoxy,A particularly preferably represents C1-C4-alkyl,G particularly preferably represents hydrogen (a) or represents one of the groups

in whichE represents a metal ion equivalent or an ammonium ion,L represents oxygen or sulphur andM represents oxygen or sulphur andR1particularly preferably represents C1-C8-alkyl, C2-C18-alkenyl, C1-C4-alkoxy-C1-C2-alkyl, C1-C4-alkylthio-C1-C2-alkyl each of which is optionally mono- to trisubstituted by fluorine or chlorine, or C3-C6-cycloalkyl which is optionally mono- or disubstituted by fluorine, chlorine, C1-C2-alkyl or C1-C2-alkoxy and in which optionally one or two not directly adjacent ring members are replaced by oxygen,represents phenyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy, C1-C2-haloalkyl or C1-C2-haloalkoxy,R2particularly preferably represents C1-C8-alkyl, C2-C8-alkenyl or C1-C4-alkoxy-C2-C4-alkyl, each of which is optionally mono- to trisubstituted by fluorine,represents C3-C6-cycloalkyl which is optionally monosubstituted by C1-C2-alkyl or C1-C2-alkoxy orrepresents phenyl or benzyl, each of which is optionaly mono- or disubstituted by fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, C1-C3-alkoxy, trifluoromethyl or trifluoromethoxy,R3particularly preferably represents C1-C8-alkyl which is optionally mono- to trisubstituted by fluorine or represents phenyl which is optionally monosubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,R4particularly preferably represents C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylamino, di(C1-C6-alkyl)amino, C1-C6-alkylthio, C3-C4-alkenylthio, C3-C6-cycloalkylthio or represents phenyl, phenoxy or phenylthio, each of which is optionally monosubstituted by fluorine, chlorine, bromine, nitro, cyano, C1-C3-alkoxy, C1-C3-haloalkoxy, C1-C3-alkylthio, C1-C3-haloalkylthio, C1-C3-alkyl or trifluoromethyl,R5particularly preferably represents C1-C6-alkoxy or C1-C6-alkylthio,R6particularly preferably represents hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C3-C6-alkenyl, C1-C6-alkoxy-C1-C4-alkyl, represents phenyl which is optionally monosubstituted by fluorine, chlorine, bromine, trifluoromethyl, C1-C4-alkyl or C1-C4-alkoxy, represents benzyl which is optionally monosubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, trifluoromethyl or C1-C4-alkoxy,R7particularly preferably represents C1-C6-alkyl, C3-C6-alkenyl or C1-C6-alkoxy-C1-C4-alkyl,R6and R7together particularly preferably represent a C4-C5-alkylene radical which is optionally substituted by methyl or ethyl and in which optionally one methylene group is replaced by oxygen or sulphur.

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

V1, V2independently of one another very particularly preferably represent hydrogen, fluorine, chlorine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,V3very particularly preferably represents hydrogen, chlorine, methyl, methoxy, trifluoromethyl or trifluoromethoxy,A very particularly preferably represents methyl, ethyl, propyl or butyl,G very particularly preferably represents hydrogen (a) or represents one of the groups

in whichL represents oxygen or sulphur,M represents oxygen or sulphur andE represents an ammonium ion or a metal ion equivalent,R1very particularly preferably represents C1-C6-alkyl, C2-C17-alkenyl, C1-C2-alkoxy-C1-alkyl, C1-C2-alkylthio-C1-alkyl, each of which is optionally monosubstituted by chlorine, 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,R2very particularly preferably represents C1-C8-alkyl, C2-C6-alkenyl or C1-C4-alkoxy-C2-C3-alkyl, phenyl or benzyl, each of which is optionally monosubstituted by fluorine.W notably represents hydrogen or methyl,X notably represents chlorine or methyl,Y notably represents hydrogen or methyl,Z notably represents the radicals

V1, V2notably independently of one another represent hydrogen, fluorine, chlorine, or methoxy,(Z represents in particular

A notably represents methyl or ethyl,G notably represents hydrogen (a) or represents one of the groups

in whichE represents a metal ion equivalent (Na+),R1notably represents C1-C6-alkyl or cyclopropyl,R2notably represents C1-C8-alkyl.

The general or preferred radical definitions or illustrations listed above can be combined with one another as desired, i.e. including combinations between the respective ranges and preferred ranges. They apply both to the end products and, correspondingly, to precursors and intermediates.

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

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

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

Noteworthiness in accordance with the invention is accorded to the compounds of the formula (I) which contain a combination of the meanings listed above as being notable.

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

Optionally substituted radicals can be mono- or polysubstituted unless indicated otherwise, and in the case of multiple substitutions the substituents can be identical or different.

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

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

Examples of the compounds of the formula (Ha) which are very particularly preferred as herbicide safeners according to the invention are listed in the table below.

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

TABLEExamples of the compounds of the formula (IIb)Ex-(Posi-ampletion)(Position)No.X2X3A2R15IIb-1(5)—CH2OHClIIb-2(5)—CH2OCH3ClIIb-3(5)—CH2OC2H5ClIIb-4(5)—CH2OC3H7-nClIIb-5(5)—CH2OC3H7-iClIIb-6(5)—CH2OC4H9-nClIIb-7(5)—CH2OCH(CH3)C5H11-nClIIb-8(5)(2)CH2OHClFIIb-9(5)(2)CH2OHClClIIb-10(5)—CH2OCH2CH═CH2ClIIb-11(5)—CH2OC4H9-iClIIb-12(5) Cl—CH2IIb-13(5) Cl—OCH2CH═CH2IIb-14(5) Cl—OC2H5IIb-15(5) Cl—OCH3

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

TABLEExamples of the compounds of the formula (IIc)ExampleNo.R16N(R17,R18)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 herbicide safeners according to the invention are listed in the table below.

Examples of the compounds of the formula (Ile) which are very particularly preferred as herbicide safeners according to the invention are listed in the table below.

Most preferred as crop plant compatibility-improving compound [component (b′)] are cloquintocet-mexyl, fenchlorazole-ethyl, isoxadifen-ethyl, mefenpyr-diethyl, furilazole, fenclorim, cumyluron, dymron, dimepiperate and the compounds IIe-5 and IIe-11, and particular emphasis is given to cloquintocet-mexyl and mefenpyr-diethyl, but also to isoxachifen-ethyl.

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

Examples of the selective herbicidal combinations according to the invention comprising in each case one active compound of the formula (I) and one of the safeners defined above are listed in the table below.

TABLEExamples of combinations according to the inventionActive compounds of the formula(I)SafenerI-acloquintocet-mexylI-afenchlorazole-ethylI-aisoxadifen-ethylI-amefenpyr-diethylI-afurilazoleI-afenclorimI-acumyluronI-adaimuron/dymronI-adimepiperateI-aIIe-11I-aIIe-5I-bcloquintocet-mexylI-bfenchlorazole-ethylI-bisoxadifen-ethylI-bmefenpyr-diethylI-bfurilazoleI-bfenclorimI-bcumyluronI-bdaimuron/dymronI-bdimepiperateI-bIIe-11I-bIIe-5I-ccloquintocet-mexylI-cfenchlorazole-ethylI-cisoxadifen-ethylI-cmefenpyr-diethylI-cfurilazoleI-cfenclorimI-ccumyluronI-cdaimuron/dymronI-cdimepiperateI-cIIe-5I-cIIe-11I-dcloquintocet-mexylI-dfenchlorazole-ethylI-disoxadifen-ethylI-dmefenpyr-diethylI-dfurilazoleI-dfenclorimI-dcumyluronI-ddaimuron/dymronI-ddimepiperateI-dIIe-11I-dIIe-5I-ecloquintocet-mexylI-efenchlorazole-ethylI-eisoxadifen-ethylI-emefenpyr-diethylI-efurilazoleI-efenclorimI-ecumyluronI-edaimuron/dymronI-edimepiperateI-eIIe-5I-eIIe-11I-fcloquintocet-mexylI-ffenchlorazole-ethylI-fisoxadifen-ethylI-fmefenpyr-diethylI-ffurilazoleI-ffenclorimI-fcumyluronI-fdaimuron/dymronI-fdimepiperateI-fIIe-5I-fIIe-11I-gcloquintocet-mexylI-gfenchlorazole-ethylI-gisoxadifen-ethylI-gmefenpyr-diethylI-gfurilazoleI-gfenclorimI-gcumyluronI-gdaimuron/dymronI-gdimepiperateI-gIIe-5I-gIIe-11

Surprisingly, it has now been found that the active compound combinations, defined above, of cis-alkoxyspirocyclic biphenyl-substituted tetramic acid derivatives of the general formula (I) and safeners (antidotes) from group (b′) listed above, while being very well tolerated by useful plants, have a particularly high herbicidal activity and can be used in various crops, in particular in cereals (especially wheat), but also in soya beans, potatoes, maize and rice, for the selective control of weeds.

Here, it has to be considered surprising that, from a large number of known safeners or antidotes capable of antagonizing the harmful effect of a herbicide on crop plants, those suitable are in particular the compounds of group (b′) listed above which eliminate the harmful effect of cis-alkoxy-spirocyclic biphenyl-substituted tetramic acid derivatives on the crop plants virtually completely without having a major adverse effect on the herbicidal activity against the weeds.

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

In the literature it has already been described how the action of various active compounds can be boosted by addition of ammonium salts. The salts in question, however, are detersive salts (for example WO 95/017817) or salts which have relatively long alkyl substituents and/or aryl substituents and which have a permeabilizing action or which increase the active compound's solubility (for example EP-A 0 453 086, EP-A 0 664 081, FR-A 2 600 494, U.S. Pat. No. 4,844,734, U.S. Pat. No. 5,462,912, U.S. Pat. No. 5,538,937, U.S. Ser. No. 03/0224,939, U.S. Ser. No. 05/0009,880, U.S. Ser. No. 05/0096,386). Moreover, the prior art describes the action only for particular active compounds and/or particular applications of the corresponding compositions. In other cases, in turn, the salts in question are those of sulphonic acids, where the acids themselves have a paralytic action on insects (U.S. Pat. No. 2,842,476). A boost to action by ammonium sulphate, for example, is described by way of example for the herbicides glyphosate, phosphinothricin and certain cyclic ketoenols (U.S. Pat. No. 6,645,914, EP-A2 0 036 106, WO 07/068427). A corresponding action in the case of insecticides is described for certain cyclic ketoenols in WO 07/068428.

The use of ammonium sulphate as a formulating assistant has also been described for certain active compounds and applications (WO 92/16108), but its purpose therein is to stabilize the formulation, not to boost the action.

It has now been found, surprisingly, that the action of insecticides and/or acaricides and/or herbicides from the class of the cis-alkoxyspirocyclic biphenyl-substituted tetramic acid derivatives of the formula (I) can be boosted significantly through the addition of ammonium salts or phosphonium salts to the application solution or through the incorporation of these salts into a formulation comprising cis-alkoxyspirocyclic biphenyl-substituted tetramic acid derivatives of the formula (I). The present invention therefore provides for the use of ammonium salts or phosphonium salts for boosting the action of crop protection compositions which comprise as their active compound insecticidal and/or acaricidal cis-alkoxyspirocyclic biphenyl-substituted tetramic acid derivatives of the formula (I). The invention likewise provides compositions which comprise herbicidal and/or acaricidal and/or insecticidal cis-alkoxyspirocyclic biphenyl-substituted tetramic acid derivatives of the formula (I) and action-boosting ammonium salts or phosphonium salts, including not only formulated active compounds but also ready-to-use compositions (spray liquors). The invention further provides, finally, for the use of these compositions for controlling insect pests and/or spider mites and/or unwanted plant growth.

The compounds of the formula (I) possess a broad insecticidal and/or acaricidal and/or herbicidal activity, but in specific cases the activity and/or plant tolerance leaves something to be desired. However, some or all of these properties can be improved by adding ammonium salts or phosphonium salts.

The active compounds can be used in the compositions according to the invention in a broad concentration range. The concentration of the active compounds in the formulation is typically 0.1%-50% by weight.

The formula (III′) provides a definition of the ammonium salts and phosphonium salts which, according to the invention, boost the activity of crop protection compositions comprising an active compound from the class of the cis-alkoxyspirocyclic biphenyl-substituted tetramic acid derivatives of the formula (I)

Inventively emphasized combinations of active compound, salt and penetrant are listed in the table below. “Penetrant as per test” means here that any compound that acts as a penetrant in the cuticle penetration test (Baur et al., 1997,Pesticide Science51, 131-152) is suitable.

The ammonium salts and phosphonium salts of the formula (III′) can be used in a broad concentration range to boost the activity of crop protection compositions comprising cis-alkoxyspirocyclic biphenyl-substituted tetramic acid derivatives of the formula (I). In general the ammonium salts or phosphonium salts are used in the ready-to-use crop protection composition in a concentration of 0.5 to 80 mmol/l, preferably 0.75 to 37.5 mmol/l, more preferably 1.5 to 25 mmol/l. In the case of a formulated product the ammonium salt and/or phosphonium salt concentration in the formulation is chosen such that it is within these stated general, preferred or particularly preferred ranges after the formulation has been diluted to the desired active compound concentration. The concentration of the salt in the formulation is typically 1%-50% by weight.

In one preferred embodiment of the invention the activity is boosted by adding to the crop protection compositions not only an ammonium salt and/or phosphonium salt but also, additionally, a penetrant. It is considered entirely surprising that even in these cases an even greater boost to activity is observed. The present invention therefore likewise provides for the use of a combination of penetrant and ammonium salts and/or phosphonium salts to boost the activity of crop protection compositions which comprise insecticidal cis-alkoxyspirocyclic biphenyl-substituted tetramic acid derivatives of the formula (I) as active compound. The invention likewise provides compositions which comprise herbicidal and/or acaricidal and/or insecticidal cis-alkoxyspirocyclic biphenyl-substituted tetramic acid derivatives of the formula (I), penetrants and ammonium salts and/or phosphonium salts, including specifically not only formulated active compounds but also ready-to-use compositions (spray liquors). The invention additionally provides, finally, for the use of these compositions for controlling harmful insects and/or spider mites.

In the present context, suitable penetrants are all those substances which are usually employed to improve penetration of agrochemically active compounds into plants. In this context, penetrants are defined in that they penetrate from the aqueous spray liquor and/or the spray coating into the cuticles of the plant, thus increasing the mobility of active compounds in the cuticles. The method described in the literature (Baur et al., 1997,Pesticide Science51, 131-152) can be used for determining this property.

Examples of suitable penetrants include alkanol alkoxylates. Penetrants of the invention are alkanol alkoxylates of the formula (IV′)
R—O-(-AO)v—R′  (IV′)
in whichR is linear or branched alkyl having 4 to 20 carbon atoms,R′ is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or n-hexyl,AO is an ethylene oxide radical, a propylene oxide radical, a butylene oxide radical or is mixtures of ethylene oxide and propylene oxide radicals or butylene oxide radicals, andv is a number from 2 to 30.

One preferred group of penetrants are alkanol alkoxylates of the formula
R—O-(-EO—)n—R′  (IV′-a)
in whichR is as defined above,R′ is as defined above,EO is —CH2—O—CH2—O—, andn is a number from 2 to 20.

A further preferred group of penetrants are alkanol alkoxylates of the formula
R—O-(-EO—)p—(—PO—)q—R′  (IV′-b)
in whichR is as defined above,R′ is as defined above,EO is —CH2—CH2—O—,PO is

p is a number from 1 to 10, andq is a number from 1 to 10.

A further preferred group of penetrants are alkanol alkoxylates of the formula
R—O—(—PO—)r-(EO—)s—R′  (IV′-c)
in whichR is as defined above,R′ is as defined above,EO is —CH2—CH2—O—,PO is

r is a number from 1 to 10, ands is a number from 1 to 10.

A further preferred group of penetrants are alkanol alkoxylates of the formula
R—O-(-EO—)p—(—BO—)q—R′  (IV′-d)
in whichR and R′ are as defined above,EO is CH2—CH2—O—,BO is

p is a number from 1 to 10 andq is a number from 1 to 10.

A further preferred group of penetrants are alkanol alkoxylates of the formula
R—O—(—BO—)r-(-EO—)s—R′  (IV′-e)
in whichR and R′ are as defined above,BO is

EO is CH2—CH2—O—,r is a number from 1 to 10 ands is a number from 1 to 10.

A further preferred group of penetrants are alkanol alkoxylates of the formula
CH3—(CH2)t—CH2—O—(—CH2—CH2—O—)u—R′  (IV′-f)
in whichR′ is as defined above,t is a number from 8 to 13,u is a number from 6 to 17.

As an example of an alkanol alkoxylate of the formula (IV′-c) mention may be made of 2-ethylhexyl alkoxylate of the formula

in whichEO is —CH2—CH2—O—,PO is

and the numbers 8 and 6 represent average values.

As an example of an alkanol alkoxylate of the formula (IV′-d) mention may be made of the formula
CH3—(CH2)10—O-(-EO—)6—(—BO—)2—CH3(IV′-d-1)
in whichEO is CH2—CH2—O—,BO is

and the numbers 10, 6 and 2 represent average values.

Particularly preferred alkanol alkoxylates of the formula (IV′-f) are compounds of this formula in whicht is a number from 9 to 12 andu is a number from 7 to 9.

Mention may be made with very particular preference of alkanol alkoxylate of the formula (IV′-f-1)
CH3—(CH2)t—CH2—O—(—CH2—CH2—O—)u—H  (IV′-f-1)
in whicht stands for the average value 10.5 andu stands for the average value 8.4.

A general definition of the alkanol alkoxylates is given by the formulae above. These substances are mixtures of compounds of the stated type with different chain lengths. The indices therefore have average values which may also deviate from whole numbers.

The alkanol alkoxylates of the formulae stated are known and in some cases are available commercially or can be prepared by known methods (cf. WO 98/35 553, WO 00/35 278 and EP-A 0 681 865).

Suitable penetrants also include, for example, 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 oils—modified or otherwise—which can typically be used in agrochemical compositions. Mention may be made by way of example of sunflower oil, rapeseed oil, olive oil, castor oil, colza oil, maize seed oil, cotton seed oil and soya bean oil, or the esters of said oils. Preference is given to rapeseed oil, sunflower oil and their methyl or ethyl esters.

The concentration of penetrant in the compositions of the invention can be varied within a wide range. In the case of a formulated crop protection composition it is in general 1% to 95%, preferably 1% to 55%, more preferably 15%-40% by weight. In the ready-to-use compositions (spray liquors) the concentrations are generally between 0.1 and 10 g/l, preferably between 0.5 and 5 g/l.

Crop protection compositions of the invention may also comprise further components, examples being surfactants and/or dispersing assistants or emulsifiers.

Suitable nonionic surfactants and/or dispersing assistants include all substances of this type that can typically be used in agrochemical compositions. Preferably mention may be made of polyethylene oxide-polypropylene oxide block copolymers, polyethylene glycol ethers of linear alcohols, reaction products of fatty acids with ethylene oxide and/or propylene oxide, and also polyvinyl alcohol, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and polyvinylpyrrolidone, and copolymers of (meth)acrylic acid and (meth)acrylic esters, and additionally alkyl ethoxylates and alkylaryl ethoxylates, which optionally may be phosphated and optionally may be neutralized with bases, mention being made, by way of example, of sorbitol ethoxylates, and, as well, polyoxyalkylenamine derivatives.

Suitable anionic surfactants include all substances of this type that can typically be used in agrochemical compositions. Preference is given to alkali metal salts and alkaline earth metal salts of alkylsulphonic acids or alkylarylsulphonic acids.

A further preferred group of anionic surfactants and/or dispersing assistants are the following salts that are of low solubility in plant oil: salts of polystyrenesulphonic acids, salts of polyvinylsulphonic acids, salts of naphthalenesulphonic acid-formaldehyde condensation products, salts of condensation products of naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde, and salts of lignosulphonic acid.

Suitable additives which may be included in the formulations of the invention are emulsifiers, foam inhibitors, preservatives, antioxidants, colorants and inert filling materials.

Preferred emulsifiers are ethoxylated nonylphenols, reaction products of alkylphenols with ethylene oxide and/or propylene oxide, ethoxylated arylalkylphenols, and also ethoxylated and propoxylated arylalkylphenols, and also sulphated or phosphated arylalkyl ethoxylates and/or arylalkyl ethoxypropoxylates, mention being made by way of example of sorbitan derivatives, such as polyethylene oxide-sorbitan fatty acid esters, and sorbitan fatty acid esters.

Using, for example, according to process (A) ethyl cis-N-[(2,6-dimethyl-3-(4-fluorophenyl)acetyl]-1-amino-4-methoxycyclohexane-1-carboxylate as starting material, the course of the process according to the invention can be represented by the reaction scheme below:

Using, according to process (B), cis-8-methoxy-3-(3-bromo-2,6-dimethylphenyl)-1-azaspiro-[4,5]decane-2,4-dione and 4-fluorophenylboronic acid as starting materials, the course of the reaction can be represented by the scheme below:

Using, for example, according to process (Cα) cis-8-methoxy-3-[6-methyl-3-(4-fluorophenyl)-1-phenyl]-1-azaspiro[4,5]decane-2,4-dione and pivaloyl chloride as starting materials, the course of the process according to the invention can be represented by the reaction scheme below:

Using, for example, according to process (C) (variant β) cis-8-methoxy-3-[6-methyl-3-(4-fluoro-phenyl)phenyl]-1-azaspiro[4,5]decane-2,4-dione and acetic anhydride as starting materials, the course of the process according to the invention can be represented by the reaction scheme below:

Using, for example, according to process (D) cis-8-methoxy-3-[2-chlor-5-(3,4-difluorophenyl)-phenyl]-1-azaspiro[4,5]decane-2,4-dione and ethoxyethyl chloroformate as starting materials, the course of the process according to the invention can be represented by the reaction scheme below:

Using, for example, according to process (E), variant (α), cis-8-methoxy-3-[2-chloro-5-(4-fluoro-phenyl)phenyl]-1-azaspiro[4,5]decane-2,4-dione and methyl chloromonothioformate as starting materials, the course of the reaction can be represented as follows:

Using, for example, according to process (E), variant (β), cis-8-methoxy-3-[2,6-dimethyl-3-(4-fluorophenyl)phenyl]-1-azaspiro[4,5]decane-2,4-dione, carbon disulphide and methyl iodide as starting materials, the course of the reaction can be represented as follows:

Using, for example, according to process (F) cis-8-methoxy-3-[2-chloro-5-(4-fluorophenyl)-phenyl]-1-azaspiro[4,5]decane-2,4-dione and methanesulphonyl chloride as starting materials, the course of the reaction can be represented by the reaction scheme below:

Using, for example, according to process (G) cis-8-methoxy-3-[6-methyl-3-(3,4-difluorophenyl)-phenyl]-1-azaspiro[4,5]decane-2,4-dione and 2,2,2-trifluoroethyl methanethiophosphonyl chloride as starting materials, the course of the reaction can be represented by the reaction scheme below:

Using, for example, according to process (H) cis-8-methoxy-3-[2,6-dimethyl-3-(4-fluorophenyl)-phenyl]-1-azaspiro[4,5]decane-2,4-dione and NaOH as components, the course of the process according to the invention can be represented by the reaction scheme below:

Using, for example, according to process (I) variant (α) cis-8-methoxy-3-[6-methyl-3-(3,4-difluorophenyl)phenyl]-1-azaspiro[4,5]decane-2,4-dione and ethyl isocyanate as starting materials, the course of the reaction can be represented by the reaction scheme below:

Using, for example, according to process (I) variant (β) cis-8-methoxy-3-[2-chloro-5-(4-fluoro-phenyl)phenyl]-1-azaspiro[4,5]decane-2,4-dione and dimethylcarbamoyl chloride as starting materials, the course of the reaction can be represented by the scheme below:

The compounds, required as starting materials for the process (a) according to the invention, of the formula (II)

in which
A, W, X, Y, Z and R8have the meanings given above,
are novel.

The acylamino acid esters of the formula (II) are obtained, for example, when amino acid derivatives of the formula (XIV)

in whichA and R8have the meanings given above,are acylated with substituted phenyl acetic acid derivatives of the formula (XV)

The compounds of the formula (XVI)

in which
A, W, X, Y and Z have the meanings given above,
are novel.

The compounds of the formula (XVI) are obtained when amino acids of the formula (XVII)

in which
A has the meaning given above,
are acylated with substituted phenylacetic acid derivatives of the formula (XV)

in which
W, X, Y and Z have the meanings given above and
U has the meaning given above,
for example according to Schotten-Baumann (Organikum, VEB Deutscher Verlag der Wissen-schaften, Berlin 1977, p. 505).

The compounds of the formula (XV) are novel. They can be obtained by methods known in principle (see, for example, H. Henecka, Houben-Weyl, Methoden der Organischen Chemie [Methods of organic chemistry], Vol. 8, pp. 467-469 (1952) or according to the patent applications cited at the outset).

The compounds of the formula (XV) are obtained, for example, when substituted phenylacetic acids of the formula (XVIII)

in which
W, X, Y and Z have the meaning given above
are reacted with halogenating reagents (for example thionyl chloride, thionyl bromide, oxalyl chloride, phosgene, phosphorus trichloride, phosphorus tribromide or phosphorus pentachloride) or phosphorylating reagents (for example POCl3, BOP-Cl) if appropriate in the presence of a diluent (for example optionally chlorinated aliphatic or aromatic hydrocarbons, such as toluene or methylene chloride) at temperatures of from −20° C. to 150° C., preferably from −10° C. to 100° C.

Some of the compounds of the formulae (XIV) and (XVII) are known from WO 02/002532, and/or they can be prepared by known processes.

Some of the compounds of the formula (XVIII) are known from WO 2005/016873 or can be prepared by the processes described therein.

For example, the compounds of the formula (XVIII),

in which
W, X, Y and Z have the meanings given above
are obtained
α) when compounds of the formula (XVIII-a)

in which
X and Y have the meaning given above,
Z′ represents chlorine, bromine or iodine, preferably bromine,
are reacted with boronic acids or boronic acid derivatives of the formula (III)

in which
Z and R9have the meaning given above,
in the presence of a solvent, a base and a catalyst (preferably a palladium salt or palladium complex, such as, for example, palladiumtetrakis(triphenylphosphine)) or
β) when phenylacetic esters of the formula (XIX)

in which
W, X, Y, Z and R8have the meaning given above,
are hydrolysed in the presence of acids or bases, in the presence of a solvent, under generally known standard conditions or
γ) when phenylacetic acids of the formula (XVIII-b)

in which
W, X and Z have the meaning given above
are reacted with halogen compounds of the formula (XX),
Z-Hal  (XX)
in which
Z has the meaning given above and
Hal represents chlorine, bromine or iodine, preferably bromine or iodine,
in the presence of a solvent, a base and a catalyst (preferably a palladium salt or one of the palladium complexes mentioned above).

Some of the compounds of the formulae (III) and (XX) are known, some are commercially available, or they can be prepared by processes known in principle. Some of the phenylacetic acids of the formula (XVIII-a) are known from WO 97/01 535, WO 97/36 868 and WO 98/05 638, or they can be prepared by the processes described therein.

Some of the compounds of the formula (XIX) are known from WO 2005/016873, or they can be prepared by the processes described therein.

The compounds of the formula (XVIII-b) are known from WO 05/016873.

The compounds of the formula (XIX)

in which
W, X, Y, Z and R8have the meaning given above,
are obtained, for example,
when phenylacetic esters of the formula (XIX-a)

in which
R8, W, X, Y and Z′ have the meaning given above,
are reacted with boronic acids or boronic acid derivatives of the formula (III)

in which
Z and R9have the meaning given above,
in the presence of a solvent, a base and a catalyst (preferably a palladium salt or one of the palladium complexes mentioned above).

Some of the phenyl acetic esters of the formula (XIX-a) are known from the applications WO 97/01535, WO 97/36868 and WO 98/0563, or they can be prepared by the processes described therein.

Some of the compounds, required as starting materials in the above process (C), of the formulae (I-a′) to (I-g′) in which A, W, X and Y have the meaning given above and Z′ represents chlorine, bromine or iodine, preferably bromine, are known (WO 96/35 664, WO 97/02 243 and WO 98/05 638), or they can be prepared according to the processes described therein.

Some of the boronic acids and boronic acid derivatives of the formula (III)

in which
Z and R9have the meaning given above
are commercially available, or they can be prepared in a simple manner by generally known processes.

The acid halides of the formula (IV), carboxylic anhydrides of the formula (V), chloroformic esters or chloroformic thioesters of the formula (VI), chloromonothioformic esters or chlorodithioformic esters of the formula (VII), sulphonyl chlorides of the formula (VIII), phosphorus compounds of the formula (IX) and metal hydroxides, metal alkoxides or amines of the formulae (X) and (XI), respectively, and isocyanates of the formula (XII) and carbamoyl chlorides of the formula (XIII) furthermore required as starting materials for carrying out the processes (D), (E), (F), (G), (H), (I) and (J) according to the invention are generally known compounds of organic or inorganic chemistry.

The process (A) is characterized in that compounds of the formula (II), in which A, W, X, Y, Z and R8have the meanings given above are subjected to an intramolecular condensation in the presence of a base.

Suitable diluents for use in the process (A) according to the invention are all inert organic solvents. Preference is given to using hydrocarbons, such as toluene and xylene, furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, moreover polar solvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide and N-methylpyrrolidone, and also alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol.

Suitable bases (deprotonating agents) for carrying out the process (A) according to the invention are all customary proton acceptors. Preference is given to using alkali metal and alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, which may also be used in the presence of phase-transfer catalysts, such as, for example, triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464 (=methyltrialkyl(C8-C10)ammonium chloride) or TDA 1 (=tris(methoxyethoxyethyl)amine). It is furthermore possible to use alkali metals, such as sodium or potassium. Furthermore, it is possible to employ alkali metals and alkaline earth metal amides and hydrides, such as sodium amide, sodium hydride and calcium hydride, and additionally also alkali metal alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide.

When carrying out the process (A) according to the invention, the reaction temperatures may be varied within a relatively wide range. In general, the process is carried out at temperatures between 0° C. and 250° C., preferably between 50° C. and 150° C.

The process (A) according to the invention is generally carried out under atmospheric pressure.

When carrying out the process (A) according to the invention, the reaction components of the formula (II) and the deprotonating bases are generally employed in about doubly equimolar amounts. However, it is also possible to use a relatively large excess (up to 3 mol) of one component or the other.

Suitable catalysts for carrying out the process (B) according to the invention are palladium(0) complexes. Preference is given, for example, to tetrakis(triphenylphosphine)palladium. If appropriate, it is also possible to use palladium(II) salts, for example PdCl2, Pd(NO3)2.

Suitable acid acceptors for carrying out the process (B) according to the invention are inorganic or organic bases. These preferably include alkaline earth metal or alkali metal hydroxides, acetates, carbonates or bicarbonates, such as, for example, sodium hydroxide, potassium hydroxide, barium hydroxide or ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate or ammonium acetate, sodium carbonate, potassium carbonate or ammonium carbonate, sodium bicarbonate or potassium bicarbonate, alkali metal fluorides, such as, for example, caesium fluoride, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diaza-bicycloundecene (DBU).

In the process (B) according to the invention, the reaction temperature can be varied within a relatively wide range. In general, the process is carried out at temperatures between 0° C. and +140° C., preferably between 50° C. and +100° C.

When carrying out the process (B) according to the invention, the boronic acid(s) derivatives of the formula (III) in which Z has the meaning given above and the compounds of the formulae (I-a′) to (I-g′), in which A, W, X, Y and Z′ have the meaning given above are employed in a molar ratio of from 1:1 to 3:1, preferably from 1:1 to 2:1. The catalyst is generally added in amounts of from 0.005 to 0.5 mol, preferably from 0.01 mol to 0.1 mol, per mole of the compounds of the formulae (I-a′) to (I-g′). The base is generally employed in excess.

The process (C-α) is characterized in that compounds of the formula (I-a) are each reacted with carbonyl halides of the formula (IV), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

Suitable diluents for use in the process (C-α) according to the invention are all solvents inert towards the acid halides. Preference is given to using hydrocarbons, such as benzine, benzene, toluene, xylene and tetralin, furthermore halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, moreover ketones, such as acetone and methyl isopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxane, additionally carboxylic esters, such as ethyl acetate, and also strongly polar solvents, such as dimethyl sulphoxide and sulpholane. If the acid halide is sufficiently stable to hydrolysis, the reaction can also be carried out in the presence of water.

Suitable acid binders for the reaction according to the process (C-α) according to the invention are all customary acid acceptors. Preference is given to using tertiary amines, such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Hünig base and N,N-dimethylaniline, furthermore alkaline earth metal oxides, such as magnesium oxide and calcium oxide, moreover alkali metal and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide.

The reaction temperatures in the process (C-α) according to the invention can be varied within a relatively wide range. In general, the process is carried out at temperatures between −20° C. and +150° C., preferably between 0° C. and 100° C.

When carrying out the process (C-α) according to the invention, the starting materials of the formula (I-a) and the carbonyl halide of the formula (IV) are generally each employed in approximately equivalent amounts. However, it is also possible to use a relatively large excess (up to 5 mol) of the carbonyl halide. Work-up is carried out by customary methods.

The process (C-β) is characterized in that compounds of the formula (I-a) are each reacted with carboxylic anhydrides of the formula (V), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

Suitable diluents for use in the process (C-β) according to the invention are, preferably, the diluents which are also preferred when using acid halides. Besides, excess carboxylic anhydride may simultaneously act as diluent.

Suitable acid binders, which are added, if appropriate, for process (C-β) are, preferably, the acid binders which are also preferred when using acid halides.

The reaction temperatures in the process (C-β) according to the invention may be varied within a relatively wide range. In general, the process is carried out at temperatures between −20° C. and +150° C., preferably between 0° C. and 100° C.

When carrying out the process (C-β) according to the invention, the starting materials of the formula (I-a) and the carboxylic anhydride of the formula (V) are generally each employed in approximately equivalent amounts. However, it is also possible to use a relatively large excess (up to 5 mol) of carboxylic anhydride. Work-up is carried out by customary methods.

In general, diluent and excess carboxylic anhydride and the carboxylic acid formed are removed by distillation or by washing with an organic solvent or with water.

The process (D) is characterized in that compounds of the formula (I-a) are each reacted with chloroformic esters or chloroformic thioesters of the formula (VI), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

Suitable acid binders for the reaction according to the process (D) according to the invention are all customary acid acceptors. Preference is given to using tertiary amines, such as triethylamine, pyridine, DABCO, DBU, DBA, Hünig base and N,N-dimethylaniline, furthermore alkaline earth metal oxides, such as magnesium oxide and calcium oxide, moreover alkali metal and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide.

Suitable diluents for use in the process (D) according to the invention are all solvents which are inert towards the chloroformic esters or chloroformic thioesters. Preference is given to using hydrocarbons, such as benzine, benzene, toluene, xylene and tetralin, furthermore halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, moreover ketones, such as acetone and methyl isopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxane, additionally carboxylic esters, such as ethyl acetate, and also strongly polar solvents, such as dimethyl sulphoxide and sulpholane.

When carrying out the process (D) according to the invention, the reaction temperatures can be varied within a relatively wide range. If the process is carried out in the presence of a diluent and an acid binder, the reaction temperatures are generally between −20° C. and +100° C., preferably between 0° C. and 50° C.

The process (D) according to the invention is generally carried out under atmospheric pressure.

When carrying out the process (D) according to the invention, the starting materials of the formula (I-a) and the appropriate chloroformic ester or chloroformic thioester of the formula (VI) are generally each employed in approximately equivalent amounts. However, it is also possible to use a relatively large excess (up to 2 mol) of one component or the other. Work-up is carried out by customary methods. In general, precipitated salts are removed and the reaction mixture that remains is concentrated by removing the diluent under reduced pressure.

The process (E) according to the invention is characterized in that compounds of the formula (I-a) are each reacted with compounds of the formula (VII) in the presence of a diluent and, if appropriate, in the presence of an acid binder.

In preparation process (E), about 1 mol of chloromonothioformic ester or chlorodithioformic ester of the formula (VII) is employed per mole of the starting material of the formula (I-a) at from 0 to 120° C., preferably from 20 to 60° C.

Suitable diluents which are added, if appropriate, are all inert polar organic solvents, such as ethers, amides, sulphones, sulphoxides, and also halogenated alkanes.

Preference is given to using dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or methylene chloride.

If, in a preferred embodiment, the enolate salt of the compounds (I-a) is prepared by addition of strong deprotonating agents, such as, for example, sodium hydride or potassium tert-butoxide, the further addition of acid binders may be dispensed with.

If acid binders are used, these are customary inorganic or organic bases; sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine may be mentioned by way of example.

The reaction may be carried out at atmospheric pressure or under elevated pressure and is preferably carried out at atmospheric pressure. Work-up is carried out by customary methods.

The process (F) according to the invention is characterized in that compounds of the formula (I-a) are each reacted with sulphonyl chlorides of the formula (VIII), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

In preparation process (F), about 1 mol of sulphonyl chloride of the formula (VIII) is reacted per mole of the starting material of the formula (I-a) at from −20 to 150° C., preferably from 20 to 70° C.

Suitable diluents which are added, if appropriate, are all inert polar organic solvents, such as ethers, amides, nitriles, sulphones, sulphoxides or halogenated hydrocarbons, such as methylene chloride.

Preference is given to using dimethyl sulphoxide, tetrahydrofuran, dimethylformamide, methylene chloride.

If, in a preferred embodiment, the enolate salt of the compound (I-a) is prepared by addition of strong deprotonating agents (such as, for example, sodium hydride or potassium tert-butoxide), the further addition of acid binders may be dispensed with.

If acid binders are used, these are customary inorganic or organic bases, for example sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine.

The reaction may be carried out at atmospheric pressure or under elevated pressure and is preferably carried out at atmospheric pressure. Work-up is carried out by customary methods.

The process (G) according to the invention is characterized in that compounds of the formula (I-a) are each reacted with phosphorus compounds of the formula (IX), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

In preparation process (G), to obtain compounds of the formula (I-e), from 1 to 2, preferably from 1 to 1.3, mol of the phosphorus compound of the formula (IX) are reacted per mole of the compound (I-a), at temperatures between −40° C. and 150° C., preferably between −10 and 110° C.

Suitable acid binders which are added, if appropriate, are customary inorganic or organic bases, such as hydroxides, carbonates or amines. Sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine may be mentioned by way of example.

The reaction can be carried out at atmospheric pressure or under elevated pressure and is preferably carried out at atmospheric pressure. Work-up is carried out by customary methods of organic chemistry. The end products are preferably purified by crystallization, chromatographic purification or “incipient distillation”, i.e. removal of the volatile components under reduced pressure.

The process (H) is characterized in that compounds of the formula (I-a) are reacted with metal hydroxides or metal alkoxides of the formula (X) or amines of the formula (XI), if appropriate in the presence of a diluent.

Suitable diluents for use in the process (H) according to the invention are, preferably, ethers, such as tetrahydrofuran, dioxane, diethyl ether, or else alcohols, such as methanol, ethanol, isopropanol, and also water.

The process (H) according to the invention is generally carried out under atmospheric pressure.

The reaction temperatures are generally between −20° C. and 100° C., preferably between 0° C. and 50° C.

The process (I) according to the invention is characterized in that compounds of the formula (I-a) are each reacted with (I-α) compounds of the formula (XII), if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst, or (I-β) with compounds of the formula (XIII), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

In preparation process (I-α), about 1 mol of isocyanate of the formula (XII) is reacted per mole of starting material of the formula (I-a), at from 0 to 100° C., preferably from 20 to 50° C.

Suitable diluents which are added, if appropriate, are all inert organic solvents, such as ethers, amides, nitriles, sulphones or sulphoxides.

If appropriate, catalysts may be added to accelerate the reaction. Suitable for use as catalysts are, very advantageously, organotin compounds, such as, for example, dibutyltin dilaurate. The reaction is preferably carried out at atmospheric pressure.

In preparation process (I-β), about 1 mol of carbamoyl chloride of the formula (XIII) is reacted per mole of starting compound of the formula (I-a), at from −20 to 150° C., preferably at from 0 to 70° C.

Suitable diluents which are added, if appropriate, are all inert polar organic solvents, such as ethers, amides, sulphones, sulphoxides or halogenated hydrocarbons.

Preference is given to using dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or methylene chloride.

If, in a preferred embodiment, the enolate salt of the compounds (I-a) is prepared by addition of strong deprotonating agents (such as, for example, sodium hydride or potassium tert-butoxide), the further addition of acid binders may be dispensed with.

If acid binders are used, these are customary inorganic or organic bases, for example sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine.

The reaction can be carried out at atmospheric pressure or under elevated pressure and is preferably carried out at atmospheric pressure. Work-up is carried out by customary methods.

The active compounds of the invention, in combination with good plant tolerance and favourable toxicity to warm-blooded animals and being tolerated well by the environment, are suitable for protecting plants and plant organs, for increasing the harvest yields, for improving the quality of the harvested material and for controlling animal pests, in particular insects, arachnids, helminths, nematodes and molluscs, which are encountered in agriculture, in horticulture, in animal husbandry, in forests, in gardens and leisure facilities, in the protection of stored products and of materials, and in the hygiene sector. They may be preferably employed as crop protection agents. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:

From the class of the Bivalva, for example,Dreissenaspp.

From the order of the Chilopoda, for example,Geophilusspp.,Scutigeraspp.

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

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

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

From the class of the Gastropoda, for example,Arionspp.,Biomphalariaspp.,Bulinusspp.,Derocerasspp.,Galbaspp.,Lymnaeaspp.,Oncomelaniaspp.,Succineaspp.

It is furthermore possible to control protozoa, such asEimeria.

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

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

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

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

If appropriate, the compounds according to the invention can, at certain concentrations or application rates, also be used as herbicides, safeners, growth regulators or agents to improve plant properties, or as microbicides, for example as fungicides, antimycotics, bactericides, viricides (including agents against viroids) or as agents against MLO (Mycoplasma-like organisms) and RLO (Rickettsia-like organisms). If appropriate, they can also be employed as intermediates or precursors for the synthesis of other active compounds.

All plants and plant parts can be treated in accordance with the invention. Plants are to be understood as meaning in the present context 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 plant breeding and optimization methods or by biotechnological and genetic engineering methods or by combinations of these methods, including the transgenic plants and including the plant cultivars protectable or not protectable by plant breeders' rights. Plant parts are to be understood as meaning all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested material, and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

Treatment according to the invention of the plants and plant parts with the active compounds is carried out directly or by allowing the compounds to act on the surroundings, habitat or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on, injection and, in the case of propagation material, in particular in the case of seeds, also by applying one or more coats.

The active compounds can be converted to the customary formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspension-emulsion concentrates, natural materials impregnated with active compound, synthetic materials impregnated with active compound, fertilizers and microencapsulations in polymeric substances.

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 surfactants, that is emulsifiers and/or dispersants and/or foam-formers. The formulations are prepared either in suitable plants or else before or during the application.

Suitable for use as auxiliaries are substances which are suitable for imparting to the composition itself and/or to preparations derived therefrom (for example spray liquors, seed dressings) particular properties such as certain technical properties and/or also particular biological properties. Typical suitable auxiliaries are: extenders, solvents and carriers.

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 solid carriers for granules are: for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic meals, and granules of organic material such as paper, sawdust, coconut shells, maize 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, alkylsulphonates, alkyl sulphates, arylsulphonates and also protein hydrolysates; suitable dispersants are nonionic and/or ionic substances, for example from the classes of the alcohol-POE and/or -POP ethers, acid and/or POP-POE esters, alkylaryl and/or POP-POE ethers, fat- and/or POP-POE adducts, POE- and/or POP-polyol derivatives, POE- and/or POP-sorbitan or -sugar adducts, alkyl or aryl sulphates, alkyl- or arylsulphonates and alkyl or aryl phosphates or the corresponding PO-ether adducts. Furthermore, suitable oligo- or polymers, for example those derived from vinylic monomers, from acrylic acid, from EO and/or PO alone or in combination with, for example, (poly)alcohols or (poly)amines. It is also possible to employ lignin and its sulphonic acid derivatives, unmodified and modified celluloses, aromatic and/or aliphatic sulphonic acids and their adducts with formaldehyde.

Other possible additives are perfumes, mineral or vegetable, optionally modified oils, waxes and nutrients (including trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

Stabilizers, such as low-temperature stabilizers, preservatives, antioxidants, light stabilizers or other agents which improve chemical and/or physical stability may also be present.

The formulations generally comprise between 0.01 and 98% by weight of active compound, preferably between 0.5 and 90%.

The active compound according to the invention can be used in its commercially available formulations and in the use forms, prepared from these formulations, as a mixture with other active compounds, such as insecticides, attractants, sterilizing agents, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners, fertilizers or semiochemicals.

Particularly favourable mixing components are, for example, the following compounds:

Inhibitors of nucleic acid synthesis

A mixture with other known active compounds, such as herbicides, fertilizers, growth regulators, safeners, semiochemicals, or else with agents for improving the plant properties, is also possible.

When used as insecticides, the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with synergistic agents. Synergistic agents are compounds which increase the action of the active compounds, without it being necessary for the synergistic agent added to be active itself.

When used as insecticides, the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with inhibitors which reduce degradation of the active compound after use in the environment of the plant, on the surface of parts of plants or in plant tissues.

The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits. The active compound concentration of the use forms can be from 0.00000001 to 95% by weight of active compound, preferably between 0.00001 and 1% by weight.

The compounds are employed in a customary manner appropriate for the use forms.

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 cultivars, 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 cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The terms “parts”, “parts of plants” and “plant parts” have been explained above.

Particularly preferably, plants of the plant cultivars which are in each case commercially available or in use are treated according to the invention. Plant cultivars are to be understood as meaning plants having novel properties (“traits”) which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, bio- or genotypes.

Depending on the plant species or plant cultivars, 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, higher 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 preferred transgenic plants or plant cultivars (obtained by genetic engineering) which are to be treated according to the invention include all plants which, by virtue of the genetic modification, received genetic material which imparts particular 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, higher 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 traits 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, sugar beet, tomatoes, peas and other vegetable varieties, cotton, tobacco, 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, tobacco and oilseed rape. Traits that are emphasized are in particular increased defense of the plants against insects, arachnids, nematodes and slugs and snails by virtue of toxins formed in the plants, in particular those formed in the plants by the genetic material fromBacillus thuringiensis(for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIEB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof) (referred to hereinbelow as “Bt plants”). Traits that are also particularly emphasized are the increased defence of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits that are furthermore particularly emphasized are the increased tolerance of 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 combination 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 beans), 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 cultivars having these genetic traits or genetic traits still to be developed, which plant cultivars 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 compounds of the general formula I and/or the active compound mixtures according to the invention. The preferred ranges stated above for the active compounds or mixtures also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the compounds or mixtures specifically mentioned in the present text.

The active compounds according to the invention act not only against plant, hygiene and stored product pests, but also in the veterinary medicine sector against animal parasites (ecto- and endoparasites), such as hard ticks, soft ticks, mange mites, leaf mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, feather lice and fleas. These parasites include:

From the order of the Mallophagida and the suborders Amblycerina and Ischnocerina, for example,Trimenoponspp.,Menoponspp.,Trinotonspp.,Bovicolaspp.,Werneckiellaspp.,Lepikentronspp.,Damalinaspp.,Trichodectesspp.,Felicolaspp.

From the order of the Diptera and the suborders Nematocerina and Brachycerina, for example,Aedesspp.,Anophelesspp.,Culexspp.,Simuliumspp.,Eusimuliumspp.,Phlebotomusspp.,Lutzomyiaspp.,Culicoidesspp.,Chrysopsspp.,Hybomitraspp.,Atylotusspp.,Tabanusspp.,Haematopotaspp.,Philipomyiaspp.,Braulaspp.,Muscaspp.,Hydrotaeaspp.,Stomoxysspp.,Haematobiaspp.,Morelliaspp.,Fanniaspp.,Glossinaspp.,Calliphoraspp.,Luciliaspp.,Chrysomyiaspp.,Wohlfahrtiaspp.,Sarcophagaspp.,Oestrusspp.,Hypodermaspp.,Gasterophilusspp.,Hippoboscaspp.,Lipoptenaspp.,Melophagusspp.

From the order of the Blattarida, for example,Blatta orientalis, Periplaneta americana, Blattela germanica, Supellaspp.

From the subclass of the Acari (Acarina) and the orders of the Meta- and Mesostigmata, for example,Argasspp.,Ornithodorusspp.,Otobiusspp.,Ixodesspp.,Amblyommaspp.,Boophilusspp.,Dermacentorspp.,Haemophysalisspp.,Hyalommaspp.,Rhipicephalusspp.,Dermanyssusspp.,Raillietiaspp.,Pneumonyssusspp.,Sternostomaspp.,Varroaspp.

From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for example,Acarapisspp.,Cheyletiellaspp.,Ornithocheyletiaspp.,Myobiaspp.,Psorergatesspp.,Demodexspp.,Trombiculaspp.,Listrophorusspp.,Acarusspp.,Tyrophagusspp.,Caloglyphusspp.,Hypodectesspp.,Pterolichusspp.,Psoroptesspp.,Chorioptesspp.,Otodectesspp.,Sarcoptesspp.,Notoedresspp.,Knemidocoptesspp.,Cytoditesspp.,Laminosioptesspp.

The active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which infest agricultural productive livestock, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese and bees, other pets, such as, for example, dogs, cats, caged birds and aquarium fish, and also so-called test animals, such as, for example, hamsters, guinea pigs, rats and mice. By controlling these arthropods, cases of death and reductions in productivity (for meat, milk, wool, hides, eggs, honey etc.) should be diminished, so that more economic and easier animal husbandry is possible by use of the active compounds according to the invention.

The active compounds according to the invention are used in the veterinary sector and in animal husbandry in a known manner by enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed-through process and suppositories, by parenteral administration, such as, for example, by injection (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal administration, by dermal use in the form, for example, of dipping or bathing, spraying, pouring on and spotting on, washing and powdering, and also with the aid of moulded articles containing the active compound, such as collars, ear marks, tail marks, limb bands, halters, marking devices and the like.

When used for cattle, poultry, pets and the like, the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, free-flowing compositions), which comprise the active compounds in an amount of 1 to 80% by weight, directly or after 100- to 10 000-fold dilution, or they can be used as a chemical bath.

It has furthermore been found that the compounds according to the invention also have a strong insecticidal action against insects which destroy industrial materials.

The following insects may be mentioned as examples and as preferred—but without any limitation:

Industrial materials in the present connection are to be understood as meaning non-living materials, such as, preferably, plastics, adhesives, sizes, papers and cardboards, leather, wood and processed wood products and coating compositions.

The ready-to-use compositions may, if appropriate, comprise further insecticides and, if appropriate, one or more fungicides.

With respect to possible additional additives, reference may be made to the insecticides and fungicides mentioned above.

The compounds according to the invention can likewise be employed for protecting objects which come into contact with saltwater or brackish water, in particular hulls, screens, nets, buildings, moorings and signalling systems, against fouling.

Furthermore, the compounds according to the invention, alone or in combinations with other active compounds, may be employed as antifouling agents.

In domestic, hygiene and stored-product protection, the active compounds are also suitable for controlling animal pests, in particular insects, arachnids and mites, which are found in enclosed spaces such as, for example, dwellings, factory halls, offices, vehicle cabins and the like. They can be employed alone or in combination with other active compounds and auxiliaries in domestic insecticide products for controlling these pests. They are active against sensitive and resistant species and against all developmental stages. These pests include:

From the order of the Scorpionidea, for example,Buthus occitanus.

From the order of the Araneae, for example, Aviculariidae, Araneidae.

From the order of the Opiliones, for example,Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.

From the order of the Isopoda, for example,Oniscus asellus, Porcellio scaber.From the order of the Diplopoda, for example,Blaniulus guttulatus, Polydesmusspp.

From the order of the Chilopoda, for example,Geophilusspp.

From the order of the Zygentoma, for example,Ctenolepismaspp.,Lepisma saccharina, Lepismodes inquilinus.

From the order of the Saltatoria, for example,Acheta domesticus.

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

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

From the order of the Psocoptera, for example,Lepinatusspp.,Liposcelisspp.

From the order of the Heteroptera, for example,Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.

In the field of household insecticides, they are used alone or in combination with other suitable active compounds, such as phosphoric esters, carbamates, pyrethroids, neonicotinoids, growth regulators or active compounds from other known classes of insecticides.

They are used in aerosols, pressure-free spray products, for example pump and atomizer sprays, automatic fogging systems, foggers, foams, gels, evaporator products with evaporator tablets made of cellulose or polymer, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-free, or passive, evaporation systems, moth papers, moth bags and moth gels, as granules or dusts, in baits for spreading or in bait stations.

The active compounds/active compound combinations according to the invention can also be used as defoliants, desiccants, haulm killers and, in particular, as weed killers. Weeds in the broadest sense are understood as meaning all plants which grow at locations where they are undesired. Whether the substances according to the invention act as nonselective or selective herbicides depends essentially on the application rate.

The active compounds/active compound combinations according to the invention can be used for example in the following plants:

However, the use of the active compounds/active compound combinations according to the invention is in no way restricted to these genera, but extends in the same manner to other plants.

Depending on the concentration, the active compounds/active compound combinations according to the invention are suitable for the nonselective weed control on, for example, industrial terrains and railway tracks and on paths and locations with and without trees. Likewise the active compounds according to the invention can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns, turf and pastureland, and for the selective control of weeds in annual crops.

The compounds of the formula (I)/active compound combinations according to the invention have strong herbicidal activity and a broad activity spectrum when used on the soil and on aerial plant parts. To a certain extent, they are also suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both pre- and post-emergence.

At certain concentrations or application rates, the active compounds/active compound combinations according to the invention can also be employed for controlling animal pests and fungal or bacterial plant diseases. If appropriate, they can also be used as intermediates or precursors for the synthesis of other active compounds.

The active compounds/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 very fine capsules in polymeric substances.

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

The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.

The active compounds/active compound combinations according to the invention, as such or in their formulations, can also be used for weed control purposes as a mixture with known herbicides and/or with substances which improve crop plant tolerance (“safeners”), ready mixes or tank mixes being possible. Mixtures with herbicide products which contain one or more known herbicides and a safener are hence also possible.

Herbicides which are suitable for the mixtures are known herbicides, for example

A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and soil conditioners, is also possible.

The active compounds or active compound combinations can be applied as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are applied in the customary manner, for example by watering, spraying, atomizing, spreading.

The active compounds or active compound combinations according to the invention can be applied both before and after plant emergence. They can also be incorporated into the soil prior to planting.

The application rate of active compound can vary within a substantial range. Essentially, it depends on the nature of the desired effect. In general, the application rates are between 1 g and 10 kg of active compound per hectare of soil area, preferably between 5 g and 5 kg per ha.

The advantageous effect of the compatibility with crop plants of the active compound combinations according to the invention is particularly pronounced at certain concentration ratios.

However, the weight ratios of the active compounds in the active compound combinations can be varied within relatively wide ranges. In general, from 0.001 to 1000 parts by weight, preferably from 0.01 to 100 parts by weight, particularly preferably 0.05 to 20 parts by weight, of one of the compounds which improves crop plant compatibility (antidotes/safeners) mentioned above under (b′) are present per part by weight of active compound of the formula (I).

The active compound combinations according to the invention are generally applied in the form of finished formulations. However, the active compounds contained in the active compound combinations can, as individual formulations, also be mixed during use, i.e. be applied in the form of tank mixes.

For certain applications, in particular by the post-emergence method, it may furthermore be advantageous to include, as further additives in the formulations, mineral or vegetable oils which are tolerated by plants (for example the commercial preparation “Rako Binol”), or ammonium salts, such as, for example, ammonium sulphate or ammonium thiocyanate.

The novel active compound combinations can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. Application is in the customary manner, for example by watering, spraying, atomizing, dusting or scattering.

The application rates of the active compound combinations according to the invention can be varied within a certain range; they depend, inter alia, on the weather and on soil factors. In general, the application rates are between 0.001 and 5 kg per ha, preferably between 0.005 and 2 kg per ha, particularly preferably between 0.01 and 0.5 kg per ha.

The active compound combinations according to the invention can be applied before and after emergence of the plants, that is to say by the pre-emergence and post-emergence method.

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

The term “active compounds” also includes the active compound combinations mentioned.

Preparation and use of the active compounds according to the invention is illustrated by the examples below.

At 40-50° C., 7.3 g of the compound of Example II-1 in N,N-dimethylacetamide are added dropwise to 4.59 g (38.8 mmol) of potassium tert-butoxide in 10 ml of dimethylacetamide, and the mixture is stirred at 50° C. for 3 hours.

After having been checked by thin-layer chromatography, the reaction mixture is poured into 200 ml of ice-water and, at 0-10° C., adjusted to pH 4 using 1N hydrochloric acid. The precipitate is filtered off with suction, washed and dried.

0.76 g (2 mmol) of the compound of Ex. I-5 from WO 01/89300, 0.52 g (3 mmol) of 3,4,5-trifluorophenylboronic acid and 1.06 g (10 mmol) of sodium carbonate are initially charged in 15 ml of water. 0.05 g (0.2 mmol) of palladium(II) nitrate dihydrate is added, and the mixture is heated under reflux at 120° C. for 8 h. The reaction mixture is then acidified with dilute hydrochloric acid, and the precipitate is filtered off with suction. Purification is carried out by MPLC on silica gel using cyclohexane/acetone 7:3.

Analogously to Example (I-a-1) and in accordance with the general statements on the preparation, the following compounds of the formula (I-a) are obtained

0.21 ml of triethylamine and 10 mg of 4-N,N-dimethylaminopyridine are added to 0.57 g (1.5 mmol) of the compound of Example I-a-1 in 20 ml of ethyl acetate. Under reflux, 0.12 ml (1.5 mmol) of acetyl chloride in 1 ml of ethyl acetate is added dropwise, and the mixture is stirred under reflux for one hour. The solvent is removed under reduced pressure using a rotary evaporator, and the residue is purified on silica gel using dichloromethane/ethyl acetate (gradient from 10:1 to 3:1).

Analogously to Example (I-b-1) and in accordance with the general statements on the preparation, the following compounds of the formula (I-b) are obtained

0.21 ml of triethylamine and 10 mg of 4-N,N-dimethylaminopyridine are added to 0.57 g (1.5 mmol) of the compound of Example I-a-1 in 20 ml of dichloromethane. At 20° C., 0.14 ml (1.5 mmol) of ethyl chloroformate in dichloromethane is added dropwise, and the mixture is stirred at room temperature for one hour. The solvent is removed under reduced pressure using a rotary evaporator, and the residue is purified on silica gel using dichloromethane/ethyl acetate(10:1).

Analogously to Example (I-c-1) and in accordance with the general statements on the preparation, the following compounds of the formula (I-c) are obtained

A little at a time, 0.39 g (1 mmol) of the compound of Example (I-a-2) is introduced into a solution of 5 ml of water and 1 ml of 1N aqueous sodium hydroxide solution, and the mixture is stirred at 20° C. for 1 h and concentrated using a rotary evaporator.

Analogously to Example (I-f-1), Example (I-f-2) is obtained

4.9 g (20 mmol) of 3-(4-fluorophenyl)-6-methylphenylacetic acid and 7.3 ml of thionyl chloride are heated at 80° C. until the evolution of gas has ended. Excess thionyl chloride is removed at 50° C. under reduced pressure, and the residue is taken up in 50 ml of ethyl acetate (solution 1).

4.92 g (22 mmol) of methyl cis-4-methoxy-1-aminocyclohexanecarboxylate hydrochloride are initially charged in 50 ml of ethyl acetate, and 22 ml of 1N aqueous sodium hydroxide solution are added dropwise at 0-5° C. Solution 1 and a further 20 ml of 1N sodium hydroxide solution are then simultaneously added dropwise at 0-5° C. After the reaction has ended (according to thin-layer chromatography), the mixture is extracted with ethyl acetate, the extract is dried and concentrated under reduced pressure using a rotary evaporator and the residue is chromatographed on silica using the mobile phase methylene chloride/ethyl acetate.

Analogously to Example (II-1) and in accordance with the general statements on the preparation, the following compounds of the formula (II) are obtained

Solvent: 7 parts by weight of dimethylformamide

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 emulsifier-containing water to the desired concentration. For application with ammonium salts or phosphonium salts these are added in a concentration of 1000 ppm to the spray liquor.

Cotton plants (Gossypium hirsutum) which are severely infested with cotton aphids (Aphis gossypii) are treated by spraying to runoff point with the preparation of the active substance at the desired concentration.

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.

Activity Boost Through Ammonium/Phosphonium Salts in Combination with Penetrants

Solvent: 7 parts by weight of dimethylformamide

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 water to the desired concentration. For application with ammonium salts or phosphonium salts and penetrants (rapeseed oil methyl ester 500 EW) these are added in each case in a concentration of 1000 ppm to the spray liquor.

Bell pepper plants (Capsicum annuum) which are heavily infested by the green peach aphid (Myzus persicae) are treated with the active compound preparation of the desired concentration by spraying to runoff point. After the desired period of time, the kill in % is determined. 100% means that all animals have been killed; 0% means that none of the animals have been killed.

Solvent: 7 parts by weight of dimethylformamide

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 emulsifier-containing water to the desired concentration. For application with ammonium salts or phosphonium salts and penetrant (rapeseed oil methyl ester 500 EW) these are added in each case in a concentration of 1000 ppm (a.i.) to the spray liquor.

Cotton plants (Gossypium hirsutum) which are heavily infested by the cotton aphid (Aphis gossypii) are treated with the active compound preparation of the desired concentration by spraying to runoff point.

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.

Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed in sandy loam in wood fibre pots and covered with soil. The test compounds, formulated in the form of wettable powders (WP), are then, as an aqueous suspension with a water application rate of 600 l/ha (converted) with 0.2% of wetting agent added, applied at various dosages to the surface of the covering soil.

After the treatment, the pots are placed in a greenhouse and kept under good growth conditions for the test plants. The visual assessment of the emergence damage on the test plants is carried out after a trial period of 3 weeks by comparison with the untreated control (herbicidal activity in %: 100% activity=the plants have died, 0% activity=like control plants).

Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed in sandy loam in wood fibre pots, covered with soil and cultivated in a greenhouse under good growth conditions. 2 to 3 weeks after sowing, the test plants are treated at the one-leaf stage. The test compounds, formulated as wettable powders (WP), are then, in various dosages with a water application rate of 600 l/ha (converted), with 0.2% of wetting agent added, sprayed onto the green parts of the plants. After the test plants have been kept in the greenhouse under optimum growth conditions for about 3 weeks, the effect of the preparations is rated visually in comparison to untreated controls (herbicidal activity in per cent: 100% activity=the plants have died, 0% activity=like control plants).

In addition to the compounds mentioned above, the following compounds, applied by the post-emergence method at 80 g/ha, show an activity of ≧80% againstEchinocloa crus-galliandSetaria viridis: I-a-1, I-a-2, I-b-1, I-b-2, I-c-3.

Solvents: 78.0 parts by weight of acetone1.5 parts by weight of dimethylformamide

Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether

Discs of chinese cabbage (Brassica pekinensis) which are infested by all stages of the green peach aphid (Myzus persicae) are sprayed with an active compound preparation of the desired concentration.

After the desired period of time, the effect in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.

In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 500 g/ha, an activity of ≧80%:

Solvent: 78.0 parts by weight of acetone1.5 parts by weight of dimethylformamide

Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether

Discs of chinese cabbage (Brassica pekinensis) are sprayed with an active compound preparation of the desired concentration and, after drying, populated with larvae of the mustard beetle (Phaedon cochleariae).

After the desired period of time, the effect in % is determined. 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae have been killed.

In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 500 g/ha, an activity of ≧80%:

Solvent: 78.0 parts by weight of acetone1.5 parts by weight of dimethylformamide

Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether

Discs of maize leaves (Zea mays) are sprayed with an active compound preparation of the desired concentration and, after drying, populated with caterpillars of the army worm (Spodoptera frugiperda).

After the desired period of time, the effect in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.

In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 500 g/ha, an activity of ≧80%:

Solvent: 78.0 parts by weight of acetone1.5 parts by weight of dimethylformamide

Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether

Discs of bean leaves (Phaseolus vulgaris) which are infested by all stages of the greenhouse red spidermite (Tetranychus urticae) are sprayed with an active compound preparation of the desired concentration.

After the desired period of time, the effect in % is determined. 100% means that all spidermites have been killed; 0% means that none of the spidermites have been killed.

In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 20 g/ha, an activity of ≧80%:

In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 100 g/ha, an activity of >80%:

Solvent: 7 parts by weight of dimethylformamide

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 amount of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

Cotton plants (Gossypium hirsutum) which are heavily infested by the cotton aphid (Aphis gossypii) are watered with an active compound prepartion of the desired concentration.

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.

In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 20 ppm, an activity of ≧80% after 10 days:

Solvent: 7 parts by weight of dimethylformamide

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 amount of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which are heavily infested by the green peach aphid (Myzus persicae) are watered with an active compound prepartion of the desired concentration.

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.

In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 20 ppm, an activity of ≧80% after 10 days:

Solvent: 7 parts by weight of dimethylformamide

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 amount of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.

Bean plants (Phaseolus vulgaris) which are heavily infested by the all stages of the greenhouse red spidermite (Tetranychus urticae) are watered with an active compound prepartion of the desired concentration.

After the desired period of time, the kill in % is determined. 100% means that all spidermites have been killed; 0% means that none of the spidermites have been killed.

In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 20 ppm, an activity of ≧80% after 14 days:

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

The active compound solution is injected into the abdomen (Boophilus microplus) and the animals are transferred into dishes and stored in a climatized room.

After the desired period of time the activity in % is determined. 100% means that none of the ticks has laid fertile eggs.

In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 20 μg/animal, an activity of ≧80%:

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.

Containers containing horse meat treated with the active compound preparation of the desired concentration are populated withLucilia cuprinalarvae.

After the desired period of time, the kill in % is determined. 100% means that all larvae have been killed; 0% means that none of the larvae have been killed.

In this test, for example, the following compounds of the Preparation Examples show, at an application rate of 100 ppm, an activity of ≧80%:

Heliothis virescensTest—Treatment of Transgenic Plants

Solvent: 7 parts by weight of acetone

Emulsifier: 1 part 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 amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Soya bean shoots (Glycine max) of the cultivar Roundup Ready (trade mark of Monsanto Comp. USA) are treated by being dipped into the active compound preparation of the desired concentration and are populated with the tobacco bud worm Heliothis virescens while the leaves are still moist.

After the desired period of time, the kill of the insects is determined.

Critical Concentration Test/Soil Insects—Treatment of Transgenic Plants

Test insect: Diabrotica balteata—larvae in the soil

Solvent: 7 parts by weight of acetone

Emulsifier: 1 part 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 amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The active compound preparation is poured onto the soil Here, the concentration of active compound in the preparation is virtually immaterial; only the amount by weight of active compound per volume unit of soil, which is stated in ppm (mg/l) matters. The soil is filled into 0.25 l pots, and these are allowed to stand at 20° C.

Immediately after the preparation, 5 pregerminated maize corns of the cultivar YIELD GUARD (trade mark of Monsanto Comp., USA) are placed into each pot. After 2 days, the appropriate test insects are placed into the treated soil. After a further 7 days, the efficacy of the active compound is determined by counting the maize plants that have emerged (1 plant=20% activity).