Pyrazolyl derivatives as pest control agents

The invention comprises novel pyrazolyl derivatives of the general formula (I)Also described are processes for preparing the compounds of the formula (I). The compounds according to the invention are especially suitable for controlling insects and archnids in agriculture, and ectoparasites in veterinary medicine.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a § 371 National State Application of PCT/EP2016/054955, filed Mar. 9, 2016, which claims priority to European Application No. 15158341.6 filed Mar. 10, 2015.

BACKGROUND OF THE INVENTION

Field of the Invention

The present application relates to pyrazolyl derivatives, to processes for preparation thereof and to the use thereof for controlling animal pests, especially arthropods and in particular insects and arachnids.

Description of Related Art

SUMMARY

It was an object of the present invention to provide compounds which broaden the spectrum of the pesticides in various aspects and/or improve their activity.

It has now been found that, surprisingly, certain pyrazolyl derivatives and their N-oxides and salts have biological properties superior to the prior art and are especially suitable for controlling animal pests, and therefore have particularly good usability in the agrochemical sector and in the animal health sector.

Abstract

One aspect of the present invention relates to compounds of the formula (I)

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

A preferred embodiment is directed to a compound as described above where B1is CR6, B2is CR7, B3is CR8, B4is CR9and B5is CR10.

A further preferred embodiment is directed to a compound as described above where R6is halogen or optionally halogenated C1-C6-alkyl or optionally halogenated C1-C6-alkoxy, R7is hydrogen, R8is C1-C6-halogenated alkyl, R9is hydrogen and R10is halogen or optionally halogenated C1-C6-alkyl or optionally halogenated C1-C6-alkoxy. A more preferred embodiment is directed to a compound as described above where R6is halogen or optionally halogenated C1-C6-alkyl, R7is hydrogen, R8is halogenated C1-C6-alkyl, R9is hydrogen and R10is halogen or optionally halogenated C1-C6-alkyl.

A further preferred embodiment is directed to a compound as described above, where R11and R12are hydrogen and W is oxygen.

A further preferred embodiment is directed to a compound as described above, where A1is CR2, A2is CR3or N, A3is CR4or N and A4is CR5and R2is hydrogen or C1-C6-alkyl and R3, R4and R5are each independently of one another hydrogen, halogen, CN, optionally halogenated C1-C6-alkyl or N,N-di-C1-C6-alkylamino.

A further preferred embodiment is directed to a compound as described above, where Q is

C1-C6-alkyl optionally substituted by one, two or three substituents selected from the group consisting of oxo, cyano, nitro and amino,

C3-C6-alkyl optionally substituted by one, two or three substituents selected from the group consisting of halogen, cyano, nitro, C1-C3-alkyl and amino,

C2-C5-heterocyclyl optionally substituted by one, two or three substituents selected from the group consisting of halogen, cyano, nitro, C1-C3-alkyl and amino,

an aryl substituted by 0, 1, 2, 3 or 4 V substituents or

V is each independently of one another halogen, cyano, C1-C6-alkyl or C1-C6-alkoxy.

A further preferred embodiment is directed to a compound as described above, where Q iscyclopropyl optionally substituted by cyano or C1-C3-alkyl, orthietanyl (thiacyclobutanyl) optionally substituted by cyano or C1-C3-alkyl, orphenyl substituted by 0, 1 or 2 V substituents each selected independently of one another from the group consisting of F, Cl, C1-C3-alkoxy (such as methoxy and ethoxy), C1-C3-alkyl (such as methyl), halogenated C1-C3-alkyl (such as CF3) and cyano, orpyridyl, pyrimidinyl and thiophenyl substituted by 0, 1 or 2 V substituents each selected independently of one another from the group consisting of F, Cl, C1-C3-alkyl (such as methyl), halogenated C1-C3-alkyl (such as CF3) and cyano, orpyridyl, pyrimidinyl, thienyl, oxazolyl or thiophenyl substituted by 0, 1 or 2 V substituents each selected independently of one another from the group consisting of F, Cl, C1-C3-alkyl (such as methyl), halogenated C1-C3-alkyl (such as CF3) and cyano.

A further preferred embodiment is directed to a compound as described above, whereA2represents CR2, where R2represents hydrogen,A2represents CR3or N, where R3 represents hydrogen,A3represents CR4or N, where R4is hydrogen, Cl, F, or C1-C3-alkyl (such as CH3) or —N(C1-C3-alkyl)2(such as —N(CH3)2),A4represents CR5, where R5represents hydrogen or F,B1represents CR6,B2represents CR7, where R7represents hydrogen,B3represents CR8,B4represents CR9, where R9represents hydrogen,B5represents CR10R6represents Cl, Br or C1-C3-alkyl (such as CH3),R8represents perhalogeniertes C1-C6-alkyl, more preferably perfluorinated C1-C4-alkyl such as CF3, C2F5, C3F7, C4F9,R10represents Cl, C1-C3-alkyl (such as methyl) or perfluorinated C1-C3-alkyl (such as CF3),R11and R12represent hydrogen,W is oxygen,Q represents (a) C3-C6-cycloalkyl optionally substituted by one substituent selected from the group consisting of halogen, C1-C3-alkyl and cyano (such as, for example, cyclopropyl optionally substituted by cyano or C1-C3-alkyl), (b) C2-C5-heterocyclyl optionally substituted by one substituent selected from the group consisting of halogen or cyano, such as, for example, thietanyl (thiacyclobutanyl) optionally substituted by cyano or C1-C3-alkyl, (c) an aryl substituted by 0, 1 or 2 V substituents or a 5- or 6-membered heteroaryl substituted by 0, 1, 2, 3 or 4 V substituents, wherein V is each independently of one another halogen (e.g. F, Cl), cyano, optionally halogenated C1-C6-alkyl, optionally halogenated C1-C6-alkoxy (such as phenyl optionally substituted by 0, 1 or 2 V substituents each selected independently of one another from the group consisting of halogen (such as F, Cl), C1-C3-alkoxy (such as methoxy and ethoxy), C1-C3-alkyl (such as methyl), halogenated C1-C3-alkyl (such as CF3) and cyano; or pyridyl, pyrimidinyl, thienyl, oxazolyl or thiophenyl optionally substituted by 0, 1 or 2 V substituents V each selected independently of one another from the group consisting of halogen (such as F, Cl), C1-C3-alkyl (such as methyl) halogenated C1-C3-alkyl (such as CF3) and cyano).

A further preferred embodiment is directed to a compound as described above, where a compound of the formula (I) is a compound of the formula (I′):

A further preferred embodiment is directed to a compound as described above, where a compound of the formula (I) is a compound of the formula (Ia):

A further preferred embodiment is directed to a compound as described above, where a compound of the formula (I) is a compound of the formula (Ib):

where R6, R8, R10and Q are defined as described above.

A further aspect relates to a compound of the formula (II)

A further aspect relates to a compound of the formula (III)

A further aspect relates to a pharmaceutical composition comprising at least one compound as described above.

A further aspect relates to compounds as described above specifically for use as a medicaments.

A further aspect relates to the use of compounds as described above for production of pharmaceutical compositions for control of parasites in animals.

A further aspect relates to the use of compounds as described above for protecting the propagation material of plants, preferably for protecting seed.

Definitions

The person skilled in the art is aware that the expressions “a” or “an” as used in the present application may, depending on the situation, mean “one (1)”, “one (1) or more” or “at least one (1)”.

The expression “optionally substituted” means, if no specific substituents are stated, that the group in question may be mono- or polysubstituted by a substituent M1, where in the case of polysubstitutions the substituents M1can be identical or different.

It is obvious to the person skilled in the art that examples given in the present application are not to be considered as limiting, but rather merely describe some embodiments in more detail.

The expressions “(Cn-Cm)” and “Cn-Cm-” are exchangeable and relate to the minimum and maximum number of carbon atoms in an organic group. “(C1-C6)” and “C1-C6-” alkyl, for example, relate to an alkyl group having 1, 2, 3, 4, 5 or 6 carbon atoms. The expressions “(Cn)” and “Cn—” are likewise exchangeable and relate to the number of carbon atoms in an organic group. The expressions “C3-cycloalkyl” and “(C3)-alkyl”, for example, relate to cyclopropyl.

In the definitions of the symbols given in the above formulae, collective terms which are generally representative of the following substituents were used:

According to the invention, “alkyl”—on its own or as a part of a chemical group—represents straight-chain or branched hydrocarbons having preferably 1 to 6 carbon atoms, particularly preferably 1, 2, 3 or 4 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl. The alkyl radicals according to the invention may optionally be substituted by one or more identical or different radicals M1.

According to the invention, “alkenyl”—on its own or as a part of a chemical group—represents straight-chain or branched hydrocarbons having preferably 2 to 6 carbon atoms, particularly preferably 2, 3 or 4 carbon atoms, and at least one double bond, for example vinyl, 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, etc. The alkenyl radicals according to the invention may optionally be substituted by one or more identical or different radicals M1.

According to the invention, “alkynyl”—on its own or as a part of a chemical group—represents straight-chain or branched hydrocarbons having preferably 2 to 6 carbon atoms, particularly preferably 2, 3 or 4 carbon atoms, and at least one triple bond, for example ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, etc. The alkynyl radicals according to the invention may optionally be substituted by one or more identical or different radicals M1.

According to the invention, “cycloalkyl”—on its own or as part of a chemical group—represents mono-, bi- or tricyclic hydrocarbons preferably having 3 to 10 carbons, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl or adamantyl, particularly preferably cycloalkyl radicals having 3, 4, 5, 6 or 7 carbon atoms, for example cyclopropyl or cyclobutyl. The cycloalkyl radicals according to the invention may optionally be substituted by one or more identical or different radicals M1.

According to the invention, “alkylcycloalkyl” represents mono-, bi- or tricyclic alkylcycloalkyl preferably having 4 to 10 or 4 to 7 carbon atoms, particularly preferably alkylcycloalkyl radicals having 4, 5 or 7 carbon atoms, for example ethylcyclopropyl or 4-methylcyclohexyl, where the alkylcycloalkyl is attached via the cycloalkyl moiety to the parent structure. The alkylcycloalkyl radicals according to the invention may optionally be substituted by one or more identical or different radicals M1.

According to the invention, “cycloalkylalkyl” represents mono-, bi- or tricyclic cycloalkylalkyl preferably having 4 to 10 or 4 to 7 carbon atoms, particularly preferably cycloalkylalkyl radicals having 4, 5 or 7 carbon atoms, inter alia cyclopropylmethyl or cyclobutylmethyl, where the alkylcycloalkyl is attached via the alkyl moiety to the parent structure. The cycloalkylalkyl radicals according to the invention may optionally be substituted by one or more identical or different radicals M1.

According to the invention, “alkoxy” represents straight-chain or branched O-alkyl preferably having 1 to 6 carbon atoms, more preferably alkoxy groups having 1 to 4 carbon atoms, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy or t-butoxy. The alkoxy groups according to the invention may optionally be substituted by one or more identical or different radicals M1.

According to the invention, “alkylsulfanyl” represents straight-chain or branched S-alkyl preferably having 1 to 6 carbon atoms, more preferably alkylsulfanyl groups having 1 to 4 carbon atoms, for example methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, s-butylthio and t-butylthio. The alkylsulfanyl groups according to the invention may optionally be substituted by one or more identical or different radicals M1.

According to the invention, “alkylsulfinyl” represents straight-chain or branched alkylsulfinyl preferably having 1 to 6 carbon atoms, more preferably alkylsulfinyl groups having 1 to 4 carbon atoms, for example methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, s-butylsulfinyl and t-butylsulfinyl. The alkylsulfinyl groups according to the invention may optionally be substituted by one or more identical or different radicals M1.

According to the invention, “alkylsulfonyl” represents straight-chain or branched alkylsulfonyl preferably having 1 to 6 carbon atoms, more preferably alkylsulfonyl groups having 1 to 4 carbon atoms, for example methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, s-butylsulfonyl and t-butylsulfonyl. The alkylsulfonyl groups according to the invention may optionally be substituted by one or more identical or different radicals M1.

According to the invention, “acyl” represents radicals containing an X1—C(═O)—X2group, where X1and X2independently of one another represent an organic radical as defined in the present application or represent hydrogen or represent a bond to the parent structure of a compound of the formula (I). In particular, “acyl” is understood to mean organic acids, esters, aldehydes, alkylcarbonyl (alkyl-C(═O)—) and amides. Preferably, X1and X2each independently of one another represent a group, optionally substituted by one or more identical or different radicals M1, selected from alkyl, alkylene (—CnH2n—), alkoxy, alkoxylene (—O—CnH2n—), amino, mono- or dialkylamino, or hydrogen, or a radical X1or X2represents a bond to the parent structure of a compound of the formula (I).

According to the invention “alkylcarbonyl” represents straight-chain or branched alkyl-C(═O)-preferably having 2 to 7 carbon atoms (including the carbon atom of the C(═O) group), more preferably alkylcarbonyl radicals having 2 to 5 carbon atoms ((C1-C4)-alkyl-C(═O)—), such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, s-butylcarbonyl and t-butylcarbonyl. The alkylcarbonyl groups according to the invention may optionally be substituted by one or more identical or different radicals M1.

According to the invention, “cycloalkylcarbonyl” represents straight-chain or branched cycloalkylcarbonyl preferably having 3 to 10 carbon atoms in the cycloalkyl moiety, more preferably cycloalkylcarbonyl having 3, 5 or 7 carbon atoms in the cycloalkyl moiety, for example cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cycloheptylcarbonyl, cyclooctylcarbonyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octylcarbonyl and adamantylcarbonyl. The cycloalkylcarbonyl groups according to the invention may optionally be substituted by one or more identical or different radicals M1.

According to the invention, “alkoxycarbonyl”—on its own or as part of a chemical group—represents straight-chain or branched alkoxycarbonyl preferably having 1 to 6 carbon atoms, more preferably having 1, 2, 3 or 4 carbon atoms in the alkoxy moiety, for example methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, s-butoxycarbonyl and t-butoxycarbonyl. The alkoxycarbonyl groups according to the invention may optionally be substituted by one or more identical or different radicals M1.

An amino group (—NH2) may optionally be substituted by one or more identical or different radicals M1.

Substituted amino such as mono- or disubstituted amino is a radical from the group of the substituted amino radicals N-substituted, for example, by one or two identical or different radicals from the group of alkyl, hydroxyl, amino, alkoxy, acyl and aryl; preferably N-mono- and N,N-dialkylamino (e.g. methylamino, ethylamino, N,N-dimethylamino, N,N-diethylamino, N,N-di-n-propylamino, N,N-diisopropylamino or N,N-dibutylamino), N-mono- or N,N-dialkoxyalkylamino groups (e.g. N-methoxymethylamino, N-methoxyethylamino, N,N-di(methoxymethyl)amino or N,N-di(methoxyethyl)amino), N-mono- and N,N-diarylamino, such as optionally substituted anilines, acylamino, N,N-diacylamino, N-alkyl-N-arylamino, N-alkyl-N-acylamino and saturated N-heterocycles; preference is given to alkyl radicals having 1 to 4 carbon atoms; aryl is preferably phenyl or optionally substituted phenyl; acyl is as defined further above, preferably (C1-C4)alkyl-C(═O)—.

Substituted amino also includes quaternary ammonium compounds (salts) having four organic substituents on the nitrogen atom.

According to the invention, “hydroxyalkyl” represents a straight-chain or branched alcohol preferably having 1 to 6 carbon atoms, more preferably 1, 2, 3 or 4 carbon atoms, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol and t-butanol. The hydroxyalkyl groups according to the invention may be substituted by one or more identical or different radicals M1.

According to the invention, “alkylaminocarbonyl” represents straight-chain or branched alkylaminocarbonyl having preferably 1 to 6 carbon atoms, more preferably 1, 2, 3 or 4 carbon atoms in the alkyl moiety, for example methylaminocarbonyl (—CONHCH3), ethylaminocarbonyl, n-propylaminocarbonyl, isopropylaminocarbonyl, s-butylaminocarbonyl and t-butylaminocarbonyl. The alkylaminocarbonyl groups according to the invention may optionally be substituted by one or more identical or different radicals M1.

According to the invention, “N,N-dialkylaminocarbonyl” (—C(═O)N(alkyl)2) represents straight-chain or branched N,N-dialkylaminocarbonyl having preferably 1 to 6 carbon atoms per alkyl, more preferably 1, 2, 3 or 4 carbon atoms per alkyl, for example N,N-dimethylaminocarbonyl (—C(═O)N(CH3)2), N,N-diethylaminocarbonyl, N,N-di(n-propylamino)carbonyl, N,N-di(isopropylamino)carbonyl and N,N-di(s-butylamino)carbonyl. The N,N-dialkylaminocarbonyl groups according to the invention may optionally be substituted by one or more identical or different radicals M1.

“Carbocycle”, unless defined differently elsewhere, is in particular cycloalkyl, cycloalkenyl or aryl. A carbocycle is in particular mono-, bi- or tricyclic C6- to C14-aryl. A carbocycle may optionally be substituted by one or more identical or different radicals M1.

According to the invention, “aryl” represents a mono-, bi- or polycyclic aromatic system having preferably 6 to 14, in particular 6 to 10 ring carbon atoms such as, for example, phenyl, naphthyl, anthryl, phenanthrenyl, preferably phenyl. In addition, aryl also represents polycyclic systems such as tetrahydronaphthyl, indenyl, indanyl, fluorenyl, biphenyl, where the bonding site is on the aromatic system. The aryl groups according to the invention may optionally be substituted by one or more identical or different radicals M1.

According to the invention, “arylalkyl” represents an aryl-substituted alkyl radical having preferably 6 to 14, in particular 6 to 10 ring carbon atoms in the aryl moiety and 1 to 6, in particular 1 to 4 carbon atoms in the alkyl moiety. Arylalkyl may be substituted by one or more identical or different radicals in the alkyl and/or aryl moiety. Examples of such arylalkyls include benzyl and 1-phenylethyl. The arylalkyl groups according to the invention may optionally be substituted by one or more identical or different radicals M1.

According to the invention, “heterocycle”, “heterocyclic ring” or “heterocyclic ring system” represents a carbocyclic ring system having at least one ring in which at least one carbon atom is replaced by a heteroatom, preferably by a heteroatom from the group consisting of N, O, S, P, B, Si, Se, and which is saturated, unsaturated or heteroaromatic and may be unsubstituted or substituted by a substituent Z, where the point of attachment is located at a ring atom. Unless defined differently, the heterocyclic ring contains preferably 3 to 9 ring atoms, especially 3 to 6 ring atoms, and one or more, preferably 1 to 4, especially 1, 2 or 3, heteroatoms in the heterocyclic ring, preferably from the group consisting of N, O, and S, although no two oxygen atoms should be directly adjacent. The heterocyclic rings usually contain not more than 4 nitrogen atoms and/or not more than 2 oxygen atoms and/or not more than 2 sulphur atoms. If the heterocyclyl radical or the heterocyclic ring is optionally substituted, it may be fused to other carbocyclic or heterocyclic rings. In the case of optionally substituted heterocyclyl, the invention also embraces polycyclic systems, for example 8-azabicyclo[3.2.1]octanyl or 1-azabicyclo[2.2.1]heptyl. In the case of optionally substituted heterocyclyl, the invention also embraces spirocyclic systems, for example 1-oxa-5-azaspiro[2.3]hexyl. The groups “heterocycle”, “heterocyclic ring” or “heterocyclic ring system” according to the invention may optionally be substituted by one or more identical or different radicals M1.

Heteroarylene, i.e. heteroaromatic systems, has a particular meaning. According to the invention, the expression “heteroaryl” represents heteroaromatic compounds, i.e. fully unsaturated aromatic heterocyclic compounds covered by the above definition of heterocycles, preferably 5- to 7-membered rings having 1 to 3, preferably 1 or 2, identical or different heteroatoms from the abovementioned group. Heteroaryls according to the invention are, for example, furyl, thienyl, pyrazolyl, imidazolyl, 1,2,3- and 1,2,4-triazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1,3,4-, 1,2,4- and 1,2,5-oxadiazolyl, azepinyl, pyrrolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-, 1,2,4- and 1,2,3-triazinyl, 1,2,4-, 1,3,2-, 1,3,6- and 1,2,6-oxazinyl, oxepinyl, thiepinyl, 1,2,4-triazolonyl and 1,2,4-diazepinyl. Furthermore, the heteroaryl groups according to the invention may optionally be substituted by one or more identical or different radicals M1.

For the purpose of the present invention, “substituted” group or group “substituted by at least one radical M1” such as an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, phenyl, benzyl, heterocyclyl, heteroaryl or amino radical, etc., is generally a group containing at least one hydrocarbon-containing or nitrogen-hydrogen-containing fraction where the hydrogen is replaced by a different atom or an atom group M1. The term “substituted groups” also includes “halogenated” groups which may be optionally substituted by one or more M1, as long as at least one substituent is a halogen. A substituted group is derived from the unsubstituted base structure, wherein the base structure is substituted by one or more substituent(s) M1, preferably 1, 2 or 3 radicals M1, and the substituent(s) M1are in each case selected independently of one another from the group consisting of halogen, hydroxyl, nitro, formyl, carboxyl, cyano, amino, isocyano, azido, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C3-C6)-cycloalkyl (C1-C4)-alkoxy, (C1-C4)-halogalkoxy, (C1-C4)-alkoxy-(C1-C4)-alkoxy, (C1-C4)-alkoxy-(C1-C6)-alkyl, N—(C1-C4)-alkoxyimino-(C1-C3)-alkyl, (C1-C4)-alkylsulfanyl, (C1-C4)-haloalkylsulfanyl, (C1-C4)-alkoxycarbonyl, (C1-C4)-alkylcarbonyl, carbamoyl, C1-C4-alkylcarbamoyl, C3-C7-cycloalkylcarbamoyl, mono- and N,N-di(C1-C4)-alkylaminocarbonyl, amino, (C1-C6)-acylamino, mono- and N,N-di(C1-C4)-alkylamino, tri(C1-C4)-alkylsilyl, (C3-C6)-cycloalkyl, C6-aryl, heterocyclyl having 3 to 6 ring atoms, wherein any of the latter cyclic groups may also be attached via heteroatoms or a divalent functional CH2, or C2H4group, (C1-C4)-alkylsulfinyl, where both enantiomers of the (C1-C4)-alkylsulfinyl group are included, (C1-C4)-alkylsulfonyl, (C1-C4)-alkylphosphinyl, (C1-C4)—(C1-C4)-alkylsulfanyl-(C1-C4)-alkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, mono- and N,N-di(C1-C4)-alkylamino(C1-C4)-alkyl and hydroxy(C1-C4)-alkyl. The radicals M1mentioned in an exemplary manner can be unsubstituted or optionally (e.g. alkyl or amino), if they contain hydrocarbon-containing or nitrogen-hydrogen-containing fractions, substituted by one or more, preferably 1, 2 or 3 radicals M2, where M2independently of the others is selected from the group consisting of amino, hydroxy, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, carboxy and carboxamide. Substituted groups also include substituted groups explicitly mentioned. “Haloalkyl” is embraced, for example, by the expression “substituted” alkyl and represents a preferred embodiment of a substituted alkyl. This applies analogously to all other substituted groups.

If two or more radicals form one or more rings, these may be carbocyclic, heterocyclic, saturated, partially saturated, unsaturated, for example also aromatic and further-substituted.

Optionally substituted cycloalkyl is preferably cycloalkyl, which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals selected from the group consisting of halogen, haloalkyl, cyano, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkoxy-(C1-C4)-alkoxy, (C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C4)-haloalkyl and (C1-C4)-haloalkoxy.

Optionally substituted heterocyclyl is preferably heterocyclyl which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals from the group of halogen, cyano, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkoxy-(C1-C4)-alkoxy, (C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy, nitro and oxo, especially mono- or polysubstituted by radicals from the group of halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkyl and oxo, most preferably substituted by one or two (C1-C4)-alkyl radicals.

Not included are such combinations which contravene the laws of nature and which the person skilled in the art would therefore rule out on the basis of his/her expert knowledge. Ring structures having three or more adjacent oxygen atoms, for example, are excluded.

DETAILED DESCRIPTION

The inventive pyrazolyl derivatives are defined by the general formula (I)

A further preferred embodiment refers to compounds of the formula (I), in which B1is CR6, B2is CR7, B3is CR8, B4is CR9and B5is CR10and R7and R9are each independently of one another hydrogen or optionally substituted C1-C6-alkyl, preferably hydrogen.

A further preferred embodiment refers to compounds of the formula (I), in which R11and R12are each independently of one another hydrogen, halogen, cyano, nitro, amino, or a C1-C6-alkyl optionally substituted by halogen, more preferably hydrogen, halogen, or a C1-C6-alkyl optionally substituted by halogen, even more preferably hydrogen or C1-C3-alkyl, especially preferably hydrogen.

A further preferred embodiment relates to compounds of the formula (I) in which W represents oxygen.

A further preferred embodiment refers to compounds of the formula (I), in which W is oxygen, in which B1is CR6, B2is CR7, B3is CR8, B4is CR9and B5is CR10and R6, R7, R8, R9and R10are as defined above, and R11and R12are as defined above.

A further preferred embodiment relates to compounds of the formula (I), in which A1is CR2, A2is CR3or N, A3is CR4or N and A4is CR5.

A further preferred embodiment relates to compounds of the formula (I), in which A1is CR2, A2is CR3or N, A3is CR4or N and A4is CR5and R2is hydrogen, or optionally substituted C1-C6-alkyl steht, preferably hydrogen or C1-C6-alkyl, particularly preferably hydrogen.

A further preferred embodiment refers to compounds of the formula (I), in which A1is CR2, A2is CR3or N, A3is CR4or N and A4is CR5and R2is hydrogen, or optionally substituted C1-C6-alkyl, preferably hydrogen or C1-C6-alkyl, particularly preferably hydrogen and R3, R4and R5are each independently of one another hydrogen, halogen, CN, optionally substituted C1-C6-alkyl, optionally substituted C1-C6-alkoxy or optionally substituted N,N-di-C1-C6-alkylamino, more preferably hydrogen, halogen such as Cl or F, C1-C6-alkyl such as C1-C3-alkyl (e.g. CH3), halogenated C1-C6-alkyl such as halogenated C1-C3-alkyl (e.g. —CF3) or N,N-di-C1-C6-alkylamino such as N,N-di-C1-C3-alkylamino (e.g. N,N-dimethylamino).

A further preferred embodiment refers to compounds of the formula (I), in which Q is hydrogen, optionally substituted C1-C6-alkyl, optionally substituted C3-C6-cycloalkyl, optionally substituted C2-C5-heterocyclyl, optionally substituted C1-C6-alkyl-C3-C6-cycloalkyl, optionally substituted aryl-(C1-C3)-alkyl, optionally substituted heteroaryl-(C1-C3)-alkyl, an aryl substituted by 0, 1, 2, 3 or 4 V substituents or a 5- or 6-membered heteroaryl substituted by 0, 1, 2, 3 or 4 V substituents.

A further preferred embodiment relates to compounds of the formula (I), in which Q is hydrogen, C1-C6-alkyl optionally substituted by one, two or three substituents selected from the group consisting of oxo, cyano, nitro, amino; halogenated C1-C6-alkyl; C3-C6-cycloalkyl optionally substituted by one, two or three substituents selected from the group consisting of halogen, cyano, nitro, C1-C3-alkyl and amino; C2-C5-heterocyclyl optionally substituted by one, two or three substituents selected from the group consisting of halogen, cyano, nitro, C1-C3-alkyl and amino; aryl-(C1-C3)-alkyl optionally substituted by one, two or three substituents selected from the group consisting of halogen, cyano, nitro, amino; heteroaryl-(C1-C3)-alkyl optionally substituted by one, two or three substituents selected from the group consisting of halogen, cyano, nitro, amino; an aryl substituted by 0, 1, 2, 3 or 4 V substituents or a 5- or 6-membered heteroaryl substituted by 0, 1, 2, 3 or 4 V substituents, where V is independently of one another halogen, cyano; C1-C6-alkyl optionally mono- to trisubstituted independently of one another by cyano, alkoxy and alkoxycarbonyl; halogenated C1-C6-alkyl; C1-C6-alkoxy optionally mono- to trisubstituted independently of one another by cyano, alkoxy and alkoxycarbonyl; halogenated C1-C6-alkoxy.

A further preferred embodiment relates to compounds of the formula (I), in which Q is C1-C6-alkyl optionally substituted by one, two or three substituents selected from the group consisting of oxo, cyano, nitro, amino; halogenated C1-C6-alkyl; C3-C6-cycloalkyl optionally substituted by one, two or three substituents selected from the group consisting of halogen, cyano, nitro, C1-C3-alkyl and amino; C2-C5-heterocyclyl optionally substituted by one, two or three substituents selected from the group consisting of halogen, cyano, nitro, C1-C3-alkyl and amino; an aryl substituted by 0, 1, 2, 3 or 4 V substituents or a 5- or 6-membered heteroaryl substituted by 0, 1, 2, 3 or 4 V substituents, where V is independently of one another halogen, cyano; C1-C6-alkyl; halogenated C1-C6-alkyl; C1-C6-alkoxy; halogenated C1-C6-alkoxy.

A further preferred embodiment relates to compounds of the formula (I), in which Q is C3-C6-cycloalkyl optionally substituted by one, two or three substituents selected from the group consisting of halogen, cyano, nitro, C1-C3-alkyl and amino; C2-C5-heterocyclyl optionally substituted by one, two or three substituents selected from the group consisting of halogen, cyano, nitro, C1-C3-alkyl and amino; an aryl substituted by 0, 1, 2, 3 or 4 V substituents or a 5- or 6-membered heteroaryl substituted by 0, 1, 2, 3 or 4 V substituents, where V is independently of one another halogen, cyano; C1-C6-alkyl; halogenated C1-C6-alkyl; C1-C6-alkoxy; halogenated C1-C6-alkoxy.

A further preferred embodiment relates to compounds of the formula (I), in which Q is C3-C6-cycloalkyl optionally substituted by one substituent selected from the group consisting of halogen, C1-C3-alkyl and cyano (such as, for example, cyclopropyl optionally substituted by cyano or C1-C3-alkyl); C2-C5-heterocyclyl optionally substituted by one substituent selected from the group consisting of halogen or cyano, such as, for example, thietanyl (thiacyclobutanyl) optionally substituted by cyano or C1-C3-alkyl; an aryl substituted by 0, 1 or 2 V substituents or a 5- or 6-membered heteroaryl substituted by 0, 1, 2, 3 or 4 V substituents, wherein V is each independently of one another halogen (e.g. F, Cl), cyano; C1-C6-alkyl; C1-C6-alkoxy (such as phenyl optionally substituted by 0, 1 or 2 V substituents each selected independently of one another from the group consisting of halogen (such as F, Cl), C1-C3-alkoxy (such as methoxy and ethoxy), C1-C3-alkyl (such as methyl), halogenated C1-C3-alkyl (such as CF3) and cyano; or pyridyl, pyrimidinyl and thiophenyl optionally substituted by 0, 1 or 2 V substituents each selected independently of one another from the group consisting of halogen (such as F, Cl), C1-C3-alkyl (such as methyl) halogenated C1-C3-alkyl (such as CF3) and cyano); or pyridyl, pyrimidinyl, thienyl, oxazolyl or thiophenyl optionally substituted by 0, 1 or 2 V substituents each selected independently of one another from the group consisting of halogen (such as F, Cl), C1-C3-alkyl (such as methyl), halogenated C1-C3-alkyl (such as CF3) and cyano.

A further preferred embodiment relates to compounds of the formula (I), in which R1is hydrogen, C1-C3-alkyl or C3-C6-cycloalkyl.

A further preferred embodiment relates to compounds of the formula (I) in which R1is hydrogen.

Embodiments furthermore preferred relate to compounds of the formula (I′)

where A1, A2, A3, A4, R6, R8, R10and Q are defined as described in this application, preferably whereA1is CR2,A2is CR3or N,A3is CR4or N,A4is CR5,R2represents hydrogen,R3is hydrogen or C1-C3-alkyl, particularly preferably hydrogen,R4is hydrogen, halogen, CN or optionally substituted C1-C6-alkyl or —N(C1-C3-alkyl)2, particularly preferably hydrogen, Cl, F, or C1-C3-alkyl (such as CH3) or —N(C1-C3-alkyl)2(such as —N(CH3)2),R5is hydrogen or halogen, particularly preferably hydrogen or F,R6is hydrogen, halogen, cyano, optionally substituted C1-C6-alkyl, more preferably halogen or optionally halogenated C1-C6-alkyl, still more preferably F, Cl, I, Br, C1-C3-alkyl (such as methyl) or perhalogenated C1-C3-alkyl, particularly preferably Cl, Br or C1-C3-alkyl (such as CH3),R8is halogen or C1-C6-haloalkyl, preferably C1-C6-haloalkyl, more preferably perhalogenated C1-C6-alkyl, still more preferably perfluorinated C1-C6-alkyl such as perfluorinated C1-C4-alkyl: CF3, C2F5, C3F7, C4F9,R10is hydrogen, halogen, cyano, optionally substituted C1-C6-alkyl, more preferably halogen or optionally halogenated C1-C6-alkyl or optionally halogenated C1-C6-alkoxy (such as OCF3or OCHF2), still more preferably F, Cl, Br, C1-C3-alkyl (such as methyl, ethyl) or perhalogenated C1-C3-alkyl, particularly preferably Cl, C1-C3-alkyl (such as methyl, ethyl) or perfluorinated C1-C3-alkyl (such as CF3), andQ is C3-C6-cycloalkyl optionally substituted by one substituent selected from the group consisting of halogen, C1-C3-alkyl and cyano (such as, for example, cyclopropyl optionally substituted by cyano or C1-C3-alkyl); C2-C5-heterocyclyl optionally substituted by one substituent selected from the group consisting of halogen or cyano, such as, for example, thietanyl (thiacyclobutanyl) optionally substituted by cyano or C1-C3-alkyl; an aryl substituted by 0, 1 or 2 V substituents or a 5- or 6-membered heteroaryl substituted by 0, 1, 2, 3 or 4 V substituents, wherein V is each independently of one another halogen (e.g. F, Cl), cyano; optionally halogenated C1-C6-alkyl; optionally halogenated C1-C6-alkoxy (such as phenyl optionally substituted by 0, 1 or 2 V substituents each selected independently of one another from the group consisting of halogen (such as F, Cl), C1-C3-alkoxy (such as methoxy and ethoxy), C1-C3-alkyl (such as methyl), halogenated C1-C3-alkyl (such as CF3) and cyano; or pyridyl, pyrimidinyl or thiophenyl optionally substituted by 0, 1 or 2 V substituents each selected independently of one another from the group consisting of halogen (such as F, Cl), C1-C3-alkyl (such as methyl) halogenated C1-C3-alkyl (such as CF3) and cyano); or pyridyl, pyrimidinyl, thienyl, oxazolyl or thiophenyl optionally substituted by 0, 1 or 2 V substituents each selected independently of one another from the group consisting of halogen (such as F, Cl), C1-C3-alkyl (such as methyl), halogenated C1-C3-alkyl (such as CF3) and cyano.

Embodiments furthermore preferred relate to compounds of the formula (I′) whereA1represents CR2, where R2represents hydrogen,A2represents CR3or N, where R3represents hydrogen,A3represents CR4or N, where R4is hydrogen, Cl, F, or C1-C3-alkyl (such as CH3) or —N(C1-C3-alkyl)2(such as —N(CH3)2),A4represents CR5, where R5represents hydrogen or F,R6represents Cl, Br or C1-C3-alkyl (such as CH3),R8represents perhalogeniertes C1-C6-alkyl, more preferably perfluorinated C1-C4-alkyl such as CF3, C2F5, C3F7, C4F9,R10represents Cl, C1-C3-alkyl (such as methyl) or perfluorinated C1-C3-alkyl (such as CF3), andQ represents (a) C3-C6-cycloalkyl optionally substituted by one substituent selected from the group consisting of halogen, C1-C3-alkyl and cyano (such as, for example, cyclopropyl optionally substituted by cyano or C1-C3-alkyl), (b) C2-C5-heterocyclyl optionally substituted by one substituent selected from the group consisting of halogen or cyano, such as, for example, thietanyl (thiacyclobutanyl) optionally substituted by cyano or C1-C3-alkyl, (c) an aryl substituted by 0, 1 or 2 V substituents or a 5- or 6-membered heteroaryl substituted by 0, 1, 2, 3 or 4 V substituents, wherein V is each independently of one another halogen (e.g. F, Cl), cyano, optionally halogenated C1-C6-alkyl, optionally halogenated C1-C6-alkoxy (such as phenyl optionally substituted by 0, 1 or 2 V substituents each selected independently of one another from the group consisting of halogen (such as F, Cl), C1-C3-alkoxy (such as methoxy and ethoxy), C1-C3-alkyl (such as methyl), halogenated C1-C3-alkyl (such as CF3) and cyano; or pyridyl, pyrimidinyl, thienyl, oxazolyl or thiophenyl optionally substituted by 0, 1 or 2 V substituents V each selected independently of one another from the group consisting of halogen (such as F, Cl), C1-C3-alkyl (such as methyl) halogenated C1-C3-alkyl (such as CF3) and cyano).

Embodiments furthermore preferred relate to compounds of the formula (Ia)

Embodiments furthermore preferred relate to compounds of the formula (Ib)

where R6, R8, R10and Q are defined as described in this application, preferably whereR6is hydrogen, halogen, cyano, optionally substituted C1-C6-alkyl, more preferably halogen or optionally halogenated C1-C6-alkyl, still more preferably F, Cl, I, Br, C1-C3-alkyl (such as methyl) or perhalogenated C1-C3-alkyl, particularly preferably Cl, Br or C1-C3-alkyl (such as CH3), especially preferably CH3or Br,R8is halogen or C1-C6-haloalkyl, preferably C1-C6-haloalkyl, more preferably perhalogenated C1-C6-alkyl, still more preferably perfluorinated C1-C6-alkyl such as CF3, C2F5, C3F7, C4F9, especially preferably C3F7,R10is hydrogen, halogen, cyano, optionally substituted C1-C6-alkyl, more preferably halogen or optionally halogenated C1-C6-alkyl or optionally halogenated C1-C6-alkoxy (such as OCF3or OCHF2), still more preferably F, Cl, Br, C1-C3-alkyl (such as methyl, ethyl) or perhalogenated C1-C3-alkyl, particularly preferably Cl, C1-C3-alkyl (such as methyl, ethyl) or perfluorinated C1-C3-alkyl (such as CF3), especially preferably CF3, andQ represents C3-C6-cycloalkyl optionally substituted by one substituent selected from the group consisting of halogen, C1-C3-alkyl and cyano (such as, for example, cyclopropyl optionally substituted by cyano or C1-C3-alkyl); C2-C5-heterocyclyl optionally substituted by one substituent selected from the group consisting of halogen or cyano, such as, for example, thietanyl (thiacyclobutanyl) optionally substituted by cyano or C1-C3-alkyl; an aryl substituted by 0, 1 or 2 V substituents or a 5- or 6-membered heteroaryl substituted by 0, 1, 2, 3 or 4 V substituents, wherein V is each independently of one another halogen (e.g. F, Cl), cyano, optionally halogenated C1-C6-alkyl, optionally halogenated C1-C6-alkoxy (such as phenyl optionally substituted by 0, 1 or 2 V substituents each selected independently of one another from the group consisting of halogen (such as F, Cl), C1-C3-alkoxy (such as methoxy and ethoxy), C1-C3-alkyl (such as methyl), halogenated C1-C3-alkyl (such as CF3) and cyano; or pyridyl, thienyl, phenyl or oxazolyl optionally substituted by 0, 1 or 2 V substituents V each selected independently of one another from the group consisting of halogen (such as F, Cl), C1-C3-alkyl (such as methyl) halogenated C1-C3-alkyl (such as CF3) and cyano).preferably a pyridyl, thienyl, phenyl or oxazolyl substituted by 0, 1 or 2 V substituents, where V is in each case independently of one another F, Cl, CN, C1-C3-alkoxy (such as methoxy).
Isomers

Depending on the nature of the substituents, the compounds of the formula (I) may take the form of geometric and/or optically active isomers or corresponding isomer mixtures in different compositions. These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers. The invention therefore encompasses pure stereoisomers and any desired mixtures of these isomers.

Methods and Uses

The invention also relates to methods for controlling animal pests, in which compounds of the formula (I) are allowed to act on animal pests and/or their habitat. The control of the animal pests is preferably carried out in agriculture and forestry, and in material protection. This preferably excludes methods for surgical or therapeutic treatment of the human or animal body and diagnostic methods carried out on the human or animal body.

The invention further relates to the use of the compounds of the formula (I) as pesticides, especially crop protection agents.

In the context of the present application, the term “pesticide” also always encompasses the term “crop protection agent”.

The compounds of the formula (I), given good plant tolerance, favourable homeotherm toxicity and good environmental compatibility, are suitable for protecting plants and plant organs against biotic and abiotic stress factors, for increasing harvest yields, for improving the quality of the harvested material and for controlling animal pests, especially insects, arachnids, helminths, nematodes and molluscs, which are encountered in agriculture, in horticulture, in animal husbandry, in aquatic cultures, in forests, in gardens and leisure facilities, in the protection of stored products and of materials, and in the hygiene sector.

In the context of the present patent application, the term “hygiene” is understood as meaning the entirety of all measures, processes and procedures whose aim it is to prevent disorders—in particular infective diseases—and to serve to keep humans, animals and/or the environment healthy and/or to maintain cleanliness. According to the invention, this includes in particular measures for cleaning, disinfecting and sterilizing, for example, textiles or hard surfaces, mainly made of glass, wood, concrete, porcelain, ceramic, plastic or else made of metal(s), and keeping them clean of hygiene pests and/or their faeces. Excluded according to the invention are in this respect again processes for the surgical or therapeutic treatment of the human or animal body and diagnostic processes undertaken on the human or animal body.

The term “hygiene sector” thus includes all areas, technical fields and commercial utilizations in which such hygiene measures, processes and procedures are of importance, for example hygiene in kitchens, bakeries, airports, baths, swimming pools, shopping centres, hotels, hospitals, stables, etc.

Accordingly, the term “hygiene pest” is understood as meaning one or more animal pests whose presence in the hygiene sector is problematic, in particular for health reasons. Accordingly, the main aim is to minimize or prevent hygiene pests or contact therewith in the hygiene sector. This can be effected, in particular, by using a pesticide, where the agent can be employed both prophylactically and only in the case of infestation to control the pest. It is also possible to use agents which act by avoiding or reducing contact with the pest. Hygiene pests are, for example, the organisms mentioned below.

Thus, the term “hygiene protection” includes all actions which serve to maintain and/or improve such hygiene measures, processes and procedures.

The compounds of the formula (I) can preferably be used as pesticides. They are active against normally sensitive and resistant species and also against all or specific stages of development. The abovementioned pests include:

The compounds of the formula (I) can, as the case may be, at certain concentrations or application rates, also be used as herbicides, safeners, growth regulators or agents to improve plant properties, as microbicides or gametocides, for example as fungicides, antimycotics, bactericides, virucides (including agents against viroids) or as agents against MLO (mycoplasma-like organisms) and RLO (rickettsia-like organisms). They can, as the case may be, also be used as intermediates or precursors for the synthesis of other active ingredients.

Formulations

The present invention further relates to formulations and use forms prepared therefrom as pesticides, for example drench, drip and spray liquors, comprising at least one compound of the formula (I). Optionally, the use forms comprise further pesticides and/or adjuvants which improve action, such as penetrants, e.g. vegetable oils, for example rapeseed oil, sunflower oil, mineral oils, for example paraffin oils, alkyl esters of vegetable fatty acids, for example rapeseed oil methyl ester or soya oil methyl ester, or alkanol alkoxylates and/or spreaders, for example alkylsiloxanes and/or salts, for example organic or inorganic ammonium or phosphonium salts, for example ammonium sulphate or diammonium hydrogenphosphate and/or retention promoters, for example dioctyl sulphosuccinate or hydroxypropylguar polymers and/or humectants, for example glycerol and/or fertilizers, for example ammonium-, potassium- or phosphorus-containing fertilizers.

Customary formulations are, for example, water-soluble liquids (SL), emulsion concentrates (EC), emulsions in water (EW), suspension concentrates (SC, SE, FS, OD), water-dispersible granules (WG), granules (GR) and capsule concentrates (CS); these and further possible formulation types are described, for example, by Crop Life International and in Pesticide Specifications, Manual on development and use of FAO and WHO specifications for pesticides, FAO Plant Production and Protection Papers—173, prepared by the FAO/WHO Joint Meeting on Pesticide Specifications, 2004, ISBN: 9251048576. The formulations, in addition to one or more compounds of the formula (I), optionally comprise further agrochemically active ingredients.

Preference is given to formulations or use forms comprising auxiliaries, for example extenders, solvents, spontaneity promoters, carriers, emulsifiers, dispersants, frost protection agents, biocides, thickeners and/or further auxiliaries, for example adjuvants. An adjuvant in this context is a component which enhances the biological effect of the formulation, without the component itself having any biological effect. Examples of adjuvants are agents which promote retention, spreading, attachment to the leaf surface or penetration.

These formulations are prepared in a known way, for example by mixing the compounds of the formula (I) with auxiliaries, for example extenders, solvents and/or solid carriers and/or other auxiliaries, for example surfactants. The formulations are produced either in suitable facilities or else before or during application.

The auxiliaries used may be substances suitable for imparting special properties, such as certain physical, technical and/or biological properties, to the formulation of the compounds of the formula (I), or to the use forms prepared from these formulations (for example ready-to-use pesticides such as spray liquors or seed dressing products).

In principle, it is possible to use all suitable solvents. Examples of suitable solvents are aromatic hydrocarbons, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane, paraffins, mineral oil fractions, mineral and vegetable oils, alcohols, such as methanol, ethanol, isopropanol, butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethyl sulphoxide, and also water.

In principle, it is possible to use all suitable carriers. Useful carriers especially include: 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 natural or synthetic silicates, resins, waxes and/or solid fertilizers. It is likewise possible to use mixtures of such carriers. Useful carriers for granules include: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic and organic flours, and also granules of organic material such as sawdust, paper, coconut shells, maize cobs and tobacco stalks.

It is also possible to use liquefied gaseous extenders or solvents. Especially suitable are those extenders or carriers which are gaseous at standard temperature and under atmospheric pressure, for example aerosol propellants such as halogenated hydrocarbons, and also butane, propane, nitrogen and carbon dioxide.

Examples of emulsifiers and/or foam formers, dispersants or wetting agents having ionic or nonionic properties or mixtures of these surface-active substances are salts of polyacrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, with substituted phenols (preferably alkylphenols or arylphenols), salts of sulphosuccinic esters, taurine derivatives (preferably alkyl taurates), phosphoric esters of polyethoxylated alcohols or phenols, fatty acid esters of polyols, and derivatives of the compounds containing sulphates, sulphonates and phosphates, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, protein hydrolysates, lignosulphite waste liquors and methylcellulose. The presence of a surfactant is advantageous if one of the compounds of the formula (I) and/or one of the inert carriers is insoluble in water and if the application takes place in water.

Further auxiliaries which may be present in the formulations and the use forms derived therefrom are dyes such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and nutrients and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

Additional components which may be present are stabilizers, such as cold stabilizers, preservatives, antioxidants, light stabilizers, or other agents which improve chemical and/or physical stability. Foam generators or antifoams may also be present.

In addition, the formulations and the use forms derived therefrom may also comprise, as additional auxiliaries, stickers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Further auxiliaries may be mineral and vegetable oils.

It is possible if appropriate for still further auxiliaries to be present in the formulations and the use forms derived therefrom. Examples of such additives are fragrances, protective colloids, binders, adhesives, thickeners, thixotropic agents, penetrants, retention promoters, stabilizers, sequestrants, complexing agents, humectants, spreaders. In general, the compounds of the formula (I) can be combined with any solid or liquid additive commonly used for formulation purposes.

Useful retention promoters include all those substances which reduce dynamic surface tension, for example dioctyl sulphosuccinate, or increase viscoelasticity, for example hydroxypropylguar polymers.

Useful penetrants in the present context are all those substances which are typically used to improve the penetration of active agrochemical ingredients into plants. Penetrants are defined in this context by their ability to penetrate from the (generally aqueous) application liquor and/or from the spray coating into the cuticle of the plant and hence increase the mobility of the active ingredients in the cuticle. The method described in the literature (Baur et al., 1997, Pesticide Science 51, 131-152) can be used for determining this property. Examples include alcohol alkoxylates such as coconut fatty ethoxylate (10) or isotridecyl ethoxylate (12), fatty acid esters, for example rapeseed oil methyl ester or soya oil methyl ester, fatty amine alkoxylates, for example tallowamine ethoxylate (15), or ammonium and/or phosphonium salts, for example ammonium sulphate or diammonium hydrogenphosphate.

The formulations preferably comprise between 0.00000001% and 98% by weight of the compound of the formula (I), more preferably between 0.01% and 95% by weight of the compound of the formula (I), most preferably between 0.5% and 90% by weight of the compound of the formula (I), based on the weight of the formulation.

The content of the compound of the formula (I) in the use forms prepared from the formulations (in particular pesticides) may vary within wide ranges. The concentration of the compound of the formula (I) in the use forms may typically be between 0.00000001% and 95% by weight of the compound of the formula (I), preferably between 0.00001% and 1% by weight, based on the weight of the use form. Application is accomplished in a customary manner appropriate for the use forms.

Mixtures

The compounds of the formula (I) can also be used in a mixture with one or more suitable fungicides, bactericides, acaricides, molluscicides, nematicides, insecticides, microbiological agents, beneficial organisms, herbicides, fertilizers, bird repellents, phytotonics, sterilants, safeners, semiochemicals and/or plant growth regulators, in order thus, for example, to broaden the spectrum of action, prolong the period of action, enhance the rate of action, prevent repellency or prevent evolution of resistance. In addition, active ingredient combinations of this kind can improve plant growth and/or tolerance to abiotic factors, for example high or low temperatures, to drought or to elevated water content or soil salinity. It is also possible to improve flowering and fruiting performance, optimize germination capacity and root development, facilitate harvesting and improve yields, influence maturation, improve the quality and/or the nutritional value of the harvested products, prolong storage life and/or improve the processibility of the harvested products.

In addition, the compounds of the formula (I) may be present in a mixture with other active ingredients or semiochemicals such as attractants and/or bird repellents and/or plant activators and/or growth regulators and/or fertilizers. Likewise, the compounds of the formula (I) can be used in mixtures with agents to improve plant properties, for example growth, yield and quality of the harvested material.

In a particular embodiment according to the invention, the compounds of the formula (I) are present in formulations or in the use forms prepared from these formulations in a mixture with further compounds, preferably those as described below.

If one of the compounds mentioned below can occur in different tautomeric forms, these forms are also included even if not explicitly mentioned in each case.

The active compounds specified herein by their common name are known and described, for example, in “Pesticide Manual” or on the Internet (for example: http://www.alanwood.net/pesticides).

The compounds of the formula (I) can be combined with biological pesticides.

Biological pesticides especially include bacteria, fungi, yeasts, plant extracts and products formed by microorganisms, including proteins and secondary metabolites.

Biological pesticides include bacteria such as spore-forming bacteria, root-colonizing bacteria and bacteria which act as biological insecticides, fungicides or nematicides.

Examples of such bacteria which are used or can be used as biological pesticides are:

Examples of fungi and yeasts which are used or can be used as biological pesticides are:

Examples of viruses which are used or can be used as biological pesticides are:

Also included are bacteria and fungi which are added as ‘inoculant’ to plants or plant parts or plant organs and which, by virtue of their particular properties, promote plant growth and plant health. Examples include:

Examples of plant extracts and products formed by microorganisms, including proteins and secondary metabolites, which are used or can be used as biological pesticides are:

Plants and Plant Parts

All plants and plant parts can be treated in accordance with the invention. Plants are understood here to mean all plants and populations of plants, such as desirable and undesirable wild plants or crop plants (including naturally occurring crop plants), for example cereals (wheat, rice, triticale, barley, rye, oats), maize, soya bean, potato, sugar beet, sugar cane, tomatoes, peas and other vegetable species, cotton, tobacco, oilseed rape, and also fruit plants (with the fruits apples, pears, citrus fruits and grapes). Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which are protectable or non-protectable by plant breeders' rights. Plant parts shall be understood to mean all parts and organs of the plants above and below ground, such as shoot, leaf, flower and root, examples given being leaves, needles, stalks, stems, flowers, fruit bodies, fruits and seeds, and also roots, tubers and rhizomes. Plant parts also include harvested material and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, slips and seeds.

Treatment according to the invention of the plants and plant parts with the compounds of the formula (I) is carried out directly or by allowing the compounds to act on their 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.

As already mentioned above, it is possible to treat all plants and parts thereof in accordance with 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 term “parts” or “parts of plants” or “plant parts” has been explained above. Particular preference is given in accordance with the invention to treating plants of the respective commercially customary plant cultivars or those that are in use. Plant cultivars are understood to mean plants having new properties (“traits”) which have been grown by conventional breeding, by mutagenesis or by recombinant DNA techniques. They may be cultivars, varieties, biotypes or genotypes.

Transgenic Plants, Seed Treatment and Integration Events

The preferred transgenic plants or plant cultivars (those obtained by genetic engineering) which are to be treated in accordance with the invention include all plants which, through the genetic modification, received genetic material which imparts particular advantageous useful properties (“traits”) to these plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to levels of water or soil salinity, enhanced flowering performance, easier harvesting, accelerated ripening, higher harvest yields, higher quality and/or higher nutritional value of the harvested products, better capability for storage and/or processability of the harvested products. Further and particularly emphasized examples of such properties are increased resistance of the plants against animal and microbial pests, such as insects, arachnids, nematodes, mites, slugs and snails, owing, for example, to 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), CryllIA, CryIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof), and also increased resistance of the plants against phytopathogenic fungi, bacteria and/or viruses caused, for example, by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins, and also increased tolerance of the plants to certain herbicidally active ingredients, for example imidazolinones, sulfonylureas, glyphosates or phosphinothricin (for example the “PAT” gene). The genes which impart the desired properties (“traits”) in question may also be present in combinations with one another in the transgenic plants. Examples of transgenic plants include the important crop plants, such as cereals (wheat, rice, triticale, barley, rye, oats), maize, soya beans, potatoes, sugar beet, sugar cane, tomatoes, peas and other types of vegetable, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), particular emphasis being given to maize, soya beans, wheat, rice, potatoes, cotton, sugar cane, tobacco and oilseed rape. Properties (“traits”) which are particularly emphasized are the increased resistance of the plants to insects, arachnids, nematodes and slugs and snails.

Crop Protection—Types of Treatment

The plants and plant parts are treated with the compounds of the formula (I) directly or by action on their surroundings, habitat or storage space using customary treatment methods, for example by dipping, spraying, atomizing, irrigating, evaporating, dusting, fogging, broadcasting, foaming, painting, spreading-on, injecting, watering (drenching), drip irrigating and, in the case of propagation material, in particular in the case of seed, additionally by dry seed treatment, liquid seed treatment, slurry treatment, by incrusting, by coating with one or more coats, etc. It is furthermore possible to apply the compounds of the formula (I) by the ultra-low volume method or to inject the application form or the compound of the formula (I) itself into the soil.

A preferred direct treatment of the plants is foliar application, i.e. compounds of the formula (I) are applied to the foliage, where treatment frequency and the application rate should be adjusted according to the level of infestation with the pest in question.

In the case of systemically active compounds, the compounds of the formula (I) also access the plants via the root system. The plants are then treated by the action of the compounds of the formula (I) on the habitat of the plant. This can be accomplished, for example, by drenching, or by mixing into the soil or the nutrient solution, meaning that the locus of the plant (e.g. soil or hydroponic systems) is impregnated with a liquid form of the compounds of the formula (I), or by soil application, meaning that the compounds of the formula (I) are introduced in solid form (e.g. in the form of granules) into the locus of the plants. In the case of paddy rice crops, this can also be accomplished by metering the compound of the formula (I) in a solid application form (for example as granules) into a flooded paddy field.

Seed Treatment

The control of animal pests by the treatment of the seed of plants has long been known and is the subject of constant improvements. Nevertheless, the treatment of seed entails a series of problems which cannot always be solved in a satisfactory manner. Thus, it is desirable to develop methods for protecting the seed and the germinating plant which dispense with, or at least reduce considerably, the additional application of pesticides during storage, after sowing or after emergence of the plants. It is additionally desirable to optimize the amount of active ingredient used so as to provide optimum protection for the seed and the germinating plant from attack by animal pests, but without damage to the plant itself by the active ingredient used. In particular, methods for the treatment of seed should also take account of the intrinsic insecticidal or nematicidal properties of pest-resistant or -tolerant transgenic plants in order to achieve optimal protection of the seed and the germinating plant with a minimum expenditure on pesticides.

The present invention therefore in particular also relates to a method for the protection of seed and germinating plants from attack by pests, by treating the seed with one of the compounds of the formula (I). The method according to the invention for protecting seed and germinating plants against attack by pests further comprises a method in which the seed is treated simultaneously in one operation or sequentially with a compound of the formula (I) and a mixing component. It further also comprises a method where the seed is treated at different times with a compound of the formula (I) and a mixing component.

The invention also relates to the use of the compounds of the formula (I) for the treatment of seed for protecting the seed and the resulting plant from animal pests.

The invention further relates to seed which has been treated with a compound of the formula (I) for protection from animal pests. The invention also relates to seed which has been treated simultaneously with a compound of the formula (I) and a mixing component. The invention further relates to seed which has been treated at different times with a compound of the formula (I) and a mixing component. In the case of seed which has been treated at different times with a compound of the formula (I) and a mixing component, the individual substances may be present on the seed in different layers. In this case, the layers comprising a compound of the formula (I) and a mixing component may optionally be separated by an intermediate layer. The invention also relates to seed in which a compound of the formula (I) and a mixing component have been applied as part of a coating or as a further layer or further layers in addition to a coating.

The invention further relates to seed which, after the treatment with a compound of the formula (I), is subjected to a film-coating process to prevent dust abrasion on the seed.

One of the advantages encountered with a systemically acting compound of the formula (I) is the fact that, by treating the seed, not only the seed itself but also the plants resulting therefrom are, after emergence, protected against animal pests. In this way, the immediate treatment of the crop at the time of sowing or shortly thereafter can be dispensed with.

A further advantage is that the treatment of the seed with a compound of the formula (I) can enhance germination and emergence of the treated seed.

It is likewise considered to be advantageous that compounds of the formula (I) can especially also be used for transgenic seed.

Furthermore, compounds of the formula (I) can be employed in combination with compositions of signalling technology, leading to better colonization by symbionts such as, for example,rhizobia, mycorrhizae and/or endophytic bacteria or fungi, and/or to optimized nitrogen fixation.

The compounds of the formula (I) are suitable for protection of seed of any plant variety which is used in agriculture, in the greenhouse, in forests or in horticulture. More particularly, this includes seed of cereals (for example wheat, barley, rye, millet and oats), maize, cotton, soya beans, rice, potatoes, sunflowers, coffee, tobacco, canola, oilseed rape, beet (for example sugar beet and fodder beet), peanuts, vegetables (for example tomatoes, cucumbers, beans, cruciferous vegetables, onions and lettuce), fruit plants, lawns and ornamental plants. Of particular significance is the treatment of the seed of cereals (such as wheat, barley, rye and oats), maize, soya beans, cotton, canola, oilseed rape and rice.

As already mentioned above, the treatment of transgenic seed with a compound of the formula (I) is also of particular importance. This involves the seed of plants which generally contain at least one heterologous gene which controls the expression of a polypeptide having insecticidal and/or nematicidal properties in particular. The heterologous genes in transgenic seed may originate in this case from microorganisms such asBacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, GlomusorGliocladium. The present invention is particularly suitable for the treatment of transgenic seed containing at least one heterologous gene originating fromBacillussp. The heterologous gene is more preferably derived fromBacillus thuringiensis.

In the context of the present invention, the compound of the formula (I) is applied to the seed. The seed is preferably treated in a state in which it is sufficiently stable for no damage to occur in the course of treatment. In general, the seed can be treated at any time between harvest and sowing. It is customary to use seed which has been separated from the plant and freed from cobs, shells, stalks, coats, hairs or the flesh of the fruits. For example, it is possible to use seed which has been harvested, cleaned and dried down to a moisture content which allows storage. Alternatively, it is also possible to use seed which, after drying, has been treated with, for example, water and then dried again, for example priming. In the case of rice seed, it is also possible to use seed which has been pre-swollen in water up to a certain stage (pigeon breast stage) for example, which leads to improved germination and more uniform emergence.

When treating the seed, care must generally be taken that the amount of the compound of the formula (I) applied to the seed and/or the amount of further additives is chosen in such a way that the germination of the seed is not adversely affected, or that the resulting plant is not damaged. This has to be ensured particularly in the case of active ingredients which can exhibit phytotoxic effects at certain application rates.

In general, the compounds of the formula (I) are applied to the seed in the form of a suitable formulation. Suitable formulations and processes for seed treatment are known to the person skilled in the art.

The compounds of the formula (I) can be converted to the customary seed-dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other coating compositions for seed, and also ULV formulations.

These formulations are prepared in a known manner, by mixing compounds of the formula (I) with customary additives such as, for example, customary extenders and also solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins and also water.

Dyes which may be present in the seed-dressing formulations usable in accordance with the invention are all dyes which are customary for such purposes. It is possible to use either pigments, which are sparingly soluble in water, or dyes, which are soluble in water. Examples include the dyes known by the names Rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1.

Useful wetting agents which may be present in the seed-dressing formulations usable in accordance with the invention are all substances which promote wetting and which are customary for the formulation of active agrochemical ingredients. Alkyl naphthalenesulphonates, such as diisopropyl or diisobutyl naphthalenesulphonates, can be used with preference.

Suitable dispersants and/or emulsifiers which may be present in the seed-dressing formulations usable in accordance with the invention are all nonionic, anionic and cationic dispersants customary for the formulation of active agrochemical ingredients. Nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants can be used with preference. Suitable nonionic dispersants especially include ethylene oxide/propylene oxide block polymers, alkylphenol polyglycol ethers and tristyrylphenol polyglycol ethers, and the phosphated or sulphated derivatives thereof. Suitable anionic dispersants are especially lignosulphonates, polyacrylic acid salts and arylsulphonate-formaldehyde condensates.

Antifoams which may be present in the seed-dressing formulations usable in accordance with the invention are all foam-inhibiting substances customary for the formulation of active agrochemical ingredients. Silicone antifoams and magnesium stearate can be used with preference.

Preservatives which may be present in the seed-dressing formulations usable in accordance with the invention are all substances usable for such purposes in agrochemical compositions. Examples include dichlorophene and benzyl alcohol hemiformal.

Secondary thickeners which may be present in the seed-dressing formulations usable in accordance with the invention are all substances which can be used for such purposes in agrochemical compositions. Preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica.

Useful stickers which may be present in the seed-dressing formulations usable in accordance with the invention are all customary binders usable in seed-dressing products. Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.

Gibberellins which may be present in the seed-dressing formulations usable in accordance with the invention are preferably the gibberellins A1, A3 (=gibberellic acid), A4 and A7; particular preference is given to using gibberellic acid. The gibberellins are known (cf. R. Wegler “Chemie der Pflanzenschutz-und Schädlingsbekämpfungsmittel”, vol. 2, Springer Verlag, 1970, pp. 401-412).

The seed-dressing formulations usable in accordance with the invention can be used to treat a wide variety of different kinds of seed, either directly or after prior dilution with water. For instance, the concentrates or the preparations obtainable therefrom by dilution with water can be used to dress the seed of cereals, such as wheat, barley, rye, oats and triticale, and also the seed of maize, rice, oilseed rape, peas, beans, cotton, sunflowers, soya beans and beets, or else a wide variety of different vegetable seed. The seed-dressing formulations usable in accordance with the invention, or the dilute use forms thereof, can also be used to dress seed of transgenic plants.

For the treatment of seed with the seed-dressing formulations usable in accordance with the invention, or use forms prepared therefrom, all mixing units usable customarily for the seed dressing are useful. Specifically, the procedure in seed dressing is to place the seed into a mixer in batchwise or continuous operation, to add the particular desired amount of seed-dressing formulations, either as such or after prior dilution with water, and to mix until the formulation is distributed homogeneously on the seed. If appropriate, this is followed by a drying operation.

The application rate of the seed dressing formulations usable in accordance with the invention can be varied within a relatively wide range. It is guided by the particular content of the compounds of the formula (I) in the formulations and by the seed. The application rates of the compound of the formula (I) are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 15 g per kilogram of seed.

Animal Health

In the animal health field, i.e. the field of veterinary medicine, the compounds of the formula (I) are active against animal parasites, in particular ectoparasites or endoparasites. The term “endoparasites” includes especially helminths and protozoa, such as coccidia. Ectoparasites are typically and preferably arthropods, especially insects and acarids.

In the field of veterinary medicine, the compounds of the formula (I) having favourable endotherm toxicity are suitable for controlling parasites which occur in animal breeding and animal husbandry in livestock, breeding animals, zoo animals, laboratory animals, experimental animals and domestic animals. They are active against all or specific stages of development of the parasites.

Agricultural livestock include, for example, mammals such as sheep, goats, horses, donkeys, camels, buffalo, rabbits, reindeer, fallow deer, and particularly cattle and pigs; poultry such as turkeys, ducks, geese, and particularly chickens; fish and crustaceans, for example in aquaculture, and also insects such as bees.

In a preferred embodiment, the compounds of the formula (I) are administered to mammals.

In another preferred embodiment, the compounds of the formula (I) are administered to birds, namely caged birds and particularly poultry.

Use of the compounds of the formula (I) for the control of animal parasites is intended to reduce or prevent illness, cases of death and reductions in performance (in the case of meat, milk, wool, hides, eggs, honey and the like), such that more economical and simpler animal husbandry is enabled and better animal well-being is achievable.

In relation to the field of animal health, the term “control” or “controlling” means that the compounds of the formula (I) are effective in reducing the incidence of the particular parasite in an animal infected with such parasites to an innocuous degree. More specifically, “controlling” in the present context means that the compound of the formula (I) can kill the respective parasite, inhibit its growth, or inhibit its proliferation.

Thus, one embodiment of the present invention refers to the use of a compound of the formula (I) as a medicament.

A further aspect refers to the use of a compound of the formula (I) as an antiendoparasitic agent, in particular a helminthicidal agent or antiprotozoic agent. Compounds of the formula (I) are suitable for use as an antiendoparasitic agent, especially as a helminthicidal agent or antiprotozoic agent, for example in animal breeding, in animal husbandry, in animal houses and in the hygiene sector.

A further aspect in turn relates to the use of a compound of the formula (I) as an antiectoparasitic agent, in particular an arthropodicide such as an insecticide or an acaricide. A further aspect relates to the use of a compound of the formula (I) as an antiectoparasitic agent, in particular an arthropodicide such as an insecticide or an acaricide, for example in animal husbandry, in animal breeding, in animal houses or in the hygiene sector.

Anthelmintic Mixing Components

The following anthelmintic mixing components may be mentioned by way of example:

anthelmintically active compounds including trematicidally and cestocidally active compounds:

The compounds of the formula (I) can also be used in vector control. In the context of the present invention, a vector is an arthropod, especially an insect or arachnid, capable of transmitting pathogens, for example viruses, worms, single-cell organisms and bacteria, from a reservoir (plant, animal, human, etc.) to a host. The pathogens can be transmitted either mechanically (for example trachoma by non-stinging flies) to a host or after injection (for example malaria parasites by mosquitoes) into a host.

Examples of vectors in the context of the present invention are insects, such as aphids, flies, leafhoppers orthrips, which can transmit plant viruses to plants. Other vectors capable of transmitting plant viruses are spider mites, lice, beetles and nematodes.

Further examples of vectors in the context of the present invention are insects and arachnids such as mosquitoes, especially of the generaAedes, Anopheles, for exampleA. gambiae, A. arabiensis, A. funestus, A. dirus(malaria) andCulex, lice, fleas, flies, mites and ticks, which can transmit pathogens to animals and/or humans.

Vector control is also possible if the compounds of the formula (I) are resistance-breaking.

Compounds of the formula (I) are suitable for use in the prevention of diseases and/or pathogens transmitted by vectors. Thus, a further aspect of the present invention is the use of compounds of the formula (I) for vector control, for example in agriculture, in horticulture, in forests, in gardens and in leisure facilities, and also in the protection of materials and stored products.

Protection of Industrial Materials

The compounds of the formula (I) are suitable for protecting industrial materials against attack or destruction by insects, for example from the orders Coleoptera, Hymenoptera, Isoptera, Lepidoptera, Psocoptera and Zygentoma.

Industrial materials in the present context are understood to mean inanimate materials, such as preferably plastics, adhesives, sizes, papers and cards, leather, wood, processed wood products and coating compositions. The use of the invention for protection of wood is particularly preferred.

In a further embodiment, the compounds of the formula (I) are used together with at least one further insecticide and/or at least one fungicide.

In a further embodiment, the compounds of the formula (I) are present as a ready-to-use pesticide, i.e. it can be applied to the material in question without further modifications. Suitable further insecticides or fungicides are in particular those mentioned above.

Surprisingly, it has also been found that the compounds of the formula (I) can 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. It is equally possible to use the compounds of the formula (I), alone or in combinations with other active ingredients, as antifouling agents.

Control of Animal Pests in the Hygiene Sector

The compounds of the formula (I) are suitable for controlling animal pests in the hygiene sector. More particularly, the invention can be used in the domestic protection sector, in the hygiene protection sector and in the protection of stored products, particularly for control of insects, arachnids and mites encountered in enclosed spaces, for example dwellings, factory halls, offices, vehicle cabins. For controlling animal pests, the compounds of the formula (I) are used alone or in combination with other active ingredients and/or auxiliaries. They are preferably used in domestic insecticide products. The compounds of the formula (I) are effective against sensitive and resistant species, and against all developmental stages.

These pests include, for example, pests from the class Arachnida, from the orders Scorpiones, Araneae and Opiliones, from the classes Chilopoda and Diplopoda, from the class Insecta the order Blattodea, from the orders Coleoptera, Dermaptera, Diptera, Heteroptera, Hymenoptera, Isoptera, Lepidoptera, Phthiraptera, Psocoptera, Saltatoria or Orthoptera, Siphonaptera and Zygentoma and from the class Malacostraca the order Isopoda.

Application is carried out, for example, in aerosols, unpressurized spray products, for example pump and atomizer sprays, automatic fogging systems, foggers, foams, gels, evaporator products with evaporator tablets made of cellulose or plastic, 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 bait stations.

Intermediates

One aspect of the present invention relates to intermediates of the formula (II)

A further aspect of the present invention relates to intermediates of the formula (III),

Compounds according to the invention of the general structure (la) may be prepared analogously to the peptide coupling methods known from the literature from the corresponding anilines or azinylamines (III) reacted with (VII-a) or (VII-b) [WO 2010/051926; WO 2010/133312].

The intermediates of the general structure (II) and (III) may be prepared by methods known from the literature by means of palladium-catalyzed reactions of the reaction partners (IV) and (V-a, V-b) or (VI-a, VI-b) [WO 2005/040110; WO 2009/089508]. The appropriate boronic acids (V-a, VI-a) or boron pinacolates (V-b, VI-b) are commercially available. It is possible to prepare the halopyrazole (IV) analogously to DE3509567.

Alternatively, the anilines or azinylamines (III) may be prepared from the corresponding nitro precursors (II) by reduction [WO 2012/080376].

Inventive compounds of the general structure (I-b) can be produced by alkylation reactions, which are sufficiently well known to those skilled in the art, of amides of the structure (I-a) with alkylating reagents (VIII), preferably in the presence of basic reaction auxiliaries.

Inventive compounds of the general structure (I-c) can be prepared in analogy to thionating processes known from the literature from compounds of the general structure (I-a) [WO 2012/056372; WO 2003/066050].

For deblocking/detachment of protecting groups (PG), it is possible to use any known suitable acidic or basic reaction auxiliaries by the procedures described in the literature. When protecting groups of the carbamate type are used for amino groups, preference is given to using acidic reaction auxiliaries. When the t-butylcarbamate protecting group (BOC group) is used, for example, mixtures of mineral acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulphuric acid, phosphoric acid, or organic acids such as benzoic acid, formic acid, acetic acid, trifluoroacetic acid, methanesulphonic acid, benzenesulphonic acid or toluenesulphonic acid, and a suitable diluent such as water and/or an organic solvent such as tetrahydrofuran, dioxane, dichloromethane, chloroform, ethyl acetate, ethanol or methanol are used. Preference is given to mixtures of hydrochloric acid or acetic acid with water and/or an organic solvent such as ethyl acetate.

It is known that certain reactions and preparation processes can be carried out particularly efficiently in the presence of diluents or solvents and basic or acidic reaction auxiliaries. It is also possible to use mixtures of the diluents or solvents. The diluents or solvents are advantageously employed in such an amount that the reaction mixture is readily stirrable during the entire process.

If protecting groups are envisaged in the reaction schemes, it is possible to use any commonly known protecting groups. Especially those which are described by Greene T. W., Wuts P. G. W. in Protective Groups in Organic Synthesis; John Wiley & Sons, Inc. 1999, “Protection for the hydroxyl group including 1,2- and 1,3-diols”.

Also suitable are protective groups

Catalysts suitable for performance of a catalytic hydrogenation in the process according to the invention are all the customary hydrogenation catalysts, for example platinum catalysts (e.g. platinum sheet, platinum sponge, platinum black, colloidal platinum, platinum oxide, platinum wire), palladium catalysts (e.g. palladium sponge, palladium black, palladium oxide, palladium-charcoal, colloidal palladium, palladium barium sulphate, palladium barium carbonate, palladium hydroxide), nickel catalysts (e.g. reduced nickel, nickel oxide, Raney nickel), ruthenium catalysts, cobalt catalysts (e.g. reduced cobalt, Raney cobalt), copper catalysts (e.g. reduced copper, Raney copper, Ullmann copper). Preference is given to using noble metal catalysts (e.g. platinum and palladium or ruthenium catalysts) which have optionally been applied to a suitable support (e.g. carbon or silicon), rhodium catalysts (e.g. tris(triphenylphosphine)rhodium(I) chloride in the presence of triphenylphosphine). Furthermore, it is possible to use “chiral hydrogenation catalysts” (for example those comprising chiral diphosphine ligands such as (2S,3S)-(−)-2,3-bis(diphenylphosphino)butane [(S,S)-chiraphos] or (R)-(+)-2,2′- or (S)-(−)-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene [R(+)-BINAP or S(−)-BINAP]), whereby the proportion of an isomer in the isomer mixture is increased or the formation of another isomer is virtually completely suppressed.

Also representative are salts of compounds according to the invention which are formed from organic bases, for example pyridine or triethylamines, or those which are formed from inorganic bases, for example hydrides, hydroxides or carbonates of sodium, lithium, calcium, magnesium or barium, when the compounds of the general formula (I) have a structural element suitable for formation of this salt.

EXPERIMENTAL SECTION

1H-NMR data were recorded using a Bruker Avance 400 equipped with a flow cell (60 μl volume), or using a Bruker AVIII 400 equipped with a 1.7 mm cryo-CPTCI sample head, or using a Bruker AVII 600 (600.13 MHz) equipped with a 5 mm cryo-TCI sample head, or using a Bruker AVIII 600 (601.6 MHz) equipped with a 5 mm cryo-CPMNP sample head. This was done using tetramethylsilane as reference (0.0 ppm) and CD3CN, CDCl3or D6-DMSO as deuterated solvent.

A 25 ml flask was initially charged with 3.41 g (11.2 mmol) of [2,6-dimethyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]hydrazine (free base, known from US2003/187233) in 13 ml of ethanol. Then 1.84 g (11.2 mmol) of tetramethoxypropane and subsequently 0.55 g (5.6 mmol) of 96% sulphuric acid were added. The reaction mixture was heated to reflux for 2 h. Ethanol was evaporated off on a rotary evaporator under reduced pressure. The residue was partitioned between ethyl acetate and saturated aqueous sodium hydrogencarbonate solution. The organic phase was removed, dried with sodium sulphate and concentrated on a rotary evaporator under reduced pressure. The residue was distilled in a Kugelrohr under reduced pressure at 1 mbar and 150° C., and gave 2.5 g of 1-[2,6-dimethyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazole.

A 250 ml flask was initially charged with 2.5 g (7.34 mmol) of 1-[2,6-dimethyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazole in 30 ml of acetonitrile, and 8.3 g (36.9 mmol) of N-iodosuccinimide in 50 ml of acetonitrile were added dropwise. Subsequently, the mixture was heated to reflux. For workup, the mixture was concentrated and the residue was partitioned between water and ethyl acetate. The organic phase was removed, washed first with saturated aqueous sodium hydrogensulphite solution, then with saturated sodium chloride solution, dried with sodium sulphate and concentrated. The residue was purified by chromatography with silica gel by means of a gradient from 90:10 to 70:30 (v/v) in cyclohexane/ethyl acetate. After concentration of the fractions containing the product, 2.5 g of a residue were obtained, which consisted of 1-[2,6-dimethyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-4-iodopyrazole and some toluene.

1 g (2.14 mmol) of 1-[2,6-dimethyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-4-iodopyrazole and 0.675 g (3 mmol) of 3-nitro-4-chlorophenylboronic acid were initially charged in 18 ml of 1,4-dioxane, and 0.16 g (0.21 mmol) of 1,1′-bis(diphenylphosphino)ferrocenepalladium(II) chloride and 9.6 ml of a 2M aqueous Na2CO3solution were added. The mixture was stirred at 100° C. until conversion was complete. After the reaction mixture had cooled down, the complete mixture was concentrated on silica gel on a rotary evaporator and then chromatographed using silica gel (cyclohexane/ethyl acetate gradient). 0.86 g (78.1% of theory) were obtained as a colourless solid.

0.86 g (10.7 mmol) of 4-(4-chloro-3-nitrophenyl)-1-[2,6-dimethyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazole (step 1) was dissolved in 9 mL of 1,4-dioxane and 0.94 g (4.16 mmol) of tin(H) chloride dihydrate was added at room temperature. The reaction mixture was cooled to 0° C., then 6.5 ml of conc. HCl were added dropwise and then the mixture was stirred under reflux for 2 hours. After completion of the reaction, the volume of the reaction mixture was concentrated to two thirds on the rotary evaporator, then made alkaline with saturated aqueous sodium carbonate solution. The aqueous mixture was extracted repeatedly with dichloromethane, the combined organic phases were dried over magnesium sulfate, filtered and concentrated, and the residue was chromatographed over silica gel (cyclohexane/ethyl acetate gradient). 0.48 g (73.5% of theory) of a yellowish oil were obtained.

80 mg (0.17 mmol) of 2-chloro-5-[1-[2,6-dimethyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]pyrazol-4-yl]aniline (step 2) were dissolved in 3 ml of THF and 27.2 mg (0.17 mmol) of 4-fluorobenzoyl chloride and 17.4 mg (0.17 mmol) of triethylamine were added at room temperature, and the mixture was stirred under reflux until conversion was complete, with monitoring by TLC. After cooling, 5 ml of water were added and the mixture was extracted repeatedly with dichloromethane. The combined organic phases were dried over magnesium sulphate, filtered and concentrated, and the residue was chromatographed using silica gel (cyclohexane/ethyl acetate gradient). 70 mg (67.4% of theory) of the target compound were obtained as a yellowish oil.

The compounds listed in Table 1 were prepared using the preparation processes described above.

NMR Data of Selected Examples

NMR Peak Lists

The 1H-NMR data of selected examples are noted in the form of 1H-NMR peak lists. For each signal peak, first the δ value in ppm and then the signal intensity in round brackets are listed. The pairs of δ value-signal intensity numbers for different signal peaks are listed with separation from one another by semicolons.

The peak list for one example therefore takes the form of:

The intensity of sharp signals correlates with the height of the signals in a printed example of an NMR spectrum in cm and shows the true ratios of the signal intensities. In the case of broad signals, several peaks or the middle of the signal and the relative intensity thereof may be shown in comparison to the most intense signal in the spectrum.

For calibration of the chemical shift of 1H NMR spectra tetramethylsilane and/or the chemical shift of the solvent are used, particularly in the case of spectra measured in DMSO. Therefore, the tetramethylsilane peak may but need not occur in NMR peak lists.

The lists of the 1H NMR peaks are similar to the conventional 1H NMR printouts and thus usually contain all peaks listed in a conventional NMR interpretation.

In addition, like conventional 1H NMR printouts, they may show solvent signals, signals of stereoisomers of the target compounds, which likewise form part of the subject-matter of the invention, and/or peaks of impurities.

In the reporting of compound signals in the delta range of solvents and/or water, our lists of 1H NMR peaks show the usual solvent peaks, for example peaks of DMSO in DMSO-D6and the peak of water, which usually have a high intensity on average.

The peaks of stereoisomers of the target compounds and/or peaks of impurities usually have a lower intensity on average than the peaks of the target compounds (for example with a purity of >90%).

Such stereoisomers and/or impurities may be typical of the particular preparation process. Their peaks can thus help in identifying reproduction of our preparation process with reference to “by-product fingerprints”.

An expert calculating the peaks of the target compounds by known methods (MestreC, ACD simulation, but also with empirically evaluated expected values) can, if required, isolate the peaks of the target compounds, optionally using additional intensity filters. This isolation would be similar to the relevant peak picking in conventional 1H NMR interpretation.

Further details of 1H NMR peak lists can be found in the Research Disclosure Database Number 564025.

Table 4:1H-NMR data were recorded using a Bruker Avance 400 equipped with a flow cell (60 μl volume), or using a Bruker AVIII 400 equipped with a 1.7 mm cryo-CPTCI sample head, or using a Bruker AVII 600 (600.13 MHz) equipped with a 5 mm cryo-TCI sample head, or using a Bruker AVIII 600 (601.6 MHz) equipped with a 5 mm cryo-CPMNP probe head. This was done using tetramethylsilane as reference (0.0 ppm) and CD3CN, CDCl3or D6-DMSO as deuterated solvent.

Table 5: The1H-NMR data were measured using Bruker AVIII 400 spectrometers (400.13 MHz) equipped with 5 mm measuring heads or using a Bruker AVIII 500 spectrometer (500.13 MHz) with a 5 mm broadband head or a 5 mm Prodigy™ probe head. This was done using tetramethylsilane as reference (0.0 ppm) and predominantly D6-DMSO as deuterated solvent.

Biological Examples

Ctenocephalides felis—In Vitro Contact Tests with Adult Cat Fleas

For the coating of the test tubes, 9 mg of active ingredient are first dissolved in 1 ml of acetone p.a. and then diluted to the desired concentration with acetone p.a. 250 μl of the solution are distributed homogeneously on the inner walls and the base of a 25 ml glass tube by turning and rocking on an orbital shaker (rocking rotation at 30 rpm for 2 h). With 900 ppm of active ingredient solution and internal surface area 44.7 cm2, given homogeneous distribution, an area-based dose of 5 μg/cm2is achieved.

After the solvent has evaporated off, the tubes are populated with 5-10 adult cat fleas (Ctenocephalides felis), sealed with a perforated plastic lid and incubated in a horizontal position at room temperature and ambient humidity. After 48 h, efficacy is determined. To this end, the tubes are stood upright and the fleas are knocked to the base of the tube. Fleas which remain motionless at the base or move in an uncoordinated manner are considered to be dead or moribund.

A substance shows good efficacy againstCtenocephalides felisif at least 80% efficacy was achieved in this test at an application rate of 5 μg/cm2. 100% efficacy means that all the fleas were dead or moribund. 0% efficacy means that no fleas were harmed.

In this test, for example, the following compounds from the preparation examples show an efficacy of 80% at an application rate of 5 μg/cm2(500 g/ha): 58, 2-13.

Rhipicephalus sanguineus—In Vitro Contact Tests with Adult Brown Dog Ticks

For the coating of the test tubes, 9 mg of active ingredient are first dissolved in 1 ml of acetone p.a. and then diluted to the desired concentration with acetone p.a. 250 μl of the solution are distributed homogeneously on the inner walls and the base of a 25 ml glass tube by turning and rocking on an orbital shaker (rocking rotation at 30 rpm for 2 h). With 900 ppm of active ingredient solution and internal surface area 44.7 cm2, given homogeneous distribution, an area-based dose of 5 μg/cm2is achieved.

After the solvent has evaporated off, the tubes are populated with 5-10 adult dog ticks (Rhipicephalus sanguineus), sealed with a perforated plastic lid and incubated in a horizontal position in the dark at room temperature and ambient humidity. After 48 h, efficacy is determined. To this end, the ticks are knocked to the base of the tube and incubated on a hotplate at 45-50° C. for not more than 5 min. Ticks which remain motionless on the base or move in such an uncoordinated manner that they are unable to deliberately avoid the heat by climbing upwards are considered to be dead or moribund.

A substance shows good activity againstRhipicephalus sanguineusif, in this test, an efficacy of at least 80% was achieved at an application rate of 5 μg/cm2. An efficacy of 100% means that all the ticks were dead or moribund. 0% efficacy means that none of the ticks were harmed.

In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 5 μg/cm2(500 g/ha): 2, 4, 24, 66, 57, 58.

In this test, for example, the following compounds from the preparation examples show an efficacy of 80% at an application rate of 5 μg/cm2(500 g/ha): 5, 7, 11, 12, 16, 33, 43, 50, 2-13, 2-14.

In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 1 μg/cm2(100 g/ha): 6, 23, 77, 2-12.

In this test, for example, the following compounds from the preparation examples show an efficacy of 80% at an application rate of 1 μg/cm2(100 g/ha): 67.

10 mg of active ingredient are dissolved in 0.5 ml of dimethyl sulfoxide. To produce a suitable formulation, the active ingredient solution is diluted with water to the concentration desired in each case.

This active ingredient formulation is pipetted into tubes. 8-10 engorged adult female cattle ticks (Boophilus microplus) are transferred into a further tube with holes. The tube is immersed into the active ingredient formulation, and all the ticks are completely wetted. After the liquid has run out, the ticks are transferred on filter disks into plastic dishes and stored in a climate-controlled room.

Efficacy is assessed after 7 days by laying of fertile eggs. Eggs which are not visibly fertile are stored in a climate-controlled cabinet until the larvae hatch after about 42 days. An efficacy of 100% means that none of the ticks has laid any fertile eggs; 0% means that all the eggs are fertile.

In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 100 ppm: 2, 2-13.

In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 100 ppm: 31.

To produce a suitable active ingredient formulation, 10 mg of active ingredient are mixed with 0.5 ml of solvent and the concentrate is diluted to the desired concentration with solvent.

1 μl of the active ingredient solution is injected into the abdomen of 5 engorged adult female cattle ticks (Boophilus microplus). The animals are transferred into dishes and kept in a climate-controlled room.

Efficacy is assessed after 7 days by laying of fertile eggs. Eggs which are not visibly fertile are stored in a climate-controlled cabinet until the larvae hatch after about 42 days. An efficacy of 100% means that none of the ticks has laid any fertile eggs; 0% means that all the eggs are fertile.

In this test, for example, the following compounds from the preparation examples show an efficacy of 80% at an application rate of 20 μg/animal: 14, 65, 2-6.

In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 4 μg/animal: 17.

To produce a suitable active ingredient formulation, 10 mg of active ingredient are mixed with 0.5 ml of dimethyl sulphoxide. Dilution with citrated cattle blood gives the desired concentration.

About 20 unfed adult cat fleas (Ctenocephalides felis) are placed into a chamber which is closed at the top and bottom with gauze. A metal cylinder whose bottom end is closed with parafilm is placed onto the chamber. The cylinder contains the blood/active ingredient formulation, which can be imbibed by the fleas through the parafilm membrane.

Nach 2 Tagen wird die Abtötung in % bestimmt. 100% means that all of the fleas have been killed; 0% means that none of the fleas have been killed.

In this test, for example, the following compounds from the preparation examples show an efficacy of 95% at an application rate of 100 ppm: 72, 75, 2-1, 2-2, 2-4, 2-9, 2-12.

In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 100 ppm: 3, 5.

In this test, for example, the following compounds from the preparation examples show an efficacy of 80% at an application rate of 100 ppm: 29, 47.

In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 20 ppm: 17.

To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of dimethyl sulfoxide, and the concentrate is diluted with water to the desired concentration.

About 20 L1 larvae of the Australian sheep blowfly (Lucilia cuprina) are transferred into a test vessel containing minced horsemeat and the active compound formulation of the desired concentration.

After 2 days, the kill in % is determined. 100% means that all the larvae have been killed; 0% means that no larvae have been killed.

In this test, for example, the following compounds from the preparation examples show an efficacy of 98% at an application rate of 100 ppm: 2-1, 2-2.

In this test, for example, the following compounds from the preparation examples show an efficacy of 95% at an application rate of 100 ppm: 16.

In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 100 ppm: 12, 13, 27, 2-4, 2-8, 2-12, 2-14.

In this test, for example, the following compounds from the preparation examples show an efficacy of 80% at an application rate of 100 ppm: 7, 55, 75.

In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 20 ppm: 17.

To produce a suitable preparation of active compound, 10 mg of active compound are mixed with 0.5 ml of dimethyl sulfoxide, and the concentrate is diluted with water to the desired concentration.

Vessels containing a sponge treated with sugar solution and the active ingredient formulation of the desired concentration are populated with 10 adult houseflies (Musca domestica)).

After 2 days, the kill in % is determined. 100% means that all of the flies have been killed; 0% means that none of the flies have been killed.

In this test, for example, the following compounds from the preparation examples show an efficacy of 80% at an application rate of 100 ppm: 5, 13, 23.

In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 20 ppm: 17.

Solvent: 125.0 parts by weight of acetone

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

Vessels are filled with sand, active ingredient solution, an egg/larvae suspension of the southern root-knot nematode (Meloidogyne incognita) and lettuce seeds. The lettuce seeds germinate and the plants develop. The galls develop on the roots.

After 14 days, the nematicidal efficacy in % is determined by the formation of galls. 100% means that no galls were found; 0% means that the number of galls on the treated plants corresponds to the untreated control.

In this test, for example, the following compound from the preparation examples shows an efficacy of 90% at an application rate of 20 ppm: 2-3, 2-4.

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

To produce a suitable active ingredient formulation, 1 part by weight of active ingredient is dissolved with the specified parts by weight of solvent and made up to the desired concentration with water containing an emulsifier concentration of 1000 ppm. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

Discs of Chinese cabbage leaves (Brassica pekinensis) are sprayed with an active ingredient formulation of the desired concentration and, after drying, populated with larvae of the mustard beetle (Phaedon cochleariae).

After 7 days, the efficacy in % is determined. 100% means that all the beetle larvae have been killed; 0% means that no beetle larvae have been killed.

In this test, for example, the following compounds from the preparation examples show an efficacy of 83% at an application rate of 100 g/ha: 18, 2-8.

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

To produce a suitable active ingredient formulation, 1 part by weight of active ingredient is dissolved with the specified parts by weight of solvent and made up to the desired concentration with water containing an emulsifier concentration of 1000 ppm. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

Leaf discs of maize (Zea mays) are sprayed with an active compound formulation of the desired concentration and, after drying, populated with caterpillars of the armyworm (Spodoptera frugiperda).

After 7 days, the efficacy in % is determined. 100% means that all the caterpillars have been killed; 0% means that no caterpillar has been killed.

In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 500 g/ha: 2, 4, 5

In this test, for example, the following compounds from the preparation examples show an efficacy of 83% at an application rate of 100 g/ha: 7, 13, 41.

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

To produce a suitable active ingredient formulation, 1 part by weight of active ingredient is dissolved with the specified parts by weight of solvent and made up to the desired concentration with water containing an emulsifier concentration of 1000 ppm. To produce further test concentrations, the formulation is diluted with emulsifier-containing water.

Discs of bean leaves (Phaseolus vulgaris) infested with all stages of the greenhouse red spider mite (Tetranychus urticae) are sprayed with an active ingredient formulation of the desired concentration.

After 6 days, the efficacy in % is determined. 100% means that all the spider mites have been killed; 0% means that no spider mites have been killed.

In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 500 g/ha: 2, 5.

In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 500 g/ha: 3, 4.

In this test, for example, the following compounds from the preparation examples shows an efficacy of 90% at an application rate of 100 g/ha: 11, 33, 51, 2-1, 2-2, 2-3, 2-13.