PESTICIDAL COMPOUNDS

Abstract

The present invention relates to the compounds of formula (I), and the N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof wherein the variables are defined according to description formula (I). The compounds of formula (I), as well as the N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof, are useful for combating or controlling invertebrate pests, in particular arthropod pests and nematodes. The invention also relates to a method for controlling invertebrate pests by using these compounds and to plant propagation material and to an agricultural and a veterinary composition comprising said compounds.

##STR00001##

Claims

1. Compounds A compound of formula I ##STR00133## wherein A.sup.1 is N or CR.sup.A1; A.sup.2 is N or CR.sup.A2; A.sup.3 is N or CR.sup.A3; wherein at least one of the A.sup.1, A.sup.2, A.sup.3 is N; B.sup.1 is CR.sup.B1; B.sup.2 is CR.sup.B2; B.sup.3 is CR.sup.B3; R.sup.A1, R.sup.A2, and R.sup.A3 independently of each other are selected from H, halogen, N.sub.3, OH, CN, NO.sub.2, —SCN, —SF.sub.5, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, tri-C.sub.1-C.sub.6-alkylsilyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkyl-C.sub.3-C.sub.6-cycloalkoxy, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen,  C(═O)—OR.sup.a, NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, O—C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-CN, NH—C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C(═O)—NR.sup.bR.sup.c, C(═O)—R.sup.d, SO.sub.2NR.sup.bR.sup.c, or S(═O).sub.mR.sup.e, phenyl, phenoxy, phenylcarbonyl, phenylthio, or —CH.sub.2-phenyl, wherein the phenyl rings are unsubstituted or substituted with R.sup.f; R.sup.B1, R.sup.B2, and R.sup.B3, independently of each other are H, halogen, N.sub.3, OH, CN, NO.sub.2, —SCN, —SF.sub.5, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, tri-C.sub.1-C.sub.6-alkylsilyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkyl-C.sub.3-C.sub.6-cycloalkoxy, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen,  C(═O)—OR.sup.a, NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, O—C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-CN, NH—C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C(═O)—NR.sup.bR.sup.c, C(═O)—R.sup.d, SO.sub.2NR.sup.bR.sup.c, or S(═O).sub.mR.sup.e, phenyl, phenoxy, phenylcarbonyl, phenylthio, or —CH.sub.2-phenyl, wherein the phenyl rings are unsubstituted or substituted with R.sup.f; Q is —N═C(X)—, —N(R.sup.2)—C(═NR)—, or —N(R.sup.2)—C(═S)—, —C(R.sup.4R.sup.5)—O—, —C(═O)—O—, —S(═O).sub.m—C(R.sup.7R.sup.8)—, —N(R.sup.2)—S(═O).sub.m—, —N(R.sup.2)—C(R.sup.9R.sup.10)—, —C(═O)—C(R.sup.19R.sup.20)—, —N(R.sup.2)—C(═O)—, —C(R.sup.13R.sup.14)—C(R.sup.15R.sup.16)—, or —C(R.sup.17)═C(R.sup.18)—; wherein Ar is bound to either side of Q; X is identical or different, H, halogen, SR.sup.7, OR.sup.8, N(R.sup.3).sub.2, —CR.sup.4═N(OCH.sub.3), CN, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl, wherein the alkyl, alkenyl, alkynyl and cycloalkyl moieties are unsubstituted or substituted with halogen; phenyl, or —CH.sub.2-phenyl, wherein the phenyl rings are unsubstituted or substituted with R.sup.f; R is identical or different, H, CN, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl, wherein the alkyl, alkenyl, alkynyl and cycloalkyl moieties are unsubstituted or substituted with halogen,  SR.sup.7, OR.sup.8, N(R.sup.3).sub.2, phenyl, or —CH.sub.2-phenyl, wherein the phenyl rings are unsubstituted or substituted with R.sup.f; R.sup.2 is H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen,  C(O)—OR.sup.a, C.sub.1-C.sub.6-alkylen-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylen-CN, C(O)—NR.sup.bR.sup.c, C(O)—R.sup.d, SO.sub.2NR.sup.bR.sup.c, S(═O).sub.mR.sup.e, phenyl, or —CH.sub.2-phenyl, wherein the phenyl rings are unsubstituted or substituted with R.sup.f; R.sup.3 is H, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, or C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen,  C.sub.1-C.sub.6-alkylene-CN, phenyl, or —CH.sub.2-phenyl, wherein the phenyl rings are unsubstituted or substituted with R.sup.f; R.sup.4, R.sup.5, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20 are, identical or different, H, halogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen,  C(═O)—OR.sup.a, C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-CN, C(═O)—NR.sup.bR.sup.c, C(═O)—R.sup.d, SO.sub.2NR.sup.bR.sup.c, S(═O).sub.mR.sup.e, phenyl, or —CH.sub.2-phenyl, wherein the phenyl rings are unsubstituted or substituted with R.sup.f; R.sup.6 is H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen,  C(═O)—OR.sup.a, C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-CN, C(═O)—NR.sup.bR.sup.c, C(═O)—R.sup.d, SO.sub.2NR.sup.bR.sup.c, S(═O).sub.mR.sup.e, phenyl, —CH.sub.2—C(═O)—OR.sup.a, or —CH.sub.2-phenyl, wherein the phenyl rings are unsubstituted or substituted with R.sup.f; Ar is phenyl or 5- or 6-membered hetaryl, which are unsubstituted or substituted with R.sup.Ar, wherein R.sup.Ar is halogen, N.sub.3, OH, CN, NO.sub.2, —SCN, —SF.sub.5, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, tri-C.sub.1-C.sub.6-alkylsilyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen,  C(═O)—OR.sup.a, NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, O—C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-CN, NH—C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C(═O)—NR.sup.bR.sup.c, C(═O)—R.sup.d, SO.sub.2NR.sup.bR.sup.c, or S(═O).sub.mR.sup.e, phenyl, phenoxy, phenylcarbonyl, phenylthio or —CH.sub.2-phenyl, wherein phenyl rings are unsubstituted or substituted with R.sup.f; R.sup.1 is a moiety of formula Y—Z-T-R.sup.11 or Y—Z-T-R.sup.12; wherein Y is —CR.sup.ya═N—, wherein the N is bound to Z; —NR.sup.yc—C(═O)—, wherein C(═O) is bound to Z; or —NR.sup.yc—C(═S)—, wherein C(═S) is bound to Z; Z is a single bond; —NR.sup.zc—C(═O)—, wherein C(═O) is bound to T; —NR.sup.zc—C(═S)—, wherein C(═S) is bound to T; —N═C(S—R.sup.za)—, wherein T is bound to the carbon atom; —O—C(═O)—, wherein T is bound to the carbon atom; or —NR.sup.zc—C(S—R.sup.za)═, wherein T is bound to the carbon atom; T is O, N or N—R.sup.T; R.sup.11 is C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkyl-C.sub.3-C.sub.6-cycloalkoxy, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen,  C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-CN, C(═O)—NR.sup.bR.sup.c, C(═O)—R.sup.d, aryl, aryl-carbonyl, aryl-C.sub.1-C.sub.4-alkyl, aryloxy-C.sub.1-C.sub.4-alkyl, heteroaryl, carbonyl-heteroaryl, heteroaryl-C.sub.1-C.sub.4-alkyl or heteroaryloxy-C.sub.1-C.sub.4-alkyl, wherein the phenyl rings are unsubstituted or substituted with R.sup.g and wherein the heteroaryl is a 5- or 6-membered monocyclic heteroaryl or a 8-, 9- or 10-membered bicyclic heteroaryl; R.sup.12 is a radical of the formula A.sup.1; ##STR00134## wherein # indicates the point of attachment to T; R.sup.121, R.sup.122, R.sup.123 are, identical or different, H, halogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.6-alkylcarbonlyoxy, C.sub.1-C.sub.6-alkenylcarbonlyoxy, C.sub.3-C.sub.6-cycloalkylcarbonlyoxy, wherein the alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy and cycloalkyl moieties are unsubstituted or substituted with halogen, or NR.sup.bR.sup.c, or one of R.sup.121, R.sup.122, R.sup.123 may also be oxo; R.sup.124 is H, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy, or C.sub.2-C.sub.6-alkenyloxy, wherein the alkyl, alkoxy, alkenyl and alkenyloxy moieties are unsubstituted or substituted with halogen; and where R.sup.ya is H, halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.4-alkyl-C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.4-alkyl-C.sub.3-C.sub.6-cycloalkoxy, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen,  C(═O)—OR.sup.a, C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-CN, C(═O)—NR.sup.bR.sup.c, C(═O)—R.sup.d, SO.sub.2NR.sup.bR.sup.c, S(═O).sub.mR.sup.e, phenyl, or —CH.sub.2-phenyl, wherein the phenyl rings are unsubstituted or substituted with R.sup.f; R.sup.yc, R.sup.zc are, identical or different, H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.4-alkyl-C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.4-alkyl-C.sub.3-C.sub.6-cycloalkyl, or C.sub.1-C.sub.4-alkyl-C.sub.3-C.sub.6-cycloalkoxy, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen; R.sup.T is H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.4-alkyl-C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen,  C(═O)—OR.sup.a, C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-CN, C(═O)—NR.sup.bR.sup.c, C(═O)—R.sup.d, SO.sub.2NR.sup.bR.sup.c, S(═O).sub.mR.sup.e, phenyl, or —CH.sub.2-phenyl, wherein the phenyl rings are unsubstituted or substituted with R.sup.f; R.sup.zc together with R.sup.T if present, may form C.sub.1-C.sub.6-alkylene or a linear C.sub.2-C.sub.6-alkenylene group, where in the linear C.sub.1-C.sub.6-alkylene and the linear C.sub.2-C.sub.6-alkenylene a CH.sub.2 moiety may be replaced by a carbonyl or a C═N—R′ and/or wherein 1 or 2 CH.sub.2 moieties may be replaced by O or S and/or wherein the linear C.sub.1-C.sub.6-alkylene and the linear C.sub.2-C.sub.6-alkenylene may be unsubstituted or substituted with R.sup.h; R.sup.za is H, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, tri-C.sub.1-C.sub.6-alkylsilyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.4-alkyl-C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.4-alkyl-C.sub.3-C.sub.6-cycloalkoxy, C.sub.1-C.sub.4-alkyl-C.sub.3-C.sub.6-cycloalkyl, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen,  C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-CN, C(═O)—NR.sup.bR.sup.c, C(═O)—R.sup.d, phenyl, phenylcarbonyl, or —CH.sub.2-phenyl, wherein the phenyl rings are unsubstituted or substituted with R.sup.f; R.sup.za together with R.sup.T if present, may form C.sub.1-C.sub.6-alkylene or a linear C.sub.2-C.sub.6-alkenylene group, where in the linear C.sub.1-C.sub.6-alkylene and the linear C.sub.2-C.sub.6-alkenylene a CH.sub.2 moiety may be replaced by a carbonyl or a C═N—R′ and/or wherein 1 or 2 CH.sub.2 moieties may be replaced by O or S and/or wherein the linear C.sub.1-C.sub.6-alkylene and the linear C.sub.2-C.sub.6-alkenylene may be unsubstituted or substituted with R.sup.h; R.sup.a, R.sup.b and R.sup.c are, identical or different, H, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen, C.sub.1-C.sub.6-alkylene-CN, phenyl, or —CH.sub.2-phenyl, wherein the phenyl rings are unsubstituted or substituted with R.sup.f; R.sup.b and R.sup.c together with the nitrogen they are attached may form 5- or 6-membered saturated, partially or fully unsaturated heterocyclic ring; R.sup.d is H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen,  phenyl, or —CH.sub.2-phenyl, wherein the phenyl rings are unsubstituted or substituted with R.sup.f; R.sup.e is C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, wherein the alkyl, cycloalkyl moieties are unsubstituted or substituted with halogen,  phenyl and —CH.sub.2-phenyl, wherein the phenyl rings are unsubstituted or substituted with R.sup.f; R.sup.f is halogen, N.sub.3, OH, CN, NO.sub.2, —SCN, —SF.sub.5, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, tri-C.sub.1-C.sub.6-alkylsilyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxyx-C.sub.1-C.sub.4-alkyl, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen,  C(═O)—OR.sup.a, NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, O—C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-CN, NH—C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C(═O)—NR.sup.bR.sup.c, C(═O)—R.sup.d, SO.sub.2NR.sup.bR.sup.c, or S(═O).sub.mR.sup.e; R.sup.g is halogen, N.sub.3, OH, CN, NO.sub.2, —SCN, —SF.sub.5, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, tri-C.sub.1-C.sub.6-alkylsilyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, wherein the alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy moieties are unsubstituted or substituted with halogen,  C(═O)—OR.sup.a, NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, O—C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylene-CN, NH—C.sub.1-C.sub.6-alkylene-NR.sup.bR.sup.c, C(═O)—NR.sup.bR.sup.c, C(═O)—R.sup.d, SO.sub.2NR.sup.bR.sup.c, or S(═O).sub.mR.sup.e; R.sup.h is halogen, OH, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, or CN; m is 0, 1, or 2; and the N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof.

2. The compound of formula I according to claim 1, wherein A.sup.1 is CR.sup.A1, A.sup.2 is CR.sup.A2, A.sup.3 is N.

3. The compound of formula I according to claim 1, wherein A.sup.1 is CR.sup.A1, A.sup.2 is N, A.sup.3 is CR.sup.A3.

4. The compound of formula I according to claim 11, wherein A.sup.1 is CR.sup.A1, A.sup.2 is N, A.sup.3 is N.

5. The compound of formula I according to claim 1, wherein R.sup.B1, R.sup.B2, and R.sup.B3, independently of each other are H, halogen, or C.sub.1-C.sub.6-alkyl.

6. The compound of formula I according to claim 1, wherein R.sup.1 is a formula YZT-1 to YZT-9, wherein ##STR00135## denotes attachment to the 10 membered hetaryl; ##STR00136## wherein R.sup.11, R.sup.12, R.sup.T, R.sup.ya, R.sup.yc, R.sup.za and R.sup.zc are as defined in claim 1.

7. The compound of formula I according to claim 1, wherein Ar are formulas Ar-1 to Ar-20 ##STR00137##

8. A composition comprising compound of formula I according to claim 1, an N-oxide or an agriculturally acceptable salt thereof, and a further active substance.

9. A method for combating or controlling invertebrate pests comprising contacting the pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound according to claim 1.

10. A method for protecting growing plants from attack or infestation by invertebrate pests comprising contacting a plant, or soil or water wherein the plant is growing, with a pesticidally effective amount of at least one compound according to claim 1.

11. A seed comprising a compound according to claim 1, or the enantiomers, diastereomers or salts thereof, in an amount of from 0.1 g to 10 kg per 100 kg of seed.

12. (canceled)

13. A method for treating or protecting an animal from infestation or infection by invertebrate pests comprising bringing the animal in contact with a pesticidally effective amount of at least one compound of the formula I according to claim 1 to 7, a stereoisomer thereof and/or at least one veterinarily acceptable salt thereof.

Description

EXAMPLES

[0662] With appropriate modification of the starting materials, the procedures as described in the preparation examples below were used to obtain further compounds of formula I. The compounds obtained in this manner are listed in the table that follows, together with physical data.

[0663] Compounds can be characterized e.g. by coupled High Performance Liquid Chromatography/mass spectrometry (HPLC/MS), by .sup.1H-NMR and/or by their melting points.

[0664] Analytical HPLC/MS—Method 1: Agilent Eclipse Plus C18, 50×4.6 mm, ID 5 μm; Elution: A=10 mM Amm. Formate (0.1% Formic Acid), B=Acetonitrile (0.1% Formic Acid), Flow=1.25 ml/min. at 40° C.; Gradient: 10% B to 100% B—1.5 min, hold for 1 min, 1 min—100% B. Run Time=3.5 min.

[0665] Analytical HPLC/MS—Method 2: Kinetex XB C18 1.7μ 50×2.1 mm; A=Water+0.1% TFA, B=Acetonitrile, Flow=0.8 ml/min-1.0 ml/min in 1.5 min. at 60° C.; Gradient: 5% B to 100% B—1.5 min.

[0666] .sup.1H-NMR: The signals are characterized by chemical shift (ppm, δ[delta]) vs. tetramethylsilane respectively, CDCl.sub.3 for .sup.13C-NMR, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: m=multiplet, h=heptet, q=quartet, t=triplet, d=doublet and s=singlet.

[0667] Abbreviations used are: d for day(s), h for hour(s), min for minute(s), r.t./room temperature for 20-25° C., R.sub.t for retention time; DMSO for dimethyl sulfoxide, OAc for acetate, EtOAc for ethyl acetate, THE for tetrahydrofuran, t-BuOH for tert-butanol, dppfPdCl for [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II), DIPEA for diisopropylethylamine, DCM for dichloromethane and DMAP for 4-Dimethylaminopyridine

Preparation Examples

Example C-1: 6-[(E)-[(2-isopropylphenyl)carbamothioylhydrazono]methyl]-N-[4-(trifluoromethoxy)phenyl]isoquinoline-1-carboxamide (C-1)

Step 1: 6-bromo-N-[4-(trifluoromethoxy)phenyl]isoquinoline-1-carboxamide

[0668] To a stirred solution of 6-bromoisoquinoline-1-carboxylic acid (1.68 g) and 4-(trifluoromethoxy)aniline (1.2 g) in CH.sub.2Cl.sub.2 (20 mL) were added EDCl (1.53 g) and DMAP (0.81 g) and the reaction mixture was stirred at r.t. for 16 h. An additional portion of and 4-(trifluoromethoxy)aniline (0.9 mL) and EDCl (0.2 g) were added and the reaction was stirred for an additional 20 h. The reaction mixture was then quenched with a solution of aq. HCl (1 M) then extracted with CH.sub.2Cl.sub.2. The organic phase was dried over MgSO.sub.4, filtered and concentrated and used without further purification (2.5 g). LC/MS (method 1): Rt: 1.47 min; MS: m/z=410 (M+).

Step 2: 6-[(E)-prop-1-enyl]-N-[4-(trifluoromethoxy)phenyl]isoquinoline-1-carboxamide

[0669] A stirred suspension of 6-bromo-N-[4-(trifluoromethoxy)phenyl]isoquinoline-1-carboxamide (2.5 g, 6.1 mmol), [(E)-prop-1-enyl]boronic acid (0.79 g), dppfPdCl.sub.2 (0.22 g), K.sub.2CO.sub.3 (1.69 g) in DME/H.sub.2O (25 mL, 2:1) was heated at 110° C. for 16 h. The reaction mixture was allowed to cool to r.t. then extracted with EtOAc. The organic phase was dried over MgSO4, filtered and concentrated. Purification by silica gel chromatography eluting with a gradient of CH/EE afforded the title compound (2.0 g). LC/MS (method 1): Rt: 1.54 min; MS: m/z=373 (M+).

Step 3: 6-formyl-N-[4-(trifluoromethoxy)phenyl]isoquinoline-1-carboxamide

[0670] To a stirred solution of 6-[(E)-prop-1-enyl]-N-[4-(trifluoromethoxy)phenyl]isoquinoline-1-carboxamide (2.0 g) and OsO.sub.4 (1.3 mL, 2.5% in t-BuOH) in THE/H.sub.2O (80 mL, 1:1) at 0° C. was added NaIO.sub.4 (2.3 g) and the reaction mixture was stirred from 0° C. to r.t. over 16 h. The reaction mixture was then diluted with water and a saturated solution of NaS.sub.2O.sub.3 (100 mL) then extracted with EtOAc. The organic phase was dried over MgSO4, filtered and concentrated and the resultant crude material was purified by trituration with diisopropyl ether to afford 6-formyl-N-[4-(trifluoromethoxy)phenyl]isoquinoline-1-carboxamide (1.55 g, 80% yield). LC/MS (method 1): Rt: 1.27 min; MS: m/z=361 (M+).

Step 4: 6-[(E)-[(2-isopropylphenyl)carbamothioylhydrazono]methyl]-N-[4-(trifluoromethoxy)phenyl]isoquinoline-1-carboxamide

[0671] A solution of 6-formyl-N-[4-(trifluoromethoxy)phenyl]isoquinoline-1-carboxamide (1.55 g) and 1-amino-3-(2-isopropylphenyl)thiourea (1.1 g) in EtOH (30 mL) was stirred at 60° C. for 4 h. The reaction mixture was then allowed to cool to r.t. and the crude product was isolated by filtration and purified by trituration with diisopropyl ether to afford 6-[(E)-[(2-isopropylphenyl)carbamothioylhydrazono]methyl]-N-[4-(trifluoromethoxy)phenyl]isoquinoline-1-carboxamide (C-1) (1.81 g, 76% yield). LC/MS (method 1): Rt: 1.45 min; MS: m/z=552 (M+). .sup.1H NMR (400 MHz, THF-d.sub.8) δ 11.13 (s, 1H), 10.66 (s, 1H), 9.63-9.55 (m, 2H), 8.58 (d, J=5.5 Hz, 1H), 8.36 (dd, J=9.2, 1.7 Hz, 1H), 8.18 (d, J=2.6 Hz, 2H), 8.07-7.93 (m, 3H), 7.42 (dd, J=7.8, 1.4 Hz, 1H), 7.36-7.25 (m, 3H), 7.25-7.12 (m, 2H), 3.58 (dp, J=2.3, 1.1 Hz, 6H), 3.26 (p, J=6.9 Hz, 1H), 2.51 (s, 4H), 1.72 (pt, J=2.0, 0.9 Hz, 8H), 1.27 (d, J=6.9 Hz, 6H).

Example C-2: 6-[(E)-[(Z)-[3-(2-isopropylphenyl)-4-oxo-thiazolidin-2-ylidene]hydrazono]methyl]-N-[4-(trifluoromethoxy)phenyl]isoquinoline-1-carboxamide

[0672] A solution of 6-[(E)-[(2-isopropylphenyl)carbamothioylhydrazono]methyl]-N-[4-(trifluoromethoxy)phenyl]isoquinoline-1-carboxamide (C-1) (1.65 g), methyl bromoacetate (0.59 mL) and NaOAc (0.98 g) in EtOH (100 mL) was stirred at 50° C. for 16 h. The resultant precipate was isolated by filtration to afford 6-[(E)-[(Z)-[3-(2-isopropylphenyl)-4-oxo-thiazolidin-2-ylidene]hydrazono]methyl]-N-[4-(trifluoromethoxy)phenyl]isoquinoline-1-carboxamide (1.44 g, 81% yield). LC/MS (method 1): Rt: 1.49 min; MS: m/z=592 (M+). .sup.1H NMR (400 MHz, THE-d.sub.8) δ 10.65 (s, 1H), 9.60 (dd, J=9.2, 0.9 Hz, 1H), 8.57 (d, J=5.5 Hz, 1H), 8.24 (dd, J=9.1, 1.7 Hz, 1H), 8.13-8.08 (m, 1H), 8.07-7.96 (m, 3H), 7.50-7.37 (m, 2H), 7.28 (ddd, J=14.8, 7.5, 1.3 Hz, 3H), 7.16 (dd, J=7.9, 1.3 Hz, 1H), 4.14-3.99 (m, 2H), 3.57 (dq, J=2.2, 1.1 Hz, 6H), 2.88 (hept, J=6.9 Hz, 1H), 2.51 (s, 5H), 1.72 (ddp, J=3.1, 2.0, 1.0 Hz, 8H), 1.20 (dd, J=7.9, 6.9 Hz, 6H).

##STR00089##

TABLE-US-00004 Comp Ar [00090] A.sup.1 A.sup.2 A.sup.3 B.sup.1 B.sup.2 B.sup.3 R.sup.1 t.sub.R (min) M+ (m/z) C-1 [00091] [00092] CH CH N CH CH CH [00093] 1.472 552.1 C-2 [00094] [00095] CH CH N CH CH CH [00096] 1.509 592.1 C-3 [00097] [00098] N CH N CH CH CH [00099] 1.144 539.1 C-4 [00100] [00101] N CH N CH CH CH [00102] 1.082 578.9 C-5 [00103] [00104] N CH N CH CH CH [00105] 1.026 551.2 C-6 [00106] [00107] N CH N CH CH CH [00108] 2.037 538 C-7 [00109] [00110] N CH N CH CH CH [00111] 2.123 580.2 C-8 [00112] [00113] N CH N CH CH CH [00114] 2.069 577.9 C-9 [00115] [00116] CH N N CH CH CH [00117] 1.367 553  C-10 [00118] [00119] CH N N CH CH CH [00120] 1.392 593.1  C-11 [00121] [00122] CH N N CH CH CH [00123] 1.425 593  C-12 [00124] [00125] CH N N CH CH CH [00126] 1.403 567.2  C-13 [00127] [00128] CH N N CH CH CH [00129] 1.273 565.2  C-14 [00130] [00131] CH N N CH CH CH [00132] 1.425 607.1

Biological Examples

[0673] If not otherwise specified, the test solutions are prepared as follows:

[0674] The active compound is dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water:acetone. The test solution is prepared at the day of use.

[0675] Test solutions are prepared in general at concentrations of 1000 ppm, 500 ppm, 300 ppm, 100 ppm and 30 ppm (wt/vol).

B.1. Boll Weevil (Anthonomus grandis)

[0676] For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 96-well-microtiter plates containing an insect diet and 5-10 A. grandis eggs.

[0677] The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 5 μl, using a custom built micro atomizer, at two replications.

[0678] After application, microtiter plates were incubated at about 25±1° C. and about 75±5% relative humidity for 5 days. Egg and larval mortality was then visually assessed.

[0679] In this test, the following compounds at 800 ppm showed over 75% mortality in comparison with untreated controls: C-1, C-2, C-3.

B.2. Diamond Back Moth (Plutella xylostella)

[0680] The active compound is dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water:acetone. Surfactant (Alkamuls® EL 620) is added at a rate of 0.1% (vol/vol). The test solution is prepared at the day of use.

[0681] Leaves of cabbage were dipped in test solution and air-dried. Treated leaves were placed in petri dish enlined with moist filter paper and inoculated with ten 3.sup.rd instar larvae. Mortality was recorded 72 hours after treatment. Feeding damages were also recorded using a scale of 0-100%.

[0682] In this test, the following compounds at 300 ppm showed over 75% mortality in comparison with untreated controls: C-1, C-2, C-3, C-4, C-6, C-8, C-9, C-10, C-11, C-12, C-13, C-14.

B.3 Silverleaf Whitefly (Bemisia argentifolii) (Adults)

[0683] The active compounds were formulated in cyclohexanone as a 10,000 ppm solution supplied in tubes. The tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A non-ionic surfactant (Kinetic®) was included in the solution at a volume of 0.01% (v/v).

[0684] Cotton plants at the cotyledon stage (one plant per pot) were sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into a plastic cup and about 10 to 12 whitefly adults (approximately 3-5 days old) were introduced. The insects were collected using an aspirator and a nontoxic Tygon® tubing connected to a barrier pipette tip. The tip, containing the collected insects, was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding. Cups were covered with a reusable screened lid. Test plants were maintained in a growth room at about 25° C. and about 20-40% relative humidity for 3 days, avoiding direct exposure to fluorescent light (24-hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment, compared to untreated control plants.

[0685] In this test, the following compounds at 300 ppm showed over 75% mortality in comparison with untreated controls: C-2.

B.4. Southern Armyworm (Spodoptera eridania), 2nd Instar Larvae

[0686] The active compounds were formulated in cyclohexanone as a 10,000 ppm solution supplied in tubes. The tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01% (v/v).

[0687] Lima bean plants (variety Sieva) were grown 2 plants to a pot and selected for treatment at the 1.sup.st true leaf stage. Test solutions were sprayed onto the foliage by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into perforated plastic bags with a zip closure. About 10 to 11 armyworm larvae were placed into the bag and the bags zipped closed. Test plants were maintained in a growth room at about 25° C. and about 20-40% relative humidity for 4 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the bags. Mortality and reduced feeding were assessed 4 days after treatment, compared to untreated control plants.

[0688] In this test, the following compounds at 300 ppm showed over 75% mortality in comparison with untreated controls: C-1, C-2.

B.5. Tobacco Budworm (Heliothis virescens)

[0689] For evaluating control of tobacco budworm (Heliothis virescens) the test unit consisted of 96-well-microtiter plates containing an insect diet and 15-25 H. virescens eggs.

[0690] The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 10 μl, using a custom built micro atomizer, at two replications.

[0691] After application, microtiter plates were incubated at about 28±1° C. and about 80±5% relative humidity for 5 days. Egg and larval mortality was then visually assessed.

[0692] In this test, the following compounds at 800 ppm showed over 75% mortality in comparison with untreated controls: C-1, C-2, C-3, C-6, C-7, C-8, C-9, C-10, C-11, C-12, C-13, C-14.

B.6. Yellow Fever Mosquito (Aedes aegypti)

[0693] For evaluating control of yellow fever mosquito (Aedes aegypti) the test unit consisted of 96-well-microtiter plates containing 200 μl of tap water per well and 5-15 freshly hatched A. aegypti larvae. The active compounds were formulated using a solution containing 75% (v/v) water and 25% (v/v) DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 2.5 μl, using a custom built micro atomizer, at two replications.

[0694] After application, microtiter plates were incubated at 28+1° C., 80+5% RH for 2 days. Larval mortality was then visually assessed.

[0695] In this test, the following compounds at 800 ppm showed over 75% mortality in comparison with untreated controls: C-1, C-2, C-9, C-10, C-11, C-13, C-14.

B.7. Orchid Thrips (Dichromothrips corbetti)

[0696] Dichromothrips corbetti adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions. For testing purposes, the test compound is diluted in a 1:1 mixture of acetone:water (vol:vol), plus Kinetic® HV at a rate of 0.01% v/v.

[0697] Thrips potency of each compound was evaluated by using a floral-immersion technique. All petals of individual, intact orchid flowers were dipped into treatment solution and allowed to dry in Petri dishes. Treated petals were placed into individual re-sealable plastic along with about 20 adult thrips. All test arenas were held under continuous light and a temperature of about 28° C. for duration of the assay. After 3 days, the numbers of live thrips were counted on each petal. The percent mortality was recorded 72 hours after treatment.

[0698] In this test, the following compounds at 300 ppm showed over 75% mortality in comparison with untreated controls: C-1, C-2, C-10, C-11, C-12, C-13, C-14.

B.9. Western Flower Thrips (Frankliniella occidentalis)

[0699] The active compounds were formulated by a Tecan liquid handler in 100% cyclohexanone as a 10,000 ppm solution supplied in tubes. The 10,000 ppm solution was serially diluted in 100% cyclohexanone to make interim solutions. These served as stock solutions for which final dilutions were made by the Tecan in 50% acetone:50% water (v/v) into 10 or 20 ml glass vials. A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01% (v/v). The vials were then inserted into an automated electrostatic sprayer equipped with an atomizing nozzle for application to plants/insects.

[0700] Small (˜2″ in height) cotton plants are sprayed with test compounds at concentrations ranging from 300 to 0.01 ppm in acetone/water through the automated VPS. After drying, cotton leaves are removed and circular leaf discs (−1 cm diameter) are punched from the treated surface and transferred to clean 20 mL scintillation vials. Ten Western flower thrips (FRANOC) are aspirated into each scintillation vial. The vials with the leaf discs and thrips are kept in an upright incubator at 25° C. and 50% relative humidity with a 14:10 light:dark photoperiod. Each treatment is replicated twice.

[0701] Thrips mortality is assessed at 2 DAT (days after treatment), counting all thrips both dead and alive. [The average absolute mortality is calculated for each treatment.]

In this test, the following compounds at 300 ppm showed over 75% mortality in comparison with untreated controls: C-1, C-2, C-10.