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TRICYCLIC PESTICIDAL COMPOUNDS

20230141433 · 2023-05-11

    Inventors

    Cpc classification

    International classification

    Abstract

    The invention relates to compounds of formula (I), wherein the variables are as defined in the specification. It also relates to the use of compounds of formula (I) as an agrochemical pesticide; to pesticidal mixtures comprising compounds of formula (I); and to agrochemical or veterinary compositions comprising compounds of formula (I). Other objects are seed comprising compounds of formula (I); and methods for controlling invertebrate pests, infestation, or infection by invertebrate pests by application of compounds of formula (I).

    ##STR00001##

    Claims

    1. A compound of formula (I), or an agrochemically or veterinarily acceptable salt, stereoisomer, tautomer, or N-oxide thereof ##STR00096## wherein the variables in formula (I) have the following meaning, A is CH, N, or NH; E is N, O, S, NR.sup.E, or CR.sup.E; G, J are independently C or N; L is N or CR.sup.L; M is N or CR.sup.M; Q is N or CR.sup.Q; T is N or CR.sup.T; V is N or CR.sup.V; W is N or CR.sup.W; R.sup.E, R.sup.L, R.sup.M, R.sup.Q, R.sup.T, R.sup.V, and R.sup.W are independently selected from H, halogen, N.sub.3, 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, which groups are unsubstituted or substituted with halogen; C(═O)OR.sup.1, NR.sup.2R.sup.3, C.sub.1-C.sub.6-alkylen-NR.sup.2R.sup.3, O—C.sub.1-C.sub.6-alkylen-NR.sup.2R.sup.3, C.sub.1-C.sub.6-alkylen-CN, NH—C.sub.1-C.sub.6-alkylen-NR.sup.2R.sup.3, C(═O)NR.sup.2R.sup.3, C(═O)R.sup.4, SO.sub.2NR.sup.2R.sup.3, S(═O).sub.qR.sup.5, OR.sup.6, SR.sup.6, phenyl, and benzyl, wherein the phenyl ring g is unsubstituted or substituted with one or more, same or different substituents R.sup.11; R.sup.1 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, or C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, which groups are unsubstituted or substituted with halogen; C.sub.1-C.sub.6-alkylen-NR.sup.2R.sup.3, C.sub.1-C.sub.6-alkylen-CN, or phenyl or benzyl, wherein the phenyl ring is unsubstituted, or substituted with one or more, same or different substituents R.sup.11; R.sup.11 is selected from 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, 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, which groups are unsubstituted or substituted with halogen; 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, which groups are unsubstituted, or substituted with one or more, same or different substituent selected from halogen, CN and HO; C(═O)R.sup.21, C(═O)OR.sup.21, C(═O)NR.sup.21, C.sub.1-C.sub.6-alkylen-CN, or phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R.sup.11; R.sup.21 is H, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, 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, phenyl, or a saturated, partially-, or fully unsaturated 5- or 6-membered heterocycle, wherein the cyclic moieties are unsubstituted or substituted with one or more, same or different substituents R.sup.11; R.sup.3 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, which groups are unsubstituted or substituted with halogen; C.sub.1-C.sub.6-alkylen-CN, or phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R.sup.1; or NR.sup.2R.sup.3 may also form an N-bound, saturated 3- to 8-membered heterocycle, which in addition to the nitrogen atom may have 1 or 2 further heteroatoms or heteroatom moieties selected from 0, S(═O).sub.q, NH, and N—C.sub.1-C.sub.6-alkyl, and wherein the N-bound heterocycle is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy and C.sub.1-C.sub.4-haloalkoxy; R.sup.4 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, or C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, which groups are unsubstituted or substituted with one or more, same of different substituents selected from halogen, CN, and OH; phenyl or benzyl, wherein the phenyl ring unsubstituted, or substituted with one or more, same or different substituents R.sup.11; R.sup.5 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, or C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, which groups are unsubstituted or substituted with halogen; C.sub.1-C.sub.6-alkylen-NR.sup.2R.sup.3, C.sub.1-C.sub.6-alkylen-CN, phenyl or benzyl, wherein the phenyl ring is unsubstituted, or substituted with one or more, same or different substituents R.sup.11; R.sup.6 is phenyl, which is unsubstituted or substituted with one or more, same or different substituents R.sup.11; D is a moiety of formula ##STR00097## wherein the “&”-symbol signifies the connection to the remainder of formula (I), wherein the dotted circle in the 5-membered ring means that the 5-membered ring may be saturated, partially unsaturated, or fully unsaturated; R.sup.X 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, which are unsubstituted or substituted with halogen; or phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R.sup.11; X is N, S, O, CR.sup.7, or NR.sup.8; Y and Z are independently C or N, wherein at least one of the variables selected from Y and Z is C; D* is a 5- or 6-membered saturated, partially unsaturated, or fully unsaturated carbo- or heterocycle, which carbo- or heterocycle includes the atoms Y and Z as ring members and is unsubstituted or substituted with one or more, same or different substituents R.sup.9, and wherein said heterocycle comprises 0, 1, 2, or 3, same or different heteroatoms O, N, or S in addition to those that may be present as ring members Y and Z; R.sup.7 is H, halogen, OH, CN, NC, NO.sub.2, N.sub.3, SCN, NCS, NCO, SF.sub.5, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-cycloalkenyl, C.sub.2-C.sub.6-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R.sup.G1; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, and is unsubstituted, or substituted with one or more, same or different substituents R.sup.H1, and wherein said N- and S-atoms are independently oxidized, or non-oxidized; phenyl, which is unsubstituted, or substituted with one or more, same or different substituents R.sup.J1; OR.sup.K1, SR.sup.K1, OC(═O)R.sup.K1, OC(═O)OR.sup.K1, OC(═O)NR.sup.L1R.sup.M1, OC(═O)SR.sup.K1, OC(═S)NR.sup.L1R.sup.M1, OC(═S)SR.sup.K1, OS(═O).sub.qR.sup.K1, OS(═O).sub.qNR.sup.L1R.sup.M1, ONR.sup.L1R.sup.M1, ON═CR.sup.N1R.sup.O1, NR.sup.L1R.sup.M1, NOR.sup.K1, ONR.sup.L1R.sup.M1, N═CR.sup.N1R.sup.O1, NNR.sup.L1, N(R.sup.L1)C(═O)R.sup.K1, N(R.sup.L1)C(═O)OR.sup.K1, S(═O).sub.qR.sup.V1, SC(═O)SR.sup.K1, SC(═O)NR.sup.L1R.sup.M1, S(═O).sub.qNR.sup.L1R.sup.M1, C(═O)R.sup.P1, C(═S)R.sup.P1, C(═O)NR.sup.L1R.sup.M1, C(═O)OR.sup.K1, C(═S)NR.sup.L1R.sup.M1, C(═S)OR.sup.K1, C(═S)SR.sup.K1, C(═NR.sup.L1)R.sup.M1, C(═NR.sup.L1)NR.sup.M1R.sup.R1, Si(R.sup.S1).sub.2R.sup.T1; R.sup.8 is H, CN, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-cycloalkenyl, C.sub.2-C.sub.6-alkynyl, which groups are unsubstituted or substituted with one or more, same or different substituents R.sup.G1; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, and is unsubstituted, or substituted with one or more, same or different substituents R.sup.H1, and wherein said N- and S-atoms are independently oxidized, or non-oxidized; phenyl, which is unsubstituted, or substituted with one or more, same or different substituents R.sup.J1; OR.sup.K1, SR.sup.K1, OC(═O)R.sup.K1, OC(═O)OR.sup.K1, OC(═O)NR.sup.L1R.sup.M1, OC(═O)SR.sup.K1, OC(═S)NR.sup.L1R.sup.M1, OC(═S)SR.sup.K1, OS(═O).sub.qR.sup.K1, OS(═O).sub.qNR.sup.L1R.sup.M1, ONR.sup.L1R.sup.M1, ON═CR.sup.N1R.sup.O1, NR.sup.L1R.sup.M1, NOR.sup.K1, ONR.sup.L1R.sup.M1, N═CR.sup.N1R.sup.O1, NNR.sup.L1, N(R.sup.L1)C(═O)R.sup.K1, N(R.sup.L1)C(═O)OR.sup.K1, S(═O).sub.qR.sup.V1, SC(═O)SR.sup.K1, SC(═O)NR.sup.L1R.sup.M1, S(═O).sub.qNR.sup.L1R.sup.M1, C(═O)R.sup.P1, C(═S)R.sup.P1, C(═O)NR.sup.L1R.sup.M1, C(═O)OR.sup.K1, C(═S)NR.sup.L1R.sup.M1, C(═S)OR.sup.K1, C(═S)SR.sup.K1, C(═NR.sup.L1)R.sup.M1, C(═NR.sup.L1)NR.sup.M1R.sup.R1, or Si(R.sup.S1).sub.2R.sup.T1; each R.sup.9 is independently H, halogen, OH, CN, NC, NO.sub.2, N.sub.3, SCN, NCS, NCO, SF.sub.5, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-cycloalkenyl, or C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.3-alkyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R.sup.G1; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, and is unsubstituted, or substituted with one or more, same or different substituents R.sup.H1, and wherein said N- and S-atoms are independently oxidized, or non-oxidized; phenyl, which is unsubstituted, or substituted with one or more, same or different substituents R.sup.J1; OR.sup.K1, SR.sup.K1, OC(═O)R.sup.K1, OC(═O)OR.sup.K1, OC(═O)NR.sup.L1R.sup.M1, OC(═O)SR.sup.K1, OC(═S)NR.sup.L1R.sup.M1, OC(═S)SR.sup.K1, OS(═O).sub.qR.sup.K1, OS(═O).sub.qNR.sup.L1R.sup.M1, ONR.sup.L1R.sup.M1, ON═CR.sup.N1R.sup.O1, NR.sup.L1R.sup.M1, NOR.sup.K1, ONR.sup.L1R.sup.M1, N═CR.sup.N1R.sup.O1, NNR.sup.L1, N(R.sup.L1)C(═O)R.sup.K1, N(R.sup.L1)C(═O)OR.sup.K1, S(═O).sub.qR.sup.V1, SC(═O)SR.sup.K1, SC(═O)NR.sup.L1R.sup.M1, S(═O).sub.qNR.sup.L1R.sup.M1, C(═O)R.sup.P1, C(═S)R.sup.P1, C(═O)NR.sup.L1R.sup.M1, C(═O)OR.sup.K1, C(═S)NR.sup.L1R.sup.M1, C(═S)OR.sup.K1, C(═S)SR.sup.K1, C(═NR.sup.L1)R.sup.M1, C(═NR.sup.L1)NR.sup.M1R.sup.R1, or Si(R.sup.S1).sub.2R.sup.T1; or two substituents R.sup.G1 form, together with the ring members of ring D to which they are bound, a 5- or 6-membered saturated, partially unsaturated, or fully unsaturated carbo- or heterocycle, which carbo- or heterocycle is unsubstituted, or substituted with one or more, same or different substituents R.sup.J1, and wherein said heterocycle comprises one or more, same or different heteroatoms O, N, or S; each R.sup.G1 is independently halogen, OH, CN, NC, NO.sub.2, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkenyl, which groups are unsubstituted or substituted with one or more, same or different substituents selected from halogen, OH, CN, C.sub.1-C.sub.3-alkoxy, C.sub.1-C.sub.3-haloalkoxy, and C.sub.1-C.sub.3-alkyl-carbonyl; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, and is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C.sub.1-C.sub.3-alkoxy, C.sub.1-C.sub.3-haloalkoxy, and C.sub.1-C.sub.3-alkyl-carbonyl, and wherein said N- and S-atoms are independently oxidized, or non-oxidized; phenyl, which is unsubstituted or substituted with one or more, same or different substituents selected from halogen, OH, CN, NO.sub.2, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-haloalkyl, C.sub.1-C.sub.3-alkoxy, C.sub.1-C.sub.3-haloalkoxy, and C.sub.1-C.sub.3-alkyl-carbonyl; OR.sup.K1, SR.sup.K1, OC(═O)R.sup.K1, OC(═O)OR.sup.K1, OC(═O)NR.sup.L1R.sup.M1, OC(═O)SR.sup.K1, OC(═S)NR.sup.L1R.sup.M1, OC(═S)SR.sup.K1, OS(═O).sub.qR.sup.K1, OS(═O).sub.qNR.sup.L1R.sup.M1, ONR.sup.L1R.sup.M1, ON═CR.sup.N1R.sup.O1, NR.sup.L1R.sup.M1, NOR.sup.K1, ONR.sup.L1R.sup.M1, N═CR.sup.N1R.sup.O1, NNR.sup.L1, N(R.sup.L1)C(═O)R.sup.K1, N(R.sup.L1)C(═O)OR.sup.K1, S(═O).sub.qR.sup.V1, SC(═O)SR.sup.K1, SC(═O)NR.sup.L1R.sup.M1, S(═O).sub.qNR.sup.L1R.sup.M1, C(═O)R.sup.P1, C(═S)R.sup.P1, C(═O)NR.sup.L1R.sup.M1, C(═O)OR.sup.K1, C(═S)NR.sup.L1R.sup.M1, C(═S)OR.sup.K1, C(═S)SR.sup.K1, C(═NR.sup.L1)R.sup.M1, C(═NR.sup.L1)NR.sup.M1R.sup.R1, Si(R.sup.S1).sub.2R.sup.T1; each R.sup.H1 is independently halogen, CN, NC, NO.sub.2, SCN, NCS, NCO, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkenyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C.sub.1-C.sub.10-alkoxy, C.sub.1-C.sub.3-haloalkoxy, and C.sub.1-C.sub.3-alkyl-carbonyl; phenyl, which is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, NO.sub.2, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-haloalkyl, OR.sup.K1, SR.sup.K1, OC(═O)R.sup.K1, OC(═O)OR.sup.K1, OC(═O)NR.sup.L1R.sup.M1, OC(═O)SR.sup.K1, OC(═S)NR.sup.L1R.sup.M1, OC(═S)SR.sup.K1, OS(═O).sub.qR.sup.K1, OS(═O).sub.qNR.sup.L1R.sup.M1, ONR.sup.L1R.sup.M1, ON═CR.sup.N1R.sup.O1, NR.sup.L1R.sup.M1, NOR.sup.K1, ONR.sup.L1R.sup.M1, N═CR.sup.N1R.sup.O1, NNR.sup.L1, N(R.sup.L1)C(═O)R.sup.K1, N(R.sup.L1)C(═O)OR.sup.K1, S(═O).sub.qR.sup.V1, SC(═O)SR.sup.K1, SC(═O)NR.sup.L1R.sup.M1, S(═O).sub.qNR.sup.L1R.sup.M1, C(═O)R.sup.P1, C(═S)R.sup.P1, C(═O)NR.sup.L1R.sup.M1, C(═O)OR.sup.K1, C(═S)NR.sup.L1R.sup.M1, C(═S)OR.sup.K1, C(═S)SR.sup.K1, C(═NR.sup.L1)R.sup.M1, C(═NR.sup.L1)NR.sup.M1R.sup.R1, Si(R.sup.S1).sub.2R.sup.T1; or two geminal substituents R.sup.H1 form together with the atom to which they are bound a group ═O, ═S, or ═NR.sup.L; each R.sup.J1 is independently halogen, CN, NC, NO.sub.2, SCN, NCS, NCO, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkenyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C.sub.1-C.sub.10-alkoxy, C.sub.1-C.sub.3-haloalkoxy, and C.sub.1-C.sub.3-alkyl-carbonyl; phenyl, which is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, NO.sub.2, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-haloalkyl, OR.sup.K1, SR.sup.K1, OC(═O)R.sup.K1, OC(═O)OR.sup.K1, OC(═O)NR.sup.L1R.sup.M1, OC(═O)SR.sup.K1, OC(═S)NR.sup.L1R.sup.M1, OC(═S)SR.sup.K1, OS(═O).sub.qR.sup.K1, OS(═O).sub.qNR.sup.L1R.sup.M1, ONR.sup.L1R.sup.M1, ON═CR.sup.N1R.sup.O1, NR.sup.L1R.sup.M1, NOR.sup.K1, ONR.sup.L1R.sup.M1, N═CR.sup.N1R.sup.O1, NNR.sup.L1, N(R.sup.L1)C(═O)R.sup.K1, N(R.sup.L1)C(═O)OR.sup.K1, S(═O).sub.qR.sup.V1, SC(═O)SR.sup.K1, SC(═O)NR.sup.L1R.sup.M1, S(═O).sub.qNR.sup.L1R.sup.M1, C(═O)R.sup.P1, C(═S)R.sup.P1, C(═O)NR.sup.L1R.sup.M1, C(═O)OR.sup.K1, C(═S)NR.sup.L1R.sup.M1, C(═S)OR.sup.K1, C(═S)SR.sup.K1, C(═NR.sup.L1)R.sup.M1, C(═NR.sup.L1)NR.sup.M1R.sup.R1, Si(R.sup.S1).sub.2R.sup.T1; each R.sup.K1 is independently 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, which groups are unsubstituted or substituted with one or more, same or different substituents selected from halogen, CN, NR.sup.M1R.sup.N1; C(═O)NR.sup.M1R.sup.N1, C(═O)R.sup.T1; or phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R.sup.X1; each R.sup.L1 is independently 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, which groups are unsubstituted or substituted with halogen; C.sub.1-C.sub.6-alkylen-CN; phenyl and benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents R.sup.X1; each R.sup.M1, R.sup.R1 is independently 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, which groups are unsubstituted or substituted with halogen; C.sub.1-C.sub.6-alkylen-CN; or phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R.sup.X1; each moiety NR.sup.M1R.sup.R1 or NR.sup.L1R.sup.M1 may also form an N-bound, saturated 5- to 8-membered heterocycle, which in addition to the nitrogen atom may have 1 or 2 further heteroatoms or heteroatom moieties selected from O, S(═O).sub.q, and N—R′, wherein R′ is H or C.sub.1-C.sub.6-alkyl and wherein the N-bound heterocycle is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy and C.sub.1-C.sub.4-haloalkoxy; each R.sup.N1 is independently H, halogen, CN, NO.sub.2, SCN, C.sub.1-C.sub.10-alkyl, C.sub.3-C.sub.5-cycloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-cycloalkenyl, C.sub.2-C.sub.6-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkyl, and C.sub.1-C.sub.6-haloalkoxy; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, and is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-alkoxy, C.sub.1-C.sub.3-haloalkyl, and C.sub.1-C.sub.3-haloalkoxy, and wherein said N- and S-atoms are independently oxidized, or non-oxidized; phenyl, which is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-alkoxy, C.sub.1-C.sub.3-haloalkyl, and C.sub.1-C.sub.3-haloalkoxy; each R.sup.O1 is independently H, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-cycloalkyl, C.sub.1-C.sub.2-alkoxy-C.sub.1-C.sub.2-alkyl, phenyl, or benzyl; each R.sup.P1 is independently 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, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R.sup.X1; each R.sup.S1, R.sup.T1 is independently H, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.4-haloalkoxy-C.sub.1-C.sub.4-alkyl, or phenyl; each R.sup.V1 is independently 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, which are unsubstituted or substituted with halogen; or phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with R.sup.X1; each R.sup.X1 is independently 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, 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, which groups are unsubstituted or substituted with halogen; the index m is 0, 1, or 2; the index q is 0, 1, or 2.

    2. The compound of formula (I) according to claim 1, wherein A is N.

    3. The compound of formula (I) according to claim 1, wherein formula (I) is selected from formulae (I-A), (I-C), and (I-D). ##STR00098##

    4. The compound of formula (I) according to claim 1, wherein R.sup.L, R.sup.M, R.sup.Q, R.sup.T, R.sup.V, and R.sup.W independently are selected from 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.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, and C.sub.1-C.sub.6-alkyl-S(═O).sub.q, which groups are unsubstituted or substituted with halogen.

    5. The compound of formula (I) according to claim 1, wherein D is selected from the formulae D1, D3, D8, and D50, ##STR00099## wherein n is 0, 1, 2, 3, or 4.

    6. The compound of formula (I) according to claim 1, wherein R.sup.X is C.sub.1-C.sub.4-alkyl, which is unsubstituted or substituted with halogen.

    7. The compound of formula (I) according to claim 1, wherein R.sup.9 is independently selected from H, halogen, OH, CN, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-alkoxy, C.sub.2-C.sub.3-alkenyl, C.sub.2-C.sub.3-alkynyl, and C.sub.3-C.sub.6-cycloalkyl, which groups are unsubstituted or substituted with CN or halogen.

    8. (canceled)

    9. A pesticidal mixture comprising a compound of formula (I) as defined in claim 1, and another agrochemically active ingredient.

    10. An agrochemical or veterinary composition comprising a compound of formula (I) as defined in claim 1 and a liquid or solid carrier.

    11. A method for controlling invertebrate pests, infestation, or infection by invertebrate pests, comprising contacting the pests, their food supply, habitat, breeding grounds or their locus with a compound of formula (I) as defined in claim 1 in a pesticidally effective amount.

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

    13. A seed comprising a compound of formula (I) as defined in claim 1 in an amount of from 0.1 g to 10 kg per 100 kg of seeds.

    14. A method for treating, or protecting an animal against infestation or infection by a parasite, or controlling, or preventing infestations or infections of animals by a parasite, comprising administering or applying orally, topically, or parenterally to the animal a compound of the general formula (I) as defined in claim 1.

    15. The pesticidal mixture of claim 9 wherein the agrochemically active ingredient is an insecticide, fungicide, or mixture thereof.

    Description

    A. PREPARATION OF COMPOUNDS

    [0374] Materials: Unless otherwise noted, reagents and solvents were purchased at highest commercial quality and used without further purification. Dry tetrahydrofuran (THF), ethylacetate (EtOAc), dimethylsulfoxide (DMSO), acetone, ethanol (EtOH), benzene, dimethylformamide, (DMF), diisopropylethylamine (DIPEA), hexafluorophosphate azabenzotriazole tetramethyl uronium (HATU), pyridine, and CH2Cl2 were purchased from commercial providers.

    [0375] All reactions were monitored by thin-layer chromatography (TLC) using Merck silica gel 60 F.sub.254 pre-coated plates (0.25 mm). Flash chromatography was carried out with Kanto Chemical silica gel (Kanto Chemical, silica gel 60N, spherical neutral, 0.040-0.050 mm, Cat.-No. 37563-84). .sup.1H NMR spectra were recorded on JEOL JNM-ECA-500 (500 MHz). Chemical shifts are expressed in ppm downfield from the internal solvent peaks for acetone-d.sub.6 (.sup.1H; δ=2.05 ppm) and CD.sub.3OD (.sup.1H; δ=3.30 ppm), and J values are given in Hertz. The following abbreviations were used to explain the multiplicities: s=singlet, d=doublet, t=triplet, q=quartet, dd=double doublet, dt=double triplet, m=multiplet, br=broad. High-resolution mass spectra were measured on a JEOL JMS-T100LP.

    [0376] Characterization: The compounds were characterized by coupled High Performance Liquid Chromatography with mass spectrometry (HPLC/MS). Method A: UHPLC-MS on Shimadzu Nexera UHPLC & Shimadzu LCMS 20-20 ESI. Analytical UHPLC column: Phenomenex Kinetex 1.7 μm XB-C18 100A; 50×2.1 mm; mobile phase: A: water+0.1% TFA; B: acetonitrile; gradient: 5-100% B in 1.50 minutes; 100% B 0.20 min; flow: 0.8-1.0 mL/min in 1.50 minutes at 60° C. MS-method: ESI positive; mass range (m/z) 100-700. M+1 means mass of the molecule plus 1 Dalton.

    Synthesis Example A

    Example 1: 2-(3-ethylsulfonylimidazo[1,2-a]pyridin-2-yl)-1-methyl-6-(trifluoromethoxy)imidazo[4,5-c]quinoline (compound C-4)

    Step 1: Synthesis of N-methyl-3-nitro-8-(trifluoromethoxy)quinolin-4-amine

    [0377] To a solution of 4-chloro-3-nitro-8-(trifluoromethoxy)quinoline (4 g) in THF (40 mL), at 20 to 25° C., was added methylamine (40 mL, 2M solution in THF). The reaction mixture was then warmed to 50° C. and stirred for 1 h. Reaction was monitored by TLC, after the complete conversion of 4-chloro-3-nitro-8-(trifluoromethoxy)quinoline, the reaction mixture was then concentrated in vacuo, to afford a residue containing N-methyl-3-nitro-8-(trifluoromethoxy)quinolin-4-amine (3.9 g, 100% yield), which was used in Step 2 without further purification. Similar procedure is described in WO 2008117225. HPLC-MS (Method A): mass found for C.sub.11HF.sub.3N.sub.3O.sub.3 [M+H]+ 287.8; tR=0.791 min.

    Step 2: Synthesis of N4-methyl-8-(trifluoromethoxy)quinoline-3,4-diamine

    [0378] To a suspension of Zn-powder (3.6 g) in CH.sub.3COOH (60 mL) was slowly added a solution of N-methyl-3-nitro-8-(trifluoromethoxy)quinolin-4-amine (3.9 g) in 10 mL EtOAc at a temperature of up to 30° C. The reaction mixture was stirred for an additional 2 h at 20 to 25° C. After the complete conversion of N-methyl-3-nitro-8-(trifluoromethoxy)quinolin-4-amine, the reaction mixture was diluted with EtOAc and filtrated. The filtrate was washed with H.sub.2O. The combined H.sub.2O-phases were adjusted to an alkaline pH with aqueous NaOH and extracted with EtOAc. The combined organic extracts were dried and concentrated in vacuo to afford a residue containing N4-methyl-8-(trifluoromethoxy)quinoline-3,4-diamine (2.35 g, 67% yield), which was used in Step 3 without further purification. HPLC-MS (Method A): mass found for C.sub.11H.sub.10F.sub.3N.sub.3O [M+H]+ 257.8; tR=0.665 min.

    Step 3: Synthesis of 3-ethylsulfanyl-N-[4-(methylamino)-8-(trifluoromethoxy)-3-quinolyl]imidazo[1,2-a]pyridine-2-carboxamide

    [0379] To a stirred solution of N4-methyl-8-(trifluoromethoxy)quinoline-3,4-diamine (0.417 g, 0.0016 mol) in DMF (15 V) at 0° C., DIPEA (0.34 g, 0.003 mol) and 3-ethylsulfanylimidazo[1,2-a]pyridine-2-carboxylic acid (was synthesised similarly as mentioned in WO2016162318) (0.30 g, 0.0013 mol) were added, then was followed by the addition of HATU (0.82 g, 0.002 mol) portion wise. The resultant reaction mixture was stirred at the room temperature for 24 h. Reaction was monitored by TLC, after the complete conversion of starting material, reaction mixture was partitioned between ethyl acetate (150 mL×2) and water (250 mL×2). Organic layer was separated, dried over Na.sub.2SO.sub.4 and concentrated to get crude mass. Crude was purified by column chromatography eluting with 20% ethyl acetate in heptane gradient to afford 3-ethylsulfanyl-N-[4-(methylamino)-8-(trifluoromethoxy)-3-quinolyl]imidazo[1,2-a]pyridine-2-carboxamide as an off white solid. (0.60 g, 95% yield). LC-MS: mass calculated for C.sub.21H.sub.18F.sub.3N.sub.5O.sub.2S [M+H].sup.+ 462.0, found 462.0; R.sub.t=0.867 min (R.sub.t: retention time).

    Step 4: Synthesis of 2-(3-ethylsulfanylimidazo[1,2-a]pyridin-2-yl)-1-methyl-6-(trifluoromethoxy)imidazo[4,5-c]quinoline

    [0380] A suspension of 3-ethylsulfanyl-N-[4-(methylamino)-8-(trifluoromethoxy)-3-quinolyl]imidazo[1,2-a]pyridine-2-carboxamide (0.21 g, 0.46 mmol) in acetic acid (3 V) was refluxed for 5 h. Reaction was monitored by HPLC, after the complete conversion of starting material, reaction mixture was partitioned between ethyl acetate (150 mL×2) and water (250 mL×2). Organic layer was separated, washed with saturated bicarbonate solution (100 mL×2). The combined organic layers were separated, dried over Na.sub.2SO.sub.4 and concentrated to get crude mass. Crude was purified by column chromatography eluting with 10% ethyl acetate in heptane gradient to afford 2-(3-ethylsulfanylimidazo[1,2-a]pyridin-2-yl)-1-methyl-6-(trifluoromethoxy)imidazo[4,5-c]quinoline as an off white solid. (0.14 g, 67% yield). LC-MS: mass calculated for C.sub.21H.sub.16F.sub.3N.sub.5OS [M+H].sup.+ 444.0, found 444.0; R.sub.t=1.013 min (R.sub.t: retention time).

    Step 5: Synthesis of 2-(3-ethylsulfonylimidazo[1,2-a]pyridin-2-yl)-1-methyl-6-(trifluoromethoxy)imidazo[4,5-c]quinoline

    [0381] A suspension of 2-(3-ethylsulfanylimidazo[1,2-a]pyridin-2-yl)-1-methyl-6-(trifluoromethoxy)imidazo[4,5-c]quinoline (139 mg, 0.31 mmol) in acetic acid (3 mL) was stirred at RT. Then to the reaction mixture Na.sub.2WO.sub.4.H.sub.2O (3 mg, 0.0094 mmol) and 30% H.sub.2O.sub.2 (89 μL) was added and the reaction was allowed to stir at RT overnight. Reaction was monitored by HPLC, after the complete conversion of starting material, reaction mixture was completely evaporated on rotavapor. The reaction mixture was dissolved in Ethyl acetate (15 mL) and washed with saturated bicarbonate solution (20 mL×2). The combined organic layers were separated, dried over Na.sub.2SO.sub.4 and concentrated to get crude mass. Crude was purified by column chromatography eluting with 10% ethyl acetate in heptane gradient to afford 2-(3-ethylsulfonylimidazo[1,2-a]pyridin-2-yl)-1-methyl-6-(trifluoromethoxy)imidazo[4,5-c]quinoline as an off white solid. (75 mg, 50.7% yield). LC-MS: mass calculated for C.sub.21H.sub.16F.sub.3N.sub.5O.sub.3S [M+H].sup.+ 476.0, found 476.0; R.sub.t=0.966 min (R.sub.t: retention time).

    Example 2: 8-(3-ethylsulfonylimidazo[1,2-a]pyridin-2-yl)-4-(trifluoromethyl)imidazo[1,2-a][1,8]naphthyridine (compound C-7)

    Step 1: Synthesis of N-[7-hydroxy-5-(trifluoromethyl)-1,8-naphthyridin-2-yl]acetamide

    [0382] A suspension of 7-amino-4-(trifluoromethyl)-1,8-naphthyridin-2-ol (4 g, 0.017 mol) in acetic anhydride (10 V) was refluxed to 2 h. Reaction was monitored by HPLC, after the complete conversion of 7-amino-4-(trifluoromethyl)-1,8-naphthyridin-2-ol, the above reaction mixture was cooled to room temperature, obtained solid was filtered and washed with water (100×2). Solid was dried over rota to afford desired compound 2 as a brown solid. (3.9 g, 83% yield). The above reaction was followed by the literature Organic & Biomolecular Chemistry Volume 10. LC-MS: mass calculated for C.sub.11H.sub.8H.sub.3N.sub.3O.sub.2 [M+H].sup.+ 272.0, found 271.9; R.sub.t=0.760 min (R.sub.t: retention time).

    Step 2: Synthesis of N-[7-chloro-5-(trifluoromethyl)-1,8-naphthyridin-2-yl]acetamide

    [0383] A suspension of N-[7-hydroxy-5-(trifluoromethyl)-1,8-naphthyridin-2-yl]acetamide (3.9 g, 0.014 mol) in POCl.sub.3 (10 V) at 0° C., then the resultant reaction mixture was gradually heated to 100° C. for 90 minutes. Reaction was monitored by HPLC, after the complete conversion of SM, the above reaction mixture was cooled to room temperature, quenched with water (200 mL) maintaining the exothermicity of reaction mixture. Then, was followed by the addition of 10% ammonia solution until pH 9. Obtained solid was filtered and washed with water (100×2). Solid was dried over rota to afford desired N-[7-chloro-5-(trifluoromethyl)-1,8-naphthyridin-2-yl]acetamide as a brown solid. (3.9 g, 95% yield). The above reaction was followed by literature as Journal of the American Chemical Society Volume 123. LC-MS: mass calculated for C.sub.11H.sub.7ClF.sub.3N.sub.3O [M+H].sup.+ 290.0, found 289.7; R.sub.t=1.001 min (R.sub.t: retention time).

    Step 3: Synthesis of 7-chloro-5-(trifluoromethyl)-1,8-naphthyridin-2-amine

    [0384] A suspension of N-[7-chloro-5-(trifluoromethyl)-1,8-naphthyridin-2-yl]acetamide (3.9 g, 0.013 mol) in 10% sulphuric acid (20 V) was refluxed for 2 h. Reaction was monitored by HPLC, after the complete conversion of SM, the above reaction mixture was cooled to room temperature, quenched with water (200 mL) maintaining the exothermicity of reaction mixture. Then, was followed by the addition of 10% ammonia solution until pH 9. Obtained solid was filtered and washed with water (100×2). Solid was dried over rota to afford desired 7-chloro-5-(trifluoromethyl)-1,8-naphthyridin-2-amine as a yellow solid. (3.5 g, 90% yield). The above reaction was followed by literature as WO 2016210234 A1. LC-MS: mass calculated for C.sub.9H.sub.5ClF.sub.3N.sub.3[M+H].sup.+ 248.0, found 247.8; R.sub.t=0.759 min (R.sub.t: retention time).

    Step 4: Synthesis of 2-chloro-8-(3-ethylsulfonylimidazo[1,2-a]pyridin-2-yl)-4-(trifluoromethyl)imidazo[1,2-a][1,8]naphthyridine

    [0385] To a stirred solution of 7-chloro-5-(trifluoromethyl)-1,8-naphthyridin-2-amine (1 g, 0.004 mol) in tert-butanol (10 V) was added 2-bromo-1-(3-ethylsulfonylimidazo[1,2-a]pyridin-2-yl)ethanone (synthesised as described in WO2016129684 A1) (1.34 g, 0.004 mol) and the resultant reaction mixture was heated in Radley's to 95° C. for 5 days. Reaction was monitored by TLC, after the complete conversion of SM, the above reaction mixture was filtered through celite bed, celite bed was washed with ethyl acetate (30 mL×3), filtrate was collected and concentrated under reduced pressure to get crude mass. Crude was purified by column chromatography eluting 40% with ethyl acetate in heptane gradient to afford 2-chloro-8-(3-ethylsulfonylimidazo[1,2-a]pyridin-2-yl)-4-(trifluoromethyl)imidazo[1,2-a][1,8]naphthyridine as a brown solid (0.5 g, 34% yield). The compound was synthesized using similar procedure as described in WO 2017/167832. LC-MS: mass calculated for C.sub.20H.sub.13ClF.sub.3N.sub.5O.sub.2S [M+H].sup.+ 480.0, found 480.0; R.sub.t=1.031 min (R.sub.t: retention time).

    Step 5: Synthesis of 8-(3-ethylsulfonylimidazo[1,2-a]pyridin-2-yl)-4-(trifluoromethyl) imidazo[1,2-a][1,8]naphthyridine

    [0386] To a stirred solution of 2-chloro-8-(3-ethylsulfonylimidazo[1,2-a]pyridin-2-yl)-4-(trifluoromethyl)imidazo[1,2-a][1,8]naphthyridine (0.5 g, 0.001 mol) in methanol (5 V), were added cyclohexene (0.34 g, 0.004 mol) and Pd 10% on activated carbon (0.106 g, 0.1 mmol) in microwave at 90° C. for 30 minutes. Reaction was monitored by HPLC, after the complete conversion of SM, reaction mixture was filtered through celite bed, celite bed was washed with ethyl acetate (30 mL×3). Filtrate was concentrated on rota and the residue was subjected to purification by column chromatography eluting with 10% ethyl acetate in heptane gradient to afford desired compound as an off white solid. (0.16 g, 37% yield). LC-MS: mass calculated for C.sub.20H.sub.14F.sub.3N.sub.5O.sub.2 [M+H].sup.+ 446.0, found 446.0; R.sub.t=1.008 min (R.sub.t: retention time).

    Example 3: 2-(3-ethylsulfonylimidazo[1,2-a]pyridin-2-yl)-1-methyl-5-(trifluoromethyl)imidazo[4,5-f]quinoline (compound C-11)

    Step 1: synthesis of N-[6-nitro-8-(trifluoromethyl)-5-quinolyl]acetamide

    [0387] To a solution of 6-nitro-8-(trifluoromethyl)quinolin-5-amine (10.03 mmol) and (CH.sub.3CH.sub.2).sub.3N (30.1 mmol) in THF (25 ml) at 20 to 25° C. was added acetylacetate (50.16 mmol) dropwise. The resulting reaction mixture was stirred at 20 to 25° C. for 7 days. Then, (CH.sub.3CH.sub.2).sub.3N (10.03 mmol) and acetyl acetate (20.06 mmol) were added and the reaction mixture, which was subsequently stirred for another 7 days. The reaction mixture was then concentrated under reduced pressure to afford a residue. The residue was dissolved in H.sub.2O, and extracted. The organic layer was dried, filtered and concentrated under reduced pressure to afford N-[6-nitro-8-(trifluoromethyl)-5-quinolyl]acetamide (2.97 g) The crude product was used in the next step without further purification. LC/MS retention time: 1.048 min, m/z=300 (M+H.sup.+)

    Step 2: synthesis N-methyl-N-[6-nitro-8-(trifluoromethyl)-5-quinolyl]acetamide

    [0388] To a solution of N-[6-nitro-8-(trifluoromethyl)-5-quinolyl]acetamide (9.93 mmol) in DMF (40 ml) at 20 to 25° C. was added Cs.sub.2CO.sub.3 (29.78 mmol). The reaction mixture was then cooled to 0° C. and iodomethane (14.89 mmol) was added dropwise. The resulting mixture was allowed to warm up to 20 to 25° C. and stirred for 12-16 hours. The reaction mixture was then concentrated under reduced pressure to afford a residue. The residue was dissolved in CH.sub.2Cl.sub.2 and washed with H.sub.2O. The organic layer was dried, filtered and concentrated under reduced pressure to afford N-methyl-N-[6-nitro-8-(trifluoromethyl)-5-quinolyl]acetamide (2.85 g). The crude product was used in the next step without further purification. LC/MS retention time: 0.962 min, m/z=314 (M+H.sup.+)

    Step 3: synthesise of N-methyl-6-nitro-8-(trifluoromethyl)quinolin-5-amine

    [0389] To a solution of N-methyl-N-[6-nitro-8-(trifluoromethyl)-5-quinolyl]acetamide (9.10 mmol) in CH.sub.3COOH (conc., 25 ml) at 20 to 25° C. was added sulfuric acid (conc., 3.5 ml). The resulting reaction mixture was heated to 100° C. and stirred for 6 hours. After cooling to 20 to 25° C., the mixture was concentrated under reduced pressure to afford a residue. The residue was dissolved in H.sub.2O, treated with an aqueous saturated solution of NaHCO.sub.3 until pH 10-11 was reached and extracted. The organic layer was dried, filtered and concentrated under reduced pressure to give N-methyl-6-nitro-8-(trifluoromethyl)quinolin-5-amine (1.19 g). The crude product was used in the next step without further purification. LC/MS retention time: 1.053 min, m/z=272 (M+H.sup.+)

    Step 4: N5-methyl-8-(trifluoromethyl)quinoline-5,6-diamine

    [0390] To a solution of N-methyl-6-nitro-8-(trifluoromethyl)quinolin-5-amine (7.04 mmol) in CH.sub.3COOCH.sub.2CH.sub.3 (50 ml) at 20 to 25° C. under N.sub.2 atmosphere was added Pd (10% on C, 750 mg, 0.70 mmol). The flask was purged with H.sub.2, and the resulting mixture stirred for 12 to 16 hours. Then, the reaction mixture was filtered und the filtrate was concentrated under reduced pressure to afford N5-methyl-8-(trifluoromethyl)quinoline-5,6-diamine (1.68 g). The crude product was used in the next step without further purification. LC/MS retention time: 0.690 min, m/z=242 (M+H.sup.+)

    Step 5: 2-(3-ethylsulfonylimidazo[1,2-a]pyridin-2-yl)-1-methyl-5-(trifluoromethyl)imidazo[4,5-f]quinoline (compound C-11)

    [0391] Compound C-11 was obtained from N5-methyl-8-(trifluoromethyl)quinoline-5,6-diamine by a series of reaction steps as described in Example 1, Steps 3-5. LC-MS retention time: 1,037 min, m/z=461.0 (M+H.sup.+)

    Example 4: Synthesis of 2-(3-ethylsulfonylimidazo[1,2-a]pyrimidin-2-yl)-6-methoxy-1-methyl-imidazo[4,5-c]quinoline (compound C-17)

    Step-1: synthesis of ethyl imidazo[1,2-a]pyrimidine-2-carboxylate

    [0392] To a stirred solution of 2-aminopyrimidine (0.010 mol) in acetone (10 mL) was added slowly ethyl 3-bromo-2-oxo-propanoate (0.010 mol) dropwise over a period of 10 min at 20 to 25° C. Subsequently, the reaction mixture was heated to reflux for 2 hours. Then the precipitate was filtered off and the resulting solid was dissolved in a mixture of CH.sub.3CH.sub.2OH:H.sub.2O mixture (10:3) and heated to 65° C. Then, one equivalent of NaHCO.sub.3 was added to the reaction mixture. The reaction mixture was allowed to cool down to 20 to 25° C., and concentrated under reduced pressure. The resulting solid was filtered off to afford ethyl imidazo[1,2-a]pyrimidine-2-carboxylate. (0.9 g). .sup.1H-NMR (d6-DMSO) 8.99-8.97 (dd, 1H), 8.68-8.67 (dd, 1H), 8.45 (S, 1H), 7.17-7.15 (dd, 1H), 4.33 (q, 2H), 1.33 (t, 3H), LC-MS (M+1)=192

    Step-2: synthesis of ethyl 3-chloroimidazo[1,2-a]pyrimidine-2-carboxylate

    [0393] Ethyl imidazo[1,2-a]pyrimidine-2-carboxylate (0.005 mol) was dissolved in CHCl.sub.3 (10 mL), upon which Palauchlor (1.31 g) was added at 20 to 25° C. under N.sub.2-atmosphere. The reaction mixture was then stirred at 20 to 25° C. for 12 to 15 hours. Upon completion of the reaction, the reaction mixture was quenched and extracted. The combined organic layers were washed, dried and concentrated under reduced pressure to afford ethyl 3-chloroimidazo[1,2-a]pyrimidine-2-carboxylate. (0.900 g). .sup.1H-NMR (d6-DMSO) 8.96-8.94 (m, 1H), 8.83-8.81 (m, 1H), 7.37-7.35 (m, 1H), 4.43 (q, 2H), 1.41 (t, 3H). LCMS (M+1)=226

    Step-3: ethyl 3-ethylsulfanylimidazo[1,2-a]pyrimidine-2-carboxylate

    [0394] To a stirred solution of ethyl 3-chloroimidazo[1,2-a]pyrimidine-2-carboxylate (0.093 mol) in DMF (100 mL) was added sodium ethane thiolate (0.120 mol) in DMF (100 mL) dropwise at 0° C., upon which the resulting reaction mixture was stirred at 0° C. for 2 hours. The reaction was then quenched and the reaction mixture was extracted. The organic layer was washed, dried and concentrated under reduced pressure to afford a crude product. The crude product was purified by flash chromatography to afford ethyl 3-ethylsulfanylimidazo[1,2-a]pyrimidine-2-carboxylate (14 g). .sup.1H-NMR (d6-DMSO) 9.08-9.07 (m, 1H), 8.77-8.76 (dd, 1H), 7.38-7.30 (dd, 1H), 4.37 (q, 2H), 2.90 (q, 2H), 1.36 (t, 3H), 1.07 (t, 3H) LCMS (M+1)=252

    Step-4: synthesis of ethyl 3-ethylsulfonylimidazo[1,2-a]pyrimidine-2-carboxylate

    [0395] To a stirred solution of ethyl 3-ethylsulfanylimidazo[1,2-a]pyrimidine-2-carboxylate (0.047 mol) in CH.sub.2Cl.sub.2 (300 mL) was added meta-chloroperoxybenzoic acid (2.3 equivalents) at 0° C. Then the resulting reaction mixture was allowed to warm up to 20 to 25° C. Subsequently, the reaction mixture was stirred 16 hours. The reaction was then quenched with H.sub.2O and a saturated aqueous solution of sodium bisulphite solution was added. Then the reaction mixture was stirred for another 10 minutes upon which an aqueous 10 wt % solution of NaHCO.sub.3 was added. The organic phase was separated off, the aqueous layer was extracted, and the combined organic phases were concentrated under reduced pressure to afford ethyl 3-ethylsulfonylimidazo[1,2-a]pyrimidine-2-carboxylate (12 g). .sup.1H-NMR (d6-DMSO): 9.32-9.31 (m, 1H), 8.92-8.91 (m, 1H), 7.47-7.45 (m, 1H), 4.41 (q, 2H), 3.67 (q, 2H), 1.38 (t, 3H), 1.26 (t, 3H). LC-MS (M+1)=284

    Step-5: synthesis of 3-ethylsulfonylimidazo[1,2-a]pyrimidine-2-carboxylic acid: hydrochloride

    [0396] To a stirred solution of ethyl 3-ethylsulfonylimidazo[1,2-a]pyrimidine-2-carboxylate (0.017 mol) in CH.sub.3CH.sub.2OH (75 mL) was added a 2N aqueous solution of KOH (0.070 mol) at 28° C. Then, the resulting reaction mixture was heated at 70° C. for 3 hours. The reaction mixture was then cooled to 20 to 25° C., and concentrated under reduced pressure. The resulting residue was diluted with 40 ml of H.sub.2O and acidified with an aqueous 1N solution of HCl up to pH 3. The mixture was extracted and the combined organic layers were dried under reduced pressure to afford 3-ethylsulfonylimidazo[1,2-a]pyrimidine-2-carboxylic acid; hydrochloride. (3.0 g) .sup.1H-NMR (d6-DMSO) 9.57-9.55 (m, 1H), 8.92-8.91 (m, 1H), 7.48-7.46 (m, 1H), 3.65 (q, 2H), 1.26 (t, 3H). LC-MS (M+1)=256

    Step-7: synthesis of 2-(3-ethylsulfonylimidazo[1,2-a]pyrimidin-2-yl)-6-methoxy-1-methyl-imidazo[4,5-c]quinoline

    [0397] Compounds 3-ethylsulfonylimidazo[1,2-a]pyrimidine-2-carboxylic acid; hydrochloride and N4-methyl-8-(trifluoromethoxy)quinoline-3,4-diamine were converted to afford 2-(3-ethylsulfonylimidazo[1,2-a]pyrimidin-2-yl)-6-methoxy-1-methyl-imidazo[4,5-c]quinoline in a series of reaction steps in analogy to Example 1, Steps 3 and 4. LC-MS (M+1)=476.9, retention time: 0,866 With appropriate modification of the starting materials or intermediates thereof, the procedures as described in the preparation examples above were used to obtain further compounds of formula I. The compounds obtained in this manner are listed in the below Table C, together with physical data.

    TABLE-US-00002 TABLE C List of compounds C-1 to C-20 with physical characterization data Com- pound HPLC/MS Rt no. Structure (M + 1) [g/mol] [min] C-1 [00066]embedded image 544 1.165 C-2 [00067]embedded image 528.1 1.222 C-3 [00068]embedded image 459.9 1.022 C-4 [00069]embedded image 476.0 0.968 C-5 [00070]embedded image 494.0 0.852 C-6 [00071]embedded image 460.0 0.938 C-7 [00072]embedded image 446.0 1.008 C-8 [00073]embedded image 582.0 1,351 C-9 [00074]embedded image 514.0 1.217 C-10 [00075]embedded image 446.0 1.068 C-11 [00076]embedded image 461.0 1.037 C-12 [00077]embedded image 464.3 1.008 C-13 [00078]embedded image 484.3 0.89 C-14 [00079]embedded image 480.3 0.877 C-15 [00080]embedded image 477.3 0.85 C-16 [00081]embedded image 461.3 0.86 C-17 [00082]embedded image 476.9 0.866 C-18 [00083]embedded image 460.9 0.87 C-19 [00084]embedded image 459.9 1.091 C-20 [00085]embedded image 460.2 0.956 C-21 [00086]embedded image 527.0 1.163 C-22 [00087]embedded image 543.0 1.067 C-23 [00088]embedded image 543.0 1.081 C-24 [00089]embedded image 527.0 1.058 C-25 [00090]embedded image 554.2 0.99 C-26 [00091]embedded image 553.8 1.106 C-27 [00092]embedded image 538.2 1.035 C-28 [00093]embedded image 539.8 1.174 C-29 [00094]embedded image 476.2 0.93 C-30 [00095]embedded image 512.9 1.172

    B. BIOLOGICAL EXAMPLES

    [0398] The activity of the compounds of formula (I) of the present invention could be demonstrated and evaluated in biological tests described in the following. If not otherwise specified, the test solutions are prepared as follows: 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. Test solutions are prepared in general at concentrations of 2500 ppm, 1000 ppm, 800 ppm, 500 ppm, 300 ppm, 100 ppm and 30 ppm (wt/vol).

    Boll Weevil (Anthonomus grandis)

    [0399] 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. The compounds were formula ted 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. 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. In this test, compounds C-1, C-2, C-3, C-4, C-5, C-6, C-7 at 2500 ppm showed over 75% mortality in comparison with untreated controls. In this test, compounds C-8, C-9, C-10, C-11, C-12, C-13, C-19, C-20, C-22, C-23, C-27, C-28, and C-29 at 800 ppm showed over 75% mortality in comparison with untreated controls.

    [0400] Tobacco Budworm (Heliothis virescens)

    [0401] 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. 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. 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. In this test, compounds C-1, C-2, C-3, C-4, C-5, C-6, C-7 at 2500 ppm showed over 75% mortality in comparison with untreated controls. In this test, compounds C-8, C-9, C-11, C-12, C-13, C-14, C-18, C-19, C-20, C-22, C-23, C-27, C-28, C-29 at 800 ppm showed over 75% mortality in comparison with untreated controls.

    [0402] Green Peach Aphid (Myzus persicae) For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane. The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were pipetted into the aphid diet, using a custom built pipetter, at two replications. After application, 5-8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at about 23±1° C. and about 50±5% relative humidity for 3 days. Aphid mortality and fecundity was then visually assessed. In this test, compounds C-1, C-2, C-3, C-4, C-5, C-7 at 2500 ppm showed over 75% mortality in comparison with untreated controls. In this test, compounds C-9, C-10, C-11, C-12, C-13, C-14, C-15, C-16, C-17, C-19, C-22, C-28, C-29 at 800 ppm showed over 75% mortality in comparison with untreated controls.

    Greenhouse Whitefly (Trialeurodes vaporariorum)

    [0403] For evaluating control of Greenhouse Whitefly (Trialeurodes vaporariorum) the test unit consisted of 96-well-microtiter plates containing a leaf disk of egg plant leaf disk with white fly eggs. The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated were sprayed onto the insect diet at 2.5 μl, using a custom built micro atomizer, at two replications. After application, microtiter plates were incubated at 23±1° C., 65±5% RH for 6 days. Mortality of hatched crawlers was then visually assessed. In this test, compound C-13 at 800 ppm showed over 75% mortality in comparison with untreated controls.

    [0404] Yellow Fever Mosquito (Aedes aegypti)

    [0405] 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. After application, microtiter plates were incubated at 28±1° C., 80±5% RH for 2 days. Larval mortality was then visually assessed. In this test, compounds C-1, C-2, C-3, C-4, C-5, C-7, C-9, C-12, C-19, C-27, C-28, C-29 at 800 ppm showed at least 75% mortality in comparison with untreated controls.

    [0406] Vetch Aphid (Megoura viciae)

    [0407] For evaluating control of vetch aphid (Megoura viciae) through contact or systemic means the test unit consisted of 24-well-microtiter plates containing broad bean leaf disks.

    [0408] 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 leaf disks at 2.5 μl, using a custom built micro atomizer, at two replications. After application, the leaf disks were air-dried and 5-8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids were then allowed to suck on the treated leaf disks and incubated at about 23±1° C. and about 50±5% relative humidity for 5 days. Aphid mortality and fecundity was then visually assessed. In this test, compounds C-1, C-2, C-3, C-4, at 2500 ppm showed over 75% mortality in comparison with untreated controls.