Pyrimidone Derivatives Containing Two Fused Bicyclic Rings

Abstract

The invention relates to a compound of formula (I), wherein the variables are defined in the specification. It also relates to a pesticidal mixture comprising the compound of formula (I); the use of compounds of formula (I) as an agrochemical pesticide; a method for combating or controlling invertebrate pests, a method for protecting growing plants from attack or infestation by invertebrate pests, seed comprising a compound of the formula (I); the use of a compound of the formula (I) for protecting growing plants from attack or infestation by invertebrate pests; and a method for treating or protecting an animal from infestation or infection by invertebrate pests.

##STR00001##

Claims

1. A compound of formula (I) ##STR00054## wherein the circle in ring represents that ring is fully unsaturated; Y is C═X, wherein X is O or S; P is N(R.sup.3) or C(R.sup.4); Q is N(R.sup.5) or C(R.sup.6); R.sup.1 is 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.6-alkoxy-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, C.sub.1-C.sub.6-sulfenyl, C.sub.1-C.sub.6-sulfinyl, or C.sub.1-C.sub.6-sulfonyl, which groups are unsubstituted or halogenated; R.sup.3, R.sup.5 are independently 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-cycloalkyl-C.sub.1-C.sub.4-alkyl, or C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, which are unsubstituted or halogenated; C(═O)OR.sup.A, NR.sup.BR.sup.C, C.sub.1-C.sub.6-alkylen-NR.sup.BR.sup.C, O—C.sub.1-C.sub.6-alkylen-NR.sup.BR.sup.C, C.sub.1-C.sub.6-alkylen-CN, NH—C.sub.1-C.sub.6-alkylen-NR.sup.BR.sup.C, C(═O)NR.sup.BR.sup.C, C(═O)R.sup.D, C(═S)R.sup.D, SO.sub.2NR.sup.BR.sup.C, S(═O).sub.nR.sup.E; phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R.sup.F; R.sup.2, R.sup.4, R.sup.6 are independently 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.A, NR.sup.BR.sup.C, NOR.sup.A, ONR.sup.BR.sup.C, C.sub.1-C.sub.6-alkylen-NR.sup.BR.sup.C, O—C.sub.1-C.sub.6-alkylen-NR.sup.BR.sup.C, C.sub.1-C.sub.6-alkylen-CN, NH—C.sub.1-C.sub.6-alkylen-NR.sup.BR.sup.C, C(═O)NR.sup.BR.sup.C, C(═O)R.sup.D, C(═S)R.sup.D, SO.sub.2NR.sup.BR.sup.C, S(═O).sub.nR.sup.E; phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R.sup.F; D is a fused bicyclic ring of the following formula ##STR00055## 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; and wherein A is N, S, O, CR.sup.7, or NR.sup.B; E, J are independently C or N, wherein at least one of the variables selected from E and J is C; G is a 5- or 6-membered saturated, partially unsaturated, or fully unsaturated carbo- or heterocycle, which carbo- or heterocycle includes the atoms E and J as ring members and is unsubstituted, or substituted with one or more, same or different substituents R.sup.9, and wherein said heterocycle comprises no, one or more, same or different heteroatoms O, N, or S in addition to those that may be present as ring members E and J; 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.G; 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.H, 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.J; OR.sup.K, SR.sup.K, OC(═O)R.sup.K, OC(═O)OR.sup.K, OC(═O)NR.sup.LR.sup.M, OC(═O)SR.sup.K, OC(═S)NR.sup.LR.sup.M, OC(═S)SR.sup.K, OS(═O).sub.mR.sup.K, OS(═O).sub.mNR.sup.LR.sup.M, ONR.sup.LR.sup.M, ON═CR.sup.NR.sup.O, NR.sup.LR.sup.M, NOR.sup.K, ONR.sup.LR.sup.M, N═CR.sup.NR.sup.O, NNR.sup.LN(R.sup.L)C(═O)R.sup.K, N(R.sup.L)C(═O)OR.sup.K, S(═O).sub.nR.sup.V, SC(═O)SR.sup.K, SC(═O)NR.sup.LR.sup.M, S(═O).sub.mNR.sup.LR.sup.M, C(═O)R.sup.P, C(═S)R.sup.P, C(═O)NR.sup.LR.sup.M, C(═O)OR.sup.K, C(═S)NR.sup.LR.sup.M, C(═S)OR.sup.K, C(═S)SR.sup.K, C(═NR.sup.L)R.sup.M, C(═NR.sup.L)NR.sup.MR.sup.R, Si(R.sup.S).sub.2R.sup.T; R.sup.8 is H, halogen, 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.G; 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.H, 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.J; OR.sup.K, SR.sup.K, OC(═O)R.sup.K, OC(═O)OR.sup.K, OC(═O)NR.sup.LR.sup.M, OC(═O)SR.sup.K, OC(═S)NR.sup.LR.sup.M, OC(═S)SR.sup.K, OS(═O).sub.mR.sup.K, OS(═O).sub.mNR.sup.LR.sup.M, ONR.sup.LR.sup.M, ON═CR.sup.NR.sup.O, NR.sup.LR.sup.M, NOR.sup.K, ONR.sup.LR.sup.M, N═CR.sup.NR.sup.O, NNR.sup.LN(R.sup.L)C(═O)R.sup.K, N(R.sup.L)C(═O)OR.sup.K, S(═O).sub.nR.sup.V, SC(═O)SR.sup.K, SC(═O)NR.sup.LR.sup.M, S(═O).sub.mNR.sup.LR.sup.M, C(═O)R.sup.P, C(═S)R.sup.P, C(═O)NR.sup.LR.sup.M, C(═O)OR.sup.K, C(═S)NR.sup.LR.sup.M, C(═S)OR.sup.K, C(═S)SR.sup.K, C(═NR.sup.L)R.sup.M, C(═NR.sup.L)NR.sup.MR.sup.R, Si(R.sup.S).sub.2R.sup.T; 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, 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.G; 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.H, 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.J; OR.sup.K, SR.sup.K, OC(═O)R.sup.K, OC(═O)OR.sup.K, OC(═O)NR.sup.LR.sup.M, OC(═O)SR.sup.K, OC(═S)NR.sup.LR.sup.M, OC(═S)SR.sup.K, OS(═O).sub.mR.sup.K, OS(═O).sub.mNR.sup.LR.sup.M, ONR.sup.LR.sup.M, ON═CR.sup.NR.sup.O, NR.sup.LR.sup.M, NOR.sup.K, ONR.sup.LR.sup.M, N═CR.sup.NR.sup.O, NNR.sup.LN(R.sup.L)C(═O)R.sup.K, N(R.sup.L)C(═O)OR.sup.K, S(═O).sub.nR.sup.V, SC(═O)SR.sup.K, SC(═O)NR.sup.LR.sup.M, S(═O).sub.mNR.sup.LR.sup.M, C(═O)R.sup.P, C(═S)R.sup.P, C(═O)NR.sup.LR.sup.M, C(═O)OR.sup.K, C(═S)NR.sup.LR.sup.M, C(═S)OR.sup.K, C(═S)SR.sup.K, C(═NR.sup.L)R.sup.M, C(═NR.sup.L)NR.sup.MR.sup.R, Si(R.sup.S).sub.2R.sup.T; or two substituents R.sup.9 form, together with the ring members of ring G 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.J, and wherein said heterocycle comprises one or more, same or different heteroatoms O, N, or S; each R.sup.A 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-NR.sup.bR.sup.c, 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 substitutents R.sup.F; each R.sup.B 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.F; each R.sup.C 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.F; each moiety NR.sup.BR.sup.C 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, S(═O).sub.m 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.D 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.F; each R.sup.E 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 one or more, same or different substituents R.sup.F; each R.sup.F 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; each R.sup.G 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.K, SR.sup.K, OC(═O)R.sup.K, OC(═O)OR.sup.K, OC(═O)NR.sup.LR.sup.M, OC(═O)SR.sup.K, OC(═S)NR.sup.LR.sup.M, OC(═S)SR.sup.K, OS(═O).sub.mR.sup.K, OS(═O).sub.mNR.sup.LR.sup.M, ONR.sup.LR.sup.M, ON═CR.sup.NR.sup.O, NR.sup.LR.sup.M, NOR.sup.K, ONR.sup.LR.sup.M, N═CR.sup.NR.sup.O, NNR.sup.LN(R.sup.L)C(═O)R.sup.K, N(R.sup.L)C(═O)OR.sup.K, S(═O).sub.nR.sup.V, SC(═O)SR.sup.K, SC(═O)NR.sup.LR.sup.M, S(═O).sub.mNR.sup.LR.sup.M, C(═O)R.sup.P, C(═S)R.sup.P, C(═O)NR.sup.LR.sup.M, C(═O)OR.sup.K, C(═S)NR.sup.LR.sup.M, C(═S)OR.sup.K, C(═S)SR.sup.K, C(═NR.sup.L)R.sup.M, C(═NR.sup.L)NR.sup.MR.sup.R, Si(R.sup.S).sub.2R.sup.T; each R.sup.H 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.K, SR.sup.K, OC(═O)R.sup.K, OC(═O)OR.sup.K, OC(═O)NR.sup.LR.sup.M, OC(═O)SR.sup.K, OC(═S)NR.sup.LR.sup.M, OC(═S)SR.sup.K, OS(═O).sub.mR.sup.K, OS(═O).sub.mNR.sup.LR.sup.M, ONR.sup.LR.sup.M, ON═CR.sup.NR.sup.O, NR.sup.LR.sup.M, NOR.sup.K, ONR.sup.LR.sup.M, N═CR.sup.NR.sup.O, NNR.sup.L, N(R.sup.L)C(═O)R.sup.K, N(R.sup.L)C(═O)OR.sup.K, S(═O).sub.nR.sup.V, SC(═O)SR.sup.K, SC(═O)NR.sup.LR.sup.M, S(═O).sub.mNR.sup.LR.sup.M, C(═O)R.sup.P, C(═S)R.sup.P, C(═O)NR.sup.LR.sup.M, C(═O)OR.sup.K, C(═S)NR.sup.LR.sup.M, C(═S)OR.sup.K, C(═S)SR.sup.K, C(═NR.sup.L)R.sup.M, C(═NR.sup.L)NR.sup.MR.sup.R, Si(R.sup.S).sub.2R.sup.T; or two geminal substituents R.sup.H form together with the atom to which they are bound a group ═O, ═S, or ═NR.sup.L; each R.sup.J 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.K, SR.sup.K, OC(═O)R.sup.K, OC(═O)OR.sup.K, OC(═O)NR.sup.LR.sup.M, OC(═O)SR.sup.K, OC(═S)NR.sup.LR.sup.M, OC(═S)SR.sup.K, OS(═O).sub.mR.sup.K, OS(═O).sub.mNR.sup.LR.sup.M, ONR.sup.LR.sup.M, ON═CR.sup.NR.sup.O, NR.sup.LR.sup.M, NOR.sup.K, ONR.sup.LR.sup.M, N═CR.sup.NR.sup.O, NNR.sup.L, N(R.sup.L)C(═O)R.sup.K, N(R.sup.L)C(═O)OR.sup.K, S(═O).sub.nR.sup.V, SC(═O)SR.sup.K, SC(═O)NR.sup.LR.sup.M, S(═O).sub.mNR.sup.LR.sup.M, C(═O)R.sup.P, C(═S)R.sup.P, C(═O)NR.sup.LR.sup.M, C(═O)OR.sup.K, C(═S)NR.sup.LR.sup.M, C(═S)OR.sup.K, C(═S)SR.sup.K, C(═NR.sup.L)R.sup.M, C(═NR.sup.L)NR.sup.MR.sup.R, Si(R.sup.S).sub.2R.sup.T; each R.sup.K 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.MR.sup.N; C(═O)NR.sup.MR.sup.N, C(═O)R.sup.T; or phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substitutents R.sup.X; each R.sup.L 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.X; each R.sup.M, R.sup.R 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.X; each moiety NR.sup.MR.sup.R or NR.sup.LR.sup.M 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.m 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.N is independently H, halogen, CN, NO.sub.2, SCN; C.sub.1-C.sub.10-alkyl, C.sub.3-C.sub.8-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.O 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.P 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.X; each R.sup.S, R.sup.T 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.V 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.X; each R.sup.W 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.X; each R.sup.X 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; m is 0, 1 or 2; n is 0, 1, 2, or 3; and the N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof.

2. The compound of formula (I) according to claim 1, wherein R.sup.1 is H; C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-alkoxy, which groups are unsubstituted or halogenated; R.sup.2 is H, halogen; 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, which groups are unsubstituted or halogenated,

3. The compound of formula (I) according to claim 1, wherein the compound of formula (I) is a compound of formula (I.A), (I.B) or (I.C); ##STR00056## wherein all variables have a meaning as defined for formula (I).

4. The compound of formula (I-A) according to claim 3, wherein R.sup.3 C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3-alkoxy-C.sub.1-C.sub.3-alkyl, C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6 cycloalkyl-C.sub.1-C.sub.2-alkyl, which groups are unsubstituted or halogenated; phenyl or benzyl, in which groups the phenyl ring is unsubstituted or substituted with R.sup.F; R.sup.6 is H; or C.sub.1-C.sub.3-alkyl or C.sub.1-C.sub.3-haloalkyl.

5. The compound of formula (I-B) according to claim 3, wherein R.sup.4 is H; or C.sub.1-C.sub.3 alkyl, or C.sub.1-C.sub.3-haloalkyl; R.sup.5 is C.sub.1-C.sub.3-alkyl, or C.sub.1-C.sub.3-haloalkyl.

6. The compound of formula (I) according to claim 1, wherein the variable D stands for a fused bicyclic ring of the following formulae (D1), (D3), (D8), or (D51) ##STR00057## wherein the index z is 0, 1, 2, 3, or 4 for (D1), (D3), (D51), or wherein z is 0, 1, 2, or 3 for (D8), and wherein the other variables are defined as for formula (I), and wherein the “&”-symbol signifies the connection to the remainder of formula (I).

7. The compound of formula (I) according to claim 1, wherein each R.sup.9 is independently selected from H, halogen; and C.sub.1-C.sub.3-alkyl, C.sub.2-C.sub.3-alkenyl, and C.sub.2-C.sub.3-alkynyl, which groups are unsubstituted, or halogenated.

8. The compound of formula (I) according to claim 1, wherein R.sup.W is C.sub.1-C.sub.3-alkyl or C.sub.1-C.sub.3-haloalkyl, and m is 0 or 2.

9. A pesticidal mixture comprising the compound of formula (I), as defined in claim 1, an N-oxide or an agriculturally acceptable salt thereof and a further pesticidal ingredient.

10. (canceled)

11. A method for combating or controlling invertebrate pests, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound of the formula (I) according to claim 1.

12. A method for protecting growing plants from attack or infestation by invertebrate pests, which method comprises 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. Seed comprising a compound of the formula (I), as defined in claim 1, in an amount of from 0.1 g to 10 kg per 100 kg of seed.

14. (canceled)

15. A method for treating or protecting an animal from infestation or infection by invertebrate pests which comprises bringing the animal in contact with a pesticidally effective amount of a compound of the formula (I) as defined in claim 1.

Description

A. PREPARATION OF COMPOUNDS

[1447] Materials: Unless otherwise noted, reagents and solvents were purchased at highest commercial quality and used without further purification.

[1448] 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 (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, ddd=doublet of doublets of doublets, dt=double triplet, td=triplet of doublets m=multiplet, br=broad, J=coupling constant. High-resolution mass spectra were measured on a JEOL JMS-T100LP.

[1449] 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.

Synthesis Example A: 2-[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (compound I.1)

Step 1) Manufacture of 2-bromo-1-[3-ethylsulfanyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]ethanone

[1450] A solution of 185 mg 1-[3-ethylsulfanyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]ethanone (as disclosed and synthesized in EP3257853A1, table 30, i-6-004) was dissolved in 3 ml of 25% HBr in CH.sub.3COOH and a solution of 123 mg Br.sub.2 in 3 ml CH3COOH was added at room temperature and stirred for 4 hours. Water was added and the mixture was extracted twice with methyl tert. butyl ether. The combined organic layers were dried and concentrated under reduced pressure to afford a residue. The residue was purified by column chromatography under reversed phase conditions to afford 130 mg of 2-bromo-1-[3-ethylsulfanyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]ethanone LC-MS: mass found 366.8; t.sub.R=1.215 min (t.sub.R: retention time).

Step 2) Manufacture of 2-[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one

[1451] Step 2a: A mixture of 122 mg of 2-bromo-1-[3-ethylsulfanyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]ethanone and 4-amino-1-methyl-6-(trifluoromethyl)pyrimidin-2-one (77 mg) was dissolved in 3 ml 1,4-dioxan and heated to 140° C. for 4 hours in a microwave reactor. The reaction was then cooled to 20 to 25° C. and concentrated in vacuo to afford a residue. The residue was purified by column chromatography under reversed phase conditions to afford 51 mg of 2-[3-ethylsulfanyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-methyl-7-(trifluoromethyl) imidazo[1,2-c]pyrimidin-5-one. LC-MS: mass found for C.sub.18H.sub.13N.sub.5OF.sub.6S [M+H].sup.+=461.9; t.sub.R=1.186 min (t.sub.R: retention time).

[1452] Step 2b: To a solution of 2-[3-ethylsulfanyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-6-methyl-7-(trifluoromethyl) imidazo[1,2-c]pyrimidin-5-one (51 mg) in CH.sub.2Cl.sub.2 (5 mL) at 5° C. was added meta-chloroperoxybenzoic acid (63 mg), the reaction mixture was then allowed to warm to 20 to 25° C. and stirred for 16 hours. The reaction mixture was then poured into water and extracted with CH.sub.2Cl.sub.2. The combined organic layers were dried, and concentrated under reduced pressure to afford a residue. The residue was purified by column chromatography under reversed phase conditions eluting with water/acetonitrile to afford compound I.1 (20.4 mg, 37% yield). LC-MS: mass found for C.sub.18H.sub.13N.sub.5O.sub.3F.sub.6S [M+H].sup.+ 493.9; t.sub.R=1.165 min (t.sub.R: retention time).

Synthesis Example B: 6-cyclopropyl-2-[3-(ethanesulfonyl)imidazo[1,2-a]pyridin-2-yl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (compound I.2)

Step 1) Manufacture of ethyl imidazo[1,2-a]pyridine-2-carboxylate

[1453] To a stirred composition comprising 2-aminopyridine (10 g) and CH.sub.3CH.sub.2OH (100 mL) was added ethyl bromopyruvate (24.86 g) dropwise over a period a time of 10 min at 20 to 25° C. The resulting reaction mixture was heated to boiling temperature under refluxation for 5 hours. The solvent was then evaporated under reduced pressure. Work-up of the residue by extraction and column chromatography afforded ethyl imidazo[1,2-a] pyridine-2-carboxylate (10 g, 60% yield).

[1454] .sup.1H-NMR (500 MHz, Chloroform-d) δ 8.17 (dt, J=7.0, 1.2 Hz, 1H), 7.71 (dt, J=9.3, 1.1 Hz, 1H), 7.70 (S, 1H), 7.34 (ddd, J=9.2, 6.7, 1.3 Hz, 1H), 7.04 (td, J=6.9, 1.1 Hz, 1H), 4.52 (q, J=7.1 Hz, 2H), 1.48 (t, J=7.1 Hz, 3H). LC-MS: Mass found (M+1)=190.1.

Step-2: Manufacture of ethyl 3-chloroimidazo[1,2-a]pyridine-2-carboxylate

[1455] Ethyl imidazo[1,2-a] pyridine-2-carboxylate (1 g) from step-1 was dissolved in DMF (10 mL), then N-chlorosuccinimide (0.913 g) was added at 20 to 25° C. under nitrogen atmosphere. The reaction mixture was heated to 40° C. for 4 hours. The reaction mixture quenched with water and worked-up by extraction to afford a brown colour oil of ethyl 3-chloroimidazo[1,2-a] pyridine-2-carboxylate (1.0 g, 80% yield). .sup.1H-NMR (500 MHz, Chloroform-d) δ 8.22-8.10 (m, 1H), 7.72 (d, J=9.0 Hz, 1H), 7.35 (ddd, J=9.4, 6.8, 1.4 Hz, 1H), 7.09-6.98 (m, 1H), 4.58-4.44 (m, 2H), 1.55-1.42 (m, 3H). LC-MS: Mass found (M+1)=224.1.

Step-3: Manufacture of ethyl 3-ethylsulfanylimidazo[1,2-a] pyridine-2-carboxylate

[1456] To a stirred composition comprising ethyl 3-chloroimidazo[1,2-a] pyridine-2-carboxylate (4 g) from step-2 in DMF (40 mL) was added sodium ethanethiolate (2.24 g) at 20 to 25° C. The resulting reaction mixture was stirred the reaction mixture at 20 to 25° C. for 2 hours. The reaction mixture was then quenched with water and worked-up by extraction to afford ethyl 3-ethylsulfanylimidazo[1,2-a] pyridine-2-carboxylate (3 g, 70% yield). .sup.1H-NMR (500 MHz, Chloroform-d) δ 8.49 (dt, J=7.0, 1.2 Hz, 1H), 7.64 (dt, J=9.0, 1.1 Hz, 1H), 7.30-7.20 (m, 1H), 6.92 (td, J=6.8, 1.2 Hz, 1H), 4.43 (d, J=7.1 Hz, 2H), 2.86 (d, J=7.3 Hz, 2H), 1.40 (t, J=7.1 Hz, 3H), 1.11 (t, J=7.4 Hz, 3H). LC-MS: Mass found (M+1)=250.1.

Step-4: Manufacture of ethyl 3-ethylsulfonylimidazo[1,2-a] pyridine-2-carboxylate

[1457] To a stirred composition comprising ethyl 3-ethylsulfanylimidazo[1,2-a]pyridine-2-carboxylate (13 g) from step-3 was added meta-Chloroperoxybenzoic acid (3 equivalents) at 0° C. The reaction mixture was then allowed to warm to 20 to 25° C. and stirred for 16 hours. The reaction was then quenched with water upon which a sodium bisulphite solution was added. Work-up by extraction afforded ethyl 3-ethylsulfonylimidazo[1,2-a] pyridine-2-carboxylate as yellow colour solid (14 g, 90% yield). .sup.1H-NMR (500 MHz, Chloroform-d) δ 9.27 (dt, J=7.2, 1.2 Hz, 1H), 7.85 (dt, J=9.0, 1.2 Hz, 1H), 7.53 (ddd, J=9.1, 6.8, 1.2 Hz, 1H), 7.13 (td, J=7.0, 1.3 Hz, 1H), 4.54 (q, J=7.1 Hz, 2H), 3.74 (q, J=7.4 Hz, 2H), 1.49 (t, J=7.1 Hz, 3H), 1.38 (t, J=7.4 Hz, 3H). LC-MS: Mass found (M+1)=282.1.

Step-5: Manufacture of 3-ethylsulfonylimidazo[1,2-a] pyridine-2-carboxylic acid

[1458] To a stirred composition comprising ethyl 3-ethylsulfanylimidazo[1,2-a] pyridine-2-carboxylate (1 g) from step-4 in CH.sub.3CH.sub.2OH (10 mL) was added LiOH—H.sub.2O (0.250 g) at 20 to 25° C. The reaction mixture was stirred for 2 hours upon which the solvent was removed by evaporation. The residue was diluted with an aqueous solution of HCl (1 M) to adjust the pH to approximately 2. The resulting composition was worked-up by extraction to afford 3-ethylsulfonylimidazo[1,2-a] pyridine-2-carboxylic acid (0.7 g, 80% yield).

[1459] .sup.1H NMR (500 MHz, DMSO-d.sub.6) δ 8.79 (d, J=6.9 Hz, 1H), 7.80 (d, J=9.0 Hz, 1H), 7.70 (t, J=7.9 Hz, 1H), 7.33 (t, J=6.8 Hz, 1H), 2.93 (t, J=7.3 Hz, 2H), 1.09 (t, J=7.3 Hz, 3H). LC-MS: Mass found (M−1)=253.1.

Step-6: Manufacture of 3-ethylsulfonyl-N-methoxy-N-methyl-imidazo[1,2-a]pyridine-2-carboxamide

[1460] To a stirred composition comprising 3-ethylsulfonylimidazo[1,2-a] pyridine-2-carboxylic acid (0.1 g) in dry DCM (10 mL) were added N,O-dimethylhydroxylamine (0.042 g) and diisopropylethylamine (0.203 g) at 0° C. under nitrogen atmosphere. The resulting reaction mixture was stirred at 0° C. for 10 min. After that propanephosphonic acid anhydride (0.375 g) was added and the reaction mixture was allowed to warm to 20 to 25° C. upon it was stirred overnight. The reaction mixture was then quenched with water and worked-up by extraction to afford 3-ethylsulfonyl-N-methoxy-N-methyl-imidazo[1,2-a]pyridine-2-carboxamide (0.08 g, 70% yield).

[1461] .sup.1H-NMR (500 MHz, Chloroform-d) δ 8.89 (d, J=7.0 Hz, 1H), 7.70 (dt, J=9.1, 1.2 Hz, 1H), 7.44 (t, J=7.9 Hz, 1H), 7.03 (t, J=6.9 Hz, 1H), 3.62 (s, 3H), 3.40 (t, J=7.5 Hz, 2H), 3.36 (s, 3H), 1.28 (t, J=7.4 Hz, 3H). LC-MS: Mass found (M−1)=297.1.

Step-7: Manufacture of 1-(3-ethylsulfonylimidazo[1,2-a] pyridin-2-yl)ethanone

[1462] To a stirred composition comprising 3-ethylsulfonyl-N-methoxy-N-methyl-imidazo[1,2-a]pyridine-2-carboxamide (1 g) from step-6 in THF (15 mL) was added a solution of CH.sub.3MgBr in diethyl ether (3 M, 0.006 mol) at 0° C. under nitrogen atmosphere. The resulting reaction mixture was stirred at 0° C. for 30 min. Work-up of the reaction mixture afforded 1-(3-ethylsulfonylimidazo[1,2-a] pyridin-2-yl)ethanone as white solid. (0.84 g, yield: 75%). .sup.1H-NMR (500 MHz, Chloroform-d) δ 9.23 (dt, J=7.2, 1.2 Hz, 1H), 7.72 (dt, J=9.1, 1.2 Hz, 1H), 7.44 (ddd, J=9.1, 6.8, 1.2 Hz, 1H), 7.03 (td, J=7.0, 1.3 Hz, 1H), 3.69 (q, J=7.5 Hz, 2H), 2.71 (s, 3H), 1.27 (t, J=7.4 Hz, 3H). LC-MS: Mass found (M+1)=252.1.

Step-8: Manufacture of 2-bromo-1-(3-ethylsulfonylimidazo[1,2-a] pyridin-2-yl)ethanone

[1463] To a stirred composition comprising 1-(3-ethylsulfonylimidazo[1,2-a]pyridin-2-yl)ethanone (1 g) in glacial CH.sub.3COOH (10 mL) at 0° C. was added 33 wt % HBr in acetic acid solution (10 mL), which was subsequently stirred at 0° C. for 10 min. After that, Br.sub.2 (0.04 mol) in CH2CL2 (10 mL) was added dropwise to the reaction mixture over a period of 5 min. Then, the reaction mixture was heated to 50° C. outer temperature for 2 hours. The reaction mixture was then allowed to cool to 20 to 25° C. and then slowly poured on ice, which composition was diluted with ethyl acetate (30 mL). Work-up of the composition by extraction and purification by column chromatography afforded 2-bromo-1-(3-ethylsulfonylimidazo[1,2-a] pyridin-2-yl)ethanone (1.0 g, 76% yield). .sup.1H NMR (500 MHz, Chloroform-d) δ 9.32 (dd, J=7.1, 1.1 Hz, 1H), 7.82 (d, J=9.2 Hz, 1H), 7.56 (ddd, J=8.9, 6.8, 1.2 Hz, 1H), 7.16 (td, J=7.0, 1.4 Hz, 1H), 4.82 (s, 2H), 3.76 (q, J=7.4 Hz, 2H), 1.37 (s, 3H). LC-MS: Mass found (M+1)=331.12.

Step-9: Manufacture of 6-cyclopropyl-2-[3-(ethanesulfonyl)imidazo[1,2-a]pyridin-2-yl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one

[1464] To a stirred composition comprising 2-bromo-1-[3-(ethanesulfonyl)imidazo[1,2-a]pyridin-2-yl]ethanone (0.113 g) from step-8 in (CH.sub.3).sub.3COH (2 mL) was added 4-amino-1-cyclopropyl-6-(trifluoromethyl)pyrimidin-2-one (0.05 g). Molecular sieves were added to the resulting reaction mixture (0.4 g), which was subsequently heated to 120° C. for 24 hours. Then, the reaction mixture was filtered through a celite bed, upon which the filtrate was collected and concentrated under reduced pressure. The resulting residue was purified by column chromatography to afford 6-cyclopropyl-2-[3-(ethanesulfonyl)imidazo[1,2-a]pyridin-2-yl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one with 91.96% purity as a yellow solid (0.044 g, 45% yield). .sup.1H-NMR (500 MHz, DMSO-d.sub.6) δ 9.14-9.02 (m, 1H), 8.31 (s, 1H), 7.86 (dd, J=9.0, 1.2 Hz, 1H), 7.65 (ddd, J=8.8, 6.8, 1.2 Hz, 1H), 7.48 (s, 1H), 7.27 (td, J=7.0, 1.3 Hz, 1H), 3.85 (q, J=7.4 Hz, 2H), 3.17 (s, 1H), 1.22 (t, J=7.4, Hz, 3H), 1.12 (ddt, J=23.1, 7.0, 2.7 Hz, 4H). LC-MS: mass calculated 452, LC-MS: Mass found (M+1) 452.

[1465] Table B below lists compounds of formula I.A.1 by the meaning of variables R.sup.1, R.sup.3, and D,

##STR00037##

which compounds were synthesized as described in Synthesis Examples A, B, or in analogy thereto.

TABLE-US-00002 TABLE B compounds I.1 to I.10 with physical characterization data. .sup.1H-NMR data, chemical shif (δ), Compound R.sup.1 R.sup.3 D (500 MHz, DMSO-d6) I.1 CF.sub.3 CH.sub.3 [00038] n.m., identified by LC-MS, see above Synthesis Example A I.2 CF.sub.3 cyclopropyl [00039] δ 9.14-9.02 (m, 1H), 8.31 (s, 1H), 7.86 (dd, 1H, J = 9.0, 1.2 Hz,), 7.65(ddd, 1H, J = 8.8, 6.8, 1.2 Hz), 7.48 (s, 1H), 1H, 7.27 (td, J = 7.0, 1.3 Hz), 3.85 (q, 2H, J = 7.4 Hz), 3.17 (s, 1H), 1.22 (t, 3H, J = 7.4, Hz), 1.12 (ddt, 4H, J = 23.1, 7.0, 2.7 Hz). I.3 CF.sub.3 cyclopropyl- methyl [00040] 9.10 (d, 1H, J = 5 Hz), 8.40 (s, 1H), 7.87 (d, 1H, J = 5 Hz), 7.66 (dd, 1H, J = 7 Hz), 7.56 (s, 1H), 7.28 (d, 1H, J = 5 Hz), 4.0 (d, 2H, J = 7 Hz), 3.85 (t, 2H, J = 7 Hz), 3.18 (s, 1H), 1.22 (t, 3H, J = 5 Hz), 0.55 (m, 4H) I.4 CF.sub.3 CHCCH.sub.2— [00041] 9.09 (dd, J = 7.0, 1.2 Hz, 1H), 8.43 (s, 1H), 7.87 (dt, J = 9.0, 1.2 Hz, 1H), 7.66-7.62 (m, 2H), 7.28 (td, J = 6.9, 1.3 Hz, 1H), 4.83 (d, J = 2.5 Hz, 2H), 3.83 (q, J = 7.4 Hz, 2H), 3.45(s, 1H), 1.22 (t, J = 7.3 Hz, 3H) I.5 CF.sub.3 CF.sub.3CH.sub.2 [00042] 9.09 (d, J = 7.0 Hz, 1H), 8.45 (s, 1H), 7.87 (d, J = 9.0 Hz, 1H), 7.72 (s, 1H), 7.66 (ddd, J = 8.7, 6.9, 1.2 Hz, 1H), 7.28 (td, J = 7.0, 1.2 Hz, 1H), 4.93 (d, J = 8.2 Hz, 2H), 3.84 (q, J = 7.3 Hz, 2H), 1.23 (t, J = 7.3 Hz, 3H) I.6 CF.sub.3 cyclopropyl [00043] δ 9.54-9.40 (m, 1H), 8.36 (s, 1H), 8.06 (d, 1H, J = 9.3 Hz,), 7.91 (dd, 1H, J = 9.5, 1.9 Hz,), 7.50 (s, 1H), 3.98 (q, 2H, J = 7.3 Hz,), 3.17 (d, 1H, J = 4.2 Hz,), 1.26 (t, 3H, J = 7.4 Hz,), 1.20- 1.01 (m, 4H) I.7 CF.sub.3 CH.sub.3 [00044] 9.20 (d, J = 1.8 Hz, 1H), 8.38 (s, 1H), 7.97-7.70 (m, 2H), 7.53 (s, 1H), 3.91 (q, J = 7.3 Hz, 2H), 3.61 (s, 3H), 1.24 (t, J = 7.3 Hz, 3H) I.8 CF.sub.3 cyclopropyl [00045] 9.19 (d, 1H, J = 5 Hz), 8.32 (s, 1H), 7.8 (d, 2H, J = 5 Hz), 7.47 (s, 1H), 3.90 (t, 2H, J = 7 Hz), 3.18 (s, 1H), 1.22 (t, 3H, J = 5 Hz), 1.13 (m, 4H) I.9 CF.sub.3 cyclopropyl [00046] 9.24 (d, J = 2.0 Hz, 1H), 8.32 (s, 1H), 7.93 (d, J = 9.5 Hz, 1H), 7.86 (dd, J = 9.5, 2.0 Hz, 1H), 7.48 (s, 1H), 3.90 (q, J = 7.3 Hz, 2H), 3.17 (s, 1H), 1.79 (s, 6H), 1.24 (t, J = 7.3 Hz, 3H), 1.17- 1.04 (m, 4H) I.10 CF.sub.3 CH.sub.3 [00047] 9.24 (d, J = 2.0 Hz, 1H), 8.32 (s, 1H), 7.93 (d, J = 9.5 Hz, 1H), 7.86 (dd, J = 9.5, 2.0 Hz, 1H), 7.48 (s, 1H), 3.90 (q, J = 7.3 Hz, 2H), 3.61 (s, 3H), 1.79 (s, 6H), 1.24 (t, J = 7.3 Hz, 3H) n.m. means not measured. &signifies the connection to the remainder of the molecule of formula I.A.1.

Synthesis Example C: 6-cyclopropyl-2-(3-ethylsulfonylpyrazolo[1,5-a]pyridin-2-yl)-7-(trifluoro-methyl)imidazo[1,2-c]pyrimidin-5-one (compound I.11)

Step-1: Manufacture of dimethyl pyrazolo[1,5-a]pyridine-2,3-dicarboxylate

[1466] To a composition comprising pyridine-1-ium-1-amine iodide (5 g) in DMF (50 mL) was added K.sub.2CO.sub.3 (6.21 g) in portions at 0° C. over a period of 10 min. Subsequently, dimethyl but-2-ynedioate (6.39 g) was added dropwise over a period of 15 minutes at the same temperature. The resulting reaction mixture was stirred at 20 to 25° C. for 12 hours. The reaction was then quenched with water. Work-up by extraction and purification by column chromatography yielded dimethyl pyrazolo[1,5-a]pyridine-2,3-dicarboxylate (2.3 g, 43.39% yield). .sup.1H-NMR (CDCl.sub.3) 8.52 (d, 1H), 8.17-8.19 (d, 1H), 7.45-7.49 (dd, 1H), 7.04-7.07 (dd, 1H), 4.05 (S, 3H), 3.95 (S, 3H). LC-MS: Mass found (M+1) 235.

Step-2: Manufacture of pyrazolo[1,5-a]pyridine-2-carboxylic acid

[1467] To a composition comprising dimethyl pyrazolo[1,5-a]pyridine-2,3-dicarboxylate (2.3 g) from step-1 in water (6 ml) was added H.sub.2SO.sub.4 (3 mL) at 0° C. The resulting reaction mixture was heated to 110° C. for 24 hours. Subsequently, the reaction mixture was cooled to 20 to 25° C. and quenched in an aqueous solution of NaOH (10 wt %) to adjust the pH to 8-9. Work-up by extraction afforded pyrazolo[1,5-a]pyridine-2-carboxylic acid (1.5 g, 78.6% yield). .sup.1H-NMR (DMSO-d6) 13.0 (brod S, 1H), 8.73-8.74 (d, 1H), 7.77-7.79 (d, 1H), 7.29-7.31 (dd, 1H), 7.28 (S, 1H), 7.03-7.06 (dd, 1H). LC-MS: Mass found (M+1)=163

Step-3: Manufacture of methyl pyrazolo[1,5-a]pyridine-2-carboxylate

[1468] To a composition comprising pyrazolo[1,5-a]pyridine-2-carboxylic acid (9 g) from step-2 in CH.sub.3OH (150 ml) was added H.sub.2SO.sub.4 (10 ml) at 0° C. and the resulting reaction mixture was heated under refluxation to 80° C. for 12 hours. Subsequently, the reaction mixture was concentrated by evaporation of the solvent and the reaction was quenched in cool water. The resulting precipitate was filtered and washed with cold water to afford methyl pyrazolo[1,5-a]pyridine-2-carboxylate (8 g, 81.38% yield). 1HNMR (DMSO-d6) 8.76 (d, 1H), 7.79-7.81 (d, 1H), 7.31-7.34 (dd, 1H), 7.13 (S, 1H), 7.07-7.12 (dd, 1H), 3.89 (S, 3H). LC-MS: Mass found (M+1)=177

Step-4: Manufacture of ethyl 3-iodopyrazolo[1,5-a]pyridine-2-carboxylate

[1469] To a composition comprising methyl pyrazolo[1,5-a]pyridine-2-carboxylate (0.25 g) from step-3 in CH.sub.3CN (5 ml) was added N-Iodosuccinimide (0.447 g) at 20 to 25° C. The resulting reaction mixture was stirred at 40° C. for 12 hours. The reaction was quenched with water. Work-up by extraction and purification by column chromatography afforded ethyl 3-iodopyrazolo[1,5-a]pyridine-2-carboxylate (0.36 g, 84.11% yield). .sup.1H-NMR (CDCl.sub.3) 8.51 (d, 1H), 7.61-7.63 (d, 1H), 7.28-7.31 (dd, 1H), 6.97-7.0 (dd, 1H), 4.05 (S, 3H). LC-MS: Mass found (M+1)=303.

Step-5: Manufacture of methyl 3-ethylsulfanylpyrazolo[1,5-a]pyridine-2-carboxylate

[1470] To a composition comprising ethyl 3-iodopyrazolo[1,5-a]pyridine-2-carboxylate (0.4 g) from step-4 in dioxane (10 ml) was added N,N-diisopropylethylamine (0.523 g) and the resulting reaction mixture was degassed for 20 minutes by purging with nitrogen. Then, tris(dibenzylideneacetone)-dipalladium(0) (0.030 g) and 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene (0.038 g) were added to the reaction mixture, which was subsequently was again degassed for 10 min by purging with nitrogen. Subsequently, ethanethiol (0.205 g) was added to the reaction mixture, which was subsequently heated to 90° C. for 3 hours. The reaction was then quenched with water. Work-up of the reaction mixture by extraction and column chromatography afforded methyl 3-ethylsulfanylpyrazolo[1,5-a]pyridine-2-carboxylate 0.29 g, 92.90% yield. .sup.1H-NMR (CDCl.sub.3) 8.50 (d, 1H), 7.81-7.83 (d, 1H), 7.27-7.30 (dd, 1H), 6.95-6.98 (dd, 1H), 4.05 (S, 3H), 2.85-2.90 (q, 2H), 1.15-1.18 (t, 3H). LC-MS: Mass found (M−1)=237.

Step-6: Manufacture of methyl 3-ethylsulfonylpyrazolo[1,5-a]pyridine-2-carboxylate

[1471] To a stirred solution of methyl 3-ethylsulfanylpyrazolo[1,5-a]pyridine-2-carboxylate (0.285 g, 1.20 mmol) in DCM (5 mL) was added meta-Chloroperoxybenzoic acid (3 equivalents) at 0° C. The reaction mixture was then allowed to warm to 20 to 25° C. and stirred for 16 hours. The reaction was then quenched with a saturate aqueous solution of NaHCO.sub.3. Work-up of the reaction mixture by extraction and purification by column chromatography afforded methyl 3-ethylsulfonylpyrazolo[1,5-a]pyridine-2-carboxylate (0.295 g, 91.33% yield). .sup.1H-NMR (CDCl.sub.3) 8.58-8.59 (d, 1H), 8.34-8.36 (d, 1H), 7.50-7.53 (dd, 1H), 7.14-7.17 (dd, 1H), 4.07 (S, 3H), 3.63-3.67 (q, 2H), 1.26-1.35 (t, 3H). LC-MS: Mass found (M−1)=269.

Step-7: Manufacture of 3-ethylsulfonylpyrazolo[1,5-a]pyridine-2-carboxylic acid

[1472] To a composition comprising methyl 3-ethylsulfonylpyrazolo[1,5-a]pyridine-2-carboxylate (8.2 g) in water (100 mL) was added LiOH (3.28 g) at 0° C. and stirred for 10 min. Then, CH.sub.3CH.sub.2OH (50 mL) was added and the resulting reaction mixture was heated to 100° C. for 2 hours. Subsequently, the pH of the reaction mixture was adjusted to pH 2 by addition of HCl (2M). Work-up of the reaction mixture by extraction afforded 3-ethylsulfonylpyrazolo[1,5-a]pyridine-2-carboxylic acid pure product. (6.5 g, 83.6% yield). .sup.1H-NMR (DMSO-d6) 8.96-8.94 (d, 1H), 8.09-8.11 (d, 1H), 7.68-7.71 (dd, 1H), 7.31-7.34 (dd, 1H), 3.54-3.58 (q, 2H), 1.06-1.11 (t, 3H). LC-MS: Mass found (M+1)=255.

Step-8: Manufacture of 3-ethylsulfonyl-N-methoxy-N-methyl-pyrazolo[1,5-a]pyridine-2-carboxamide

[1473] To a stirred composition comprising 3-ethylsulfonylpyrazolo[1,5-a]pyridine-2-carboxylic acid (1 g) from step-7 in dry CH.sub.2Cl.sub.2 (20 mL) were added N,O-Dimethylhydroxylamine hydrochloride (0.496 g), diisopropylethylamine (2.03 g) at 0° C. under nitrogen atmosphere. The resulting reaction mixture was then stirred at 0° C. for 10 min, after which propanephosphonic acid anhydride (3.75 g) was added. The resulting reaction mixture was slowly allowed to warm up to 20 to 25° C. and it was stirred for approximately 16 hours. The reaction was then quenched with water. Work-up of the reaction mixture by extraction afforded 3-ethylsulfonyl-N-methoxy-N-methyl-pyrazolo[1,5-a]pyridine-2-carboxamide (1 g, 85.5% yield). .sup.1H-NMR (CDCl.sub.3) 8.48 (d, 1H), 8.25-8.26 (d, 1H), 7.42-7.45 (dd, 1H), 7.01-7.04 (dd, 1H), 4.03-4.07 (q, 2H), 3.62 (S, 3H), 3.49 (S, 3H), 1.17-1.19 (t, 3H). LC-MS: Mass found (M−1)=298.

Step-9: Manufacture of 1-(3-ethylsulfonylpyrazolo[1,5-a]pyridin-2-yl)ethanone

[1474] To a stirred composition comprising 3-ethylsulfonyl-N-methoxy-N-methyl-pyrazolo[1,5-a]pyridine-2-carboxamide (1 g) in THF (10 mL) was added a solution of CH.sub.3MgBr in diethyl ether (3M, 6.73 mmol) at 0° C. under nitrogen atmosphere. The resulting reaction mixture was then stirred at 0° C. for 30 min. The reaction mixture was then diluted with a 1 N aqueous solution of HCl (10 mL). Work-up of the resulting mixture by extraction afforded off white solid 1-(3-ethylsulfonylpyrazolo[1,5-a]pyridin-2-yl)ethanone (0.6 g, 70.75% yield). .sup.1H-NMR (CDCl.sub.3) 8.44 (d, 1H), 8.27-8.29 (d, 1H), 7.41-7.43 (dd, 1H), 7.07-7.08 (dd, 1H), 3.58-3.62 (q, 2H), 2.68 (S, 3H), 1.20-1.24 (t, 3H). LC-MS: Mass found (M+1)=253.

Step-10: Manufacture of 2-bromo-1-(3-ethylsulfonylpyrazolo[1,5-a]pyridin-2-yl)ethanone

[1475] To a composition comprising 1-(3-ethylsulfonylpyrazolo[1,5-a]pyridin-2-yl)ethanone (3.8 g) from step-9 in toluene (50 ml) was added 33% HBr in CH.sub.3COOH (15 ml) at 25° C. dropwise over a period of 25 min. To this reaction mixture was added Br.sub.2 (2.44 g) dropwise over a period of 20 min, upon which the reaction mixture was stirred at 25° C. for 16 hours. The reaction was then quenched with water. Work-up by extraction and recrystallization in heptane:ethyl acetate (8:2) afforded pure 2-bromo-1-(3-ethylsulfonylpyrazolo[1,5-a]pyridin-2-yl)ethanone (3.5 g, 70.10% yield). .sup.1H-NMR (CDCl.sub.3) 8.58 (d, 1H), 8.39 (d, 1H), 7.5 (dd, 1H), 7.19 (dd, 1H), 4.74 (S, 2H) 3.65-3.67 (q, 2H), 1.31-1.34 (t, 3H). LC-MS: Mass found (M+1)=331.

Step-11: Synthesis of 6-cyclopropyl-2-(3-ethylsulfonylpyrazolo[1,5-a]pyridin-2-yl)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (compound I.11)

[1476] To a stirred composition comprising 1-cyclopropyl-4-imino-6-(trifluoromethyl)pyrimidin-2-one (2 g) in (CH.sub.3).sub.3COH (20 mL) was added 2-bromo-1-(3-ethylsulfonylpyrazolo[1,5-a]pyridin-2-yl)ethanone (3.6 g). Molecular sieves was added to the resulting reaction mixture reaction mixture (2 g), which was subsequently heated to 120° C. for 24 hours. The reaction mixture was then filtered through a celite bed and the filtrate was collected and concentrated under reduced pressure. The resulting residue was purified by column chromatography to afford 6-cyclopropyl-2-(3-ethylsulfonylpyrazolo[1,5-a]pyridin-2-yl)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one as an of white solid (1.5 g, 50% yield). H.sup.1-NMR (500 MHz, DMSO-d6): δ 8.95 (d, 1H, J=5 Hz), 8.40 (s, 1H), 8.13 (d, 1H, J=5 Hz), 7.66 (dd, 1H, J=7 Hz), 7.49 (s, 1H), 7.26 (d, 1H, J=5 Hz), 3.66 (t, 2H, J=7 Hz), 3.18 (s, 1H), 1.22 (t, 3H, J=5 Hz), 1.13 (m, 4H). LC-MS: mass calculated [M+1].sup.+ 452.42, LC-MS: Mass found 452.0.

[1477] Table C below lists compounds of formula I.A.1 by the meaning of variables R.sup.1, R.sup.3, and D,

##STR00048##

which compounds were synthesized as described in Synthesis Example C, or in analogy thereto.

TABLE-US-00003 TABLE C compounds I.11 to I.12 with physical characterization data. .sup.1H-NMR data, δ, (500 MHz), Compound R.sup.1 R.sup.3 D solvent in brackets I.11 CF.sub.3 cyclopropyl [00049] 8.95 (d, 1H, J = 5 Hz), 8.40 (s, 1H), 8.13 (d, 1H, J = 5 Hz), 7.66 (dd, 1H, J = 7 Hz), 7.49 (s, 1H), 7.26 (d, 1H, J = 5 Hz), 3.66 (t, 2H, J = 7 Hz), 3.18 (s, 1H), 1.22 (t, 3H, J = 5 Hz), 1.13 (m, 4H). (CDCl.sub.3) I.12 CF.sub.3 CH.sub.3 [00050] 8.96 (d, J = 6.9 Hz, 1H), 8.46 (s, 1H), 8.14 (d, J = 9.0 Hz, 1H), 7.6 (dd, J = 9.1, 6.9 Hz, 1H), 7.55 (s, 1H), 7.28 (t, J = 6.9 Hz, 1H), 3.65 (q, J = 7.4 Hz, 2H), 3.62 (s, 3H), 1.16 (t, J = 7.3 Hz, 3H) (DMSO-d6) &signifies the connection to the remainder of the molecule of formula I.A.1.

Synthesis Example D: 2-(3-ethylsulfonyl-5,6,7,8-tetrahydroimidazo[1,2-a]pyridin-2-yl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (compound I.13)

Step-1: Manufacture of ethyl 5,6,7,8-tetrahydroimidazo[1,2-a]pyridine-2-carboxylate

[1478] A composition comprising ethyl imidazo[1,2-a]pyridine-2-carboxylate (5.2 g) as obtained in Synthesis Example B, step-1, in THF (100 mL), CH.sub.3CH.sub.2OH (100 mL), CH.sub.3COOH (10 mL) and Pd on carbon (10%,1.44 g) was prepared. Subsequently, H.sub.2-gas at a pressure of 5 bar pressure was applied to the composition for 16 hours. The resulting composition was filtered, and concentrated by evaporation under reduced pressure. Work-up by extraction afforded ethyl 5,6,7,8-tetrahydroimidazo[1,2-a]pyridine-2-carboxylate. (4.61 g, 86.81% yield). .sup.1H-NMR (CDCl.sub.3) 7.74 (S, 1H), 4.18-4.21 (q, 2H), 3.97-3.99 (t, 2H) 2.72-2.74 (t, 2H) 1.83-1.89 (m, 4H), 1.23-1.26 (t, 3H). LC-MS: Mass found (M+1) 195.

Step-2: Manufacture of 1-(3-ethylsulfonyl-5,6,7,8-tetrahydroimidazo[1,2-a]pyridin-2-yl)ethanone

[1479] The compound ethyl 5,6,7,8-tetrahydroimidazo[1,2-a]pyridine-2-carboxylate from step-1 was converted in process steps analogous to Synthesis Example C, step-4 to step-9 to compound 1-(3-ethylsulfonyl-5,6,7,8-tetrahydroimidazo[1,2-a]pyridin-2-yl)ethanone. .sup.1H-NMR (DMSO-d6) 4.22-4.25 (t, 2H), 3.57-3.60 (t, 2H), 2.85-2.88 (t, 2H), 2.51 (S, 3H) 1.92-1.94 (t, 2H) 1.84-1.86 (t, 2H) 1.19 (t, 3H), LC-MS: Mass found (M+1) 257.

Step-3: Manufacture of 2-bromo-1-(3-ethylsulfonyl-5,6,7,8-tetrahydroimidazo[1,2-a]pyridin-2-yl)ethanone

[1480] To a solution comprising 1-(3-ethylsulfonyl-5,6,7,8-tetrahydroimidazo[1,2-a]pyridin-2-yl)ethanone (2 g) from step-2 in dioxane (30 mL) was added pyridinium tribromide (2.5 g) at 25° C. and the resulting reaction mixture was heated to 105° C. for 2 hours. Quenching with water, extraction of the reaction mixture and purification of the extracted crude product by column chromatography afforded 2-bromo-1-(3-ethylsulfonyl-5,6,7,8-tetrahydroimidazo[1,2-a]pyridin-2-yl)ethanone. (0.9 g, 35.24% yield). .sup.1H-NMR (DMSO-d6) 4.76 (s, 2H), 4.25-4.27 (t, 2H) 3.57-3.61 (q, 2H), 2.87-2.89 (t, 2H), 1.82-1.96 (m, 4H) 1.25 (t, 3H), LC-MS: Mass found (M+1) 335.

Step-4: Manufacture of 2-(3-ethylsulfonyl-5,6,7,8-tetrahydroimidazo[1,2-a]pyridin-2-yl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (compound I.13)

[1481] To a stirred composition comprising 4-amino-1-methyl-6-(trifluoromethyl)pyrimidin-2-one (0.15 g) in tert-butanol (2 mL) was added 2-bromo-1-(3-ethylsulfonyl-5,6,7,8-tetrahydroimidazo[1,2-a]pyridin-2-yl)ethanone (0.25 g) from step-3. Molecular sieves was added to the above reaction mixture (0.2 g), which was subsequently heated to 120° C. for 24 hours. Then, the reaction mixture was filtered through a celite bed, whereupon the filtrate was collected and concentrated under reduced pressure to afford a crude product. Purification of the crude product by column chromatography afforded compound I.12 as a yellow solid (0.12 g, 33.4% yield). H.sup.1 NMR (500 MHz, DMSO-d6): 8.12 (s, 1H), 7.45 (s, 1H), 4.22 (t, 2H), 3.63 (q, 2H), 3.33 (s, 3H), 2.74 (t, 2H), 1.20 (q, 2H), 1.19 (q, 2H), 1.18 (t, 3H), LC-MS: mass calculated [M+1] 429, LC-MS: Mass found (M+1) 430.0.

[1482] Table D below lists compounds of formula I.A.1 by the meaning of variables R.sup.1, R.sup.3, and D,

##STR00051##

which compounds were synthesized as described in Synthesis Example D, or in analogy thereto.

TABLE-US-00004 TABLE D compounds I.13 to I.14 with physical characterization data. .sup.1H-NMR data, δ, (500 MHz), Compound R.sup.1 R.sup.3 D solvent in brackets I.13 CF.sub.3 CH.sub.3 [00052] 8.12 (s, 1H), 7.45 (s, 1H), 4.22 (t, 2H), 3.63 (q, 2H), 3.33 (s, 3H), 2.74 (t, 2H), 1.20 (q, 2H), 1.19 (q, 2H), 1.18 (t, 3H) I.14 CF.sub.3 cyclopropyl [00053] 8.07 (s, 1H), 7.40 (s, 1H), 4.22 (m, 2H), 3.95 (t, 2H), 3.18 (s, 1H), 2.89 (m, 2H), 1.91 (m, 2H), 1.86 (m, 2H) 1.22 (t, 3H), 1.14 (s, 2H). 1.13 (s, 2H). &signifies the connection to the remainder of the molecule of formula I.A.1.

Synthesis Example E: 6-cyclopropyl-2-(3-ethylsulfonylimidazo[1,2-a]pyrimidin-2-yl)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (compound I.15)

Step-1: Manufacture of 1-imidazo[1,2-a]pyrimidin-2-ylethanone

[1483] To a composition comprising 2-aminopyrimidine (1 g) in acetone (10 mL) was added slowly 1-bromobutane-2,3-dione (1.5 g) dropwise over a period a time of 10 min at 20 to 25° C. Subsequently, the resulting reaction mixture was heated under refluxation for 2 hours. The solid precipitate was dissolved in a mixture of CH.sub.3CH.sub.2OH:H.sub.2O (weight ratio 10:3) and heated to 64° C. After cooling to 20 to 25° C. and work-up by concentration under reduced pressure, 1-imidazo[1,2-a]pyrimidin-2-ylethanone was afforded (1.0 g, 60% yield). .sup.1H-NMR (CDCl.sub.3) 9.01-8.99 (dd, 1H), 8.69-8.68 (dd, 1H), 8.45 (S, 1H), 7.17-7.15 (dd, 1H), 2.58 (S, 3H), LC-MS: Mass found (M+1) 161.1.

Step-2: Manufacture of 1-(3-chloroimidazo[1,2-a]pyrimidin-2-yl)ethanone

[1484] To a stirred composition comprising 1-imidazo[1,2-a]pyrimidin-2-ylethanone (1 g) from step-1 in CHCl.sub.3 (10 mL) was added Palau' chlor (0.913 g) at 20 to 25° C. under nitrogen atmosphere. The resulting reaction mixture was stirred at the same temperature for approximately 15 hours. The reaction was subsequently quenched by addition of water and worked-up by extraction to afford 1-(3-chloroimidazo[1,2-a]pyrimidin-2-yl)ethanone as white solid. (1.0 g, 60% yield). .sup.1H-NMR (d6-CDCl.sub.3) 8.78-8.75 (m, 2H), 7.32-7.29 (m, 1H), 2.65 (S, 3H), LC-MS: Mass found (M+1) 195.1.

Step-3: Manufacture of 1-(3-ethylsulfanylimidazo[1,2-a]pyrimidin-2-yl)ethanone

[1485] To a stirred composition comprising 1-(3-chloroimidazo[1,2-a]pyrimidin-2-yl)ethanone (4 g) from step-2 in THF (40 mL) was added sodium ethanethiolate (2.24 g) at 0° C. The resulting reaction mixture was stirred at 0° C. for 2 hours. The reaction was then quenched with water. Work-up of the resulting mixture by extraction afforded 1-(3-ethylsulfanylimidazo[1,2-a]pyrimidin-2-yl)ethanone (2.0 g, yield: 60%). .sup.1H-NMR (d6-CDCl.sub.3) 9.07-9.06 (d, 1H), 8.78-8.77 (dd, 1H), 7.30-7.27 (dd, 1H), 3.61 (S, 3H), 2.93 (q, 2H), 1.06 (t, 3H), LC-MS: Mass found (M+1) 221.1.

Step-4: Manufacture of 1-(3-ethylsulfonylimidazo[1,2-a]pyrimidin-2-yl)ethanone

[1486] To a stirred composition comprising ethyl 3-ethylsulfanylimidazo[1,2-a]pyridine-2-carboxylate (5 g) in CH.sub.2Cl.sub.2 (100 mL) was added meta-Chloroperoxybenzoic acid (3 eq) at 0° C. The resulting reaction mixture was then allowed to warm up to 20 to 25° C. and then stirred for 16 hours. The reaction was diluted with water (50 mL) and an aqueous saturated solution of sodium bisulphite was added (50 mL). The reaction mixture was stirred for another 10 minutes, upon which 50 mL of an aqueous solution of NaHCO.sub.3 (10 wt %) was added. Extraction of the reaction mixture afforded 1-(3-ethylsulfonylimidazo[1,2-a]pyrimidin-2-yl)ethanone as yellow colour solid. (3 g, yield: 65%). .sup.1H-NMR (CDCl.sub.3): 9.50-9.48 (dd, 1H), 8.99-8.98 (d, 1H), 7.61-7.55 (dd, 1H), 3.70 (s, 3H), 3.76-3.72 (q, 2H), 1.30-1.34 (t, 3H), LC-MS: Mass found (M+1) 254.2

Step-5: Manufacture of 2-bromo-1-(3-ethylsulfonylimidazo[1,2-a]pyrimidin-2-yl)ethanone

[1487] A composition comprising 1-(3-ethylsulfonylimidazo[1,2-a]pyrimidin-2-yl)ethanone (0.3 g) from step-4 in toluene (3 mL) at 0° C. was prepared. Subsequently, a composition of 33 wt % HBr in CH.sub.3COOH (1 mL) was added to the reaction mixture at 0° C. The reaction mixture was then stirred for 10 min. After that, Br.sub.2 (0.004 mol) was added dropwise to the reaction mixture, which was then stirred at 20 to 25° C. for approximately 15 hours. Work-up of the reaction mixture by quenching with water, extraction, and column chromatography afforded 2-bromo-1-(3-ethylsulfonylimidazo[1,2-a]pyrimidin-2-yl)ethanone (0.1 g, 60% yield). .sup.1H-NMR (DMSO-d6) 9.96 (m, 1H), 8.97 (m, 1H), 7.50 (m, 1H), 5.02 (S, 2H), 3.74 (q, 2H), 1.26 (t, 3H), LC-MS: Mass found (M+1) 331.12.

Step-6: Manufacture of 6-cyclopropyl-2-(3-ethylsulfonylimidazo[1,2-a]pyrimidin-2-yl)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (compound I.15)

[1488] To a stirred composition of 1-cyclopropyl-4-imino-6-(trifluoromethyl)pyrimidin-2-one (0.15 g, 6.8 mmol) in tert-butanol (2 mL) was added 2-bromo-1-(3-ethylsulfonylimidazo[1,2-a]pyrimidin-2-yl)ethanone (0.23 g, 6.8 mol). Molecular sieves was added to the above reaction mixture (0.2 g) and the resultant reaction mixture was heated to 120° C. for 24 hours. Subsequently, the reaction mixture was filtered through a celite bed, and the filtrate was collected and concentrated under reduced pressure. The resulting residue was subjected to column chromatography to afford 6-cyclopropyl-2-(3-ethylsulfonylimidazo[1,2-a]pyrimidin-2-yl)-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one as a yellow solid (0.12 g, 30.9% yield). H.sup.1 NMR (500 MHz, DMSO-d6): δ 9.42 (q, 1H), 8.85 (q, 1H), 8.37 (s, 1H), 7.50 (s, 1H), 7.38 (q, 1H), 3.95 (t, 2H), 3.18 (s, 1H), 1.22 (t, 3H), 1.14 (s, 2H). 1.13 (s, 2H). LC-MS: mass calculated [M+1].sup.+ 453.4, LC-MS: Mass found (M+1) 453.0.

B. BIOLOGICAL EXAMPLES

[1489] 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:acteone. The test solution is prepared at the day of use. Test solutions are prepared in general at concentrations of 2500 ppm, 1415 ppm, 828 ppm, 800 ppm and 300 ppm (wt/vol).

[1490] Boll Weevil (Anthonomus grandis)

[1491] 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 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. 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 I.2, I.3, I.4, I.5, and I.6 at 828 ppm showed over 75% mortality in comparison with untreated controls. In this test, compounds I.1, I.8, I.11 and I.13 at 800 ppm showed over 75% mortality in comparison with untreated controls.

[1492] Tobacco Budworm (Heliothis virescens)

[1493] 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, compound I.1, I.3, I.4, I.5, and I.6 at 2500 ppm showed over 75% mortality in comparison with untreated controls. In this test, compound I.8, and I.11 at 800 ppm showed over 75% mortality in comparison with untreated controls.

[1494] Vetch Aphid (Megoura viciae)

[1495] 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.

[1496] 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, compound I.1 at 2500 ppm showed over 75% mortality in comparison with untreated controls.

[1497] Green Peach Aphid (Myzus persicae)

[1498] 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, compound I.1, I.2, I.3, I.4, I.5, and I.6 at 2500 ppm showed over 75% mortality in comparison with untreated controls. In this test, compounds I.7, I.8, I.11, and I.12, at 800 ppm showed over 75% mortality in comparison with untreated controls.

[1499] Greenhouse Whitefly (Trialeurodes vaporarirorum)

[1500] 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% R.sup.H for 6 days. Mortality of hatched crawlers was then visually assessed. In this test, compounds I.2 and I.6 at 2500 ppm showed at least 75% mortality in comparison with untreated controls. In this test, compound I.12 at 800 ppm showed at least 75% mortality in comparison with untreated controls.

[1501] Yellow Fever Mosquito (Aedes aegypti)

[1502] 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 5 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% R.sup.H for 2 days. Larval 10 mortality was then visually assessed. In this test, compounds I.1, I.2, I.3, I.4, I.5, and I.6 at 2500 ppm showed at least 75% mortality in comparison with untreated controls. In this test, compound I.8 and I.11 at 800 ppm showed at least 75% mortality in comparison with untreated controls.

[1503] Southern Green Stink Bug (Nezara viridula)

[1504] The active compound is dissolved at the desired concentration in a mixture of 1:1 (vokvol) distilled water:acetone. Surfactant (KineticR HV) is added at a rate of 0.01% (vol/vol). The test solution is prepared at the day of use. Soybean pods were placed in 90×50 mm glass Petri dishes lined with moist filter paper and inoculated with ten late 3rd instar N. viridula. Using a hand atomizer, an approximately 2 ml solution is sprayed into each Petri dish. Treated cups were kept at about 25-26° C. and relative humidity of about 65-70%. Percent mortality was recorded after 5 days. In this test, compound I.6 and I.8 at 300 ppm showed at least 75% mortality in comparison with untreated controls.