Substituted pyrimidinium compounds and derivatives for combating animal pests

Abstract

Substituted pyrimidinium compounds of the general formula (I) and their uses for combating animal pests The present invention relates to substituted pyrimidinium compounds of formula (I), to the stereoisomers, salts, tautomers and N-oxides thereof and to compositions comprising such compounds. The invention also relates to methods and uses of these substituted pyrimidinium compounds and of compositions thereof, for combating and controlling animal pests. Furthermore the invention relates also to pesticidal methods of applying such substituted pyrimidinium compounds. The substituted pyrimidinium compounds of the present invention are defined by the following general formula (I): ##STR00001##
wherein X, Y, Z, R.sup.1, R.sup.2, A and Het are defined as in the description.

Claims

1. A substituted pyrimidinium compound of formula (I) ##STR00136## wherein X, Y are each independently O or S; Z is selected from the group consisting of a direct bond, O, S(O), NR.sup.b, C(R.sup.aR.sup.aa)O, C(═X.sup.1), C(═X.sup.1)Y.sup.1, and Y.sup.1C(═X.sup.1); X.sup.1 is selected from the group consisting of O, S, and NR.sup.b; Y.sup.1 is selected from the group consisting of O, S, and NR.sup.c; A is CH or N and, wherein the nitrogen of the pyrimidinium ring taken together with the contiguous linking carbon atom and A as depicted in formula (I), form a four- to seven-membered ring, wherein each remaining ring member is selected from carbon atoms and up to 3 heteroatoms independently selected from up to 2 O, up to 2 S, and up to 3 N(R.sup.c).sub.p, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S), and the sulfur atom ring members are independently selected from S(═O).sub.m, wherein each ring may be substituted with up to 3 R.sup.a; Het is selected from any one of the following ring systems D-1 to D-56: ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## where # denotes the bond to A in formula (I); R.sup.1 is selected from the group consisting of hydrogen, C.sub.1-C.sub.8-alkyl, C.sub.2-C.sub.8-alkenyl, C.sub.2-C.sub.8-alkynyl, C.sub.3-C.sub.10-cycloalkyl, C.sub.4-C.sub.10-cycloalkenyl, and C.sub.5-C.sub.14-cycloalkylcycloalkyl or R.sup.1 may form a three- to eleven-membered saturated, or partially unsaturated or aromatic carbo-or heterocyclic ring or ring system, which may contain 1 to 4 heteroatoms selected from the group consisting of N(R.sup.c).sub.p, O, and S, wherein S may be oxidized, and wherein the aforementioned groups and the carbo- or heterocyclic rings system may be unsubstituted, partially or fully substituted by R.sup.a; or R.sup.1 is selected from the group consisting of C(═O)R.sup.b, C(═O)OR.sup.e, NR.sup.bR.sup.c, (═O)NR.sup.bR.sup.c, C(═S)NR.sup.bR.sup.c, SO.sub.2NR.sup.bR.sup.c, OC(═O)R.sup.c, OC(═O)OR.sup.e, OC(═O)NR.sup.bR.sup.e, N(R.sup.c)C(═O)R.sup.c, N(R.sup.c)C(═O)OR.sup.e, N(R.sup.c)C(═O)NR.sup.bR.sup.c, NR.sup.cSO.sub.2R.sup.b, NR.sup.cSO.sub.2NR.sup.bR.sup.c, Si(R.sup.d).sub.3, C(═NR.sup.c)R.sup.c, C(═NOR.sup.c)R.sup.c,, C(═NNR.sup.bR.sup.c)R.sup.c, C(═NN(C(═O)R.sup.b)R.sup.c)R.sup.c, C(═NN(C═O)OR.sup.c)(R.sup.c).sub.2, S(═O).sub.o(═NR.sup.b).sub.qR.sup.c and N═CR.sup.bR.sup.c; R.sup.a is each independently selected from the group consisting of halogen, 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.6-haloalkoxy, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.3-C.sub.6-cycloalkyl, CN, OR.sup.c, NR.sup.bR.sup.c, NO.sub.2, C(═O)(O).sub.pR.sup.c, OC(═O)(O).sub.pR.sup.e, C(═O)NR.sup.bR.sup.c, OC(═O)NR.sup.bR.sup.e, NR.sup.bC(═O)(O).sub.pR.sup.e, NR.sup.bC(═O)NR.sup.bR.sup.c, C(═S)NR.sup.bR.sup.c, S(O).sub.mR.sup.b, SO.sub.2NR.sup.bR.sup.c, OSO.sub.2R.sup.c, OSO.sub.2NR.sup.bR.sup.c, NR.sup.bSO.sub.2R.sup.c, NR.sup.bSO.sub.2NR.sup.bR.sup.c, N═S(═O).sub.pR.sup.cR.sup.c, S(═O).sub.o(═NR.sup.b).sub.qR.sup.c, SF.sub.5, OCN, SCN, Si(R.sup.d).sub.3 and a three- to six-membered saturated, or partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from the group consisting of N—(R.sup.c).sub.p, O, and S which may be oxidized, and wherein the aforementioned groups and the carbo- or heterocyclic ring may be partially or fully substituted by R.sup.aa, or two geminally bound groups R.sup.a together may form a group selected from the group consisting of ═O, ═S, ═CR.sup.bR.sup.c, ═NR.sup.c, ═NOR.sup.c, and ═NNR.sup.cR.sup.c; R.sup.aa is each independently selected from the group consisting of halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-haloalkoxy; R.sup.b is each independently selected from the group consisting of hydrogen, 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.6-haloalkoxy and a three- to six-membered saturated, or partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from the group consisting of N(R.sup.c).sub.p, O, and S, wherein S may be oxidized and which carbo- or heterocyclic ring may be partially or fully substituted by R.sup.aa; R.sup.c is each independently selected from the group consisting of hydrogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkylcarbonyl, C.sub.1-C.sub.6 cycloalkyl, and a three- to six-membered saturated, partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from the group consisting of N(R.sup.aa).sub.p, O and S, wherein S may be oxidized and wherein the carbo- or heterocyclic ring may be partially or fully substituted by R.sup.aa; wherein two geminally bound groups R.sup.bR.sup.b, R.sup.cR.sup.b or R.sup.cR.sup.c together with the atom to which they are bound, may form a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 2 heteroatoms or heteroatoms groups selected from the group consisting of N, O, S, NO, SO and SO.sub.2 and wherein the carbo- or heterocyclic ring may be partially or fully substituted by R.sup.3; R.sup.d is each independently selected from the group consisting of hydrogen, phenyl, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.8-cycloalkyl, and C.sub.1-C.sub.6-alkoxyalkyl, wherein the above mentioned groups may be substituted by one or more halogen; R.sup.e is each independently selected from the group consisting of C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkylcarbonyl, C.sub.1-C.sub.6 cycloalkyl, and a three- to six-membered saturated, partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from the group consisting of N(R.sup.aa).sub.p, O and S, wherein S may be oxidized and wherein the carbo- or heterocyclic ring may be partially or fully substituted by R.sup.aa; n is 0, 1 or 2; m is 0, 1, or 2; p is 0 or 1; R.sup.2 is selected from the group consisting of H, halogen, CN, C.sub.1-C.sub.8 alkyl, C.sub.2-C.sub.8 alkenyl, C.sub.2-C.sub.8 alkynyl, C.sub.3-C.sub.10 cycloalkyl, C.sub.4-C.sub.10 alkylcycloalkyl, C.sub.4-C.sub.10 cycloalkylalkyl, C.sub.6-C.sub.14 cycloalkylcycloalkyl, C.sub.5-C.sub.10 alkylcycloalkylalkyl, and C.sub.3-C.sub.6 cycloalkenyl, wherein the aforementioned groups may be unsubstituted, partially, or fully substituted with R.sup.2a, or R.sup.2 may form a carbo-or heterocyclic three- to ten-membered ring or a seven- to eleven-membered rings system, which ring or ring system may be saturated, partially unsaturated, or aromatic, and which ring or ring system may contain 1 to 4 heteroatoms selected from the group consisting of N(R.sup.c).sub.p, O, and S, wherein S may be oxidized, and wherein the carbo- or heterocyclic ring or rings system may be unsubstituted, partially, or fully substituted by R.sup.2a; with the proviso that if R.sup.2 is halogen or CN, then Z is a direct bond; R.sup.2a is each independently selected from the group consisting of halogen, 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.6-haloalkoxy, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.3-C.sub.6-cycloalkyl, CN, OR.sup.C, NR.sup.bR.sup.c, NO.sub.2, C(═O)(O).sub.pR.sup.c, OC(═O)(O).sub.pR.sup.e, C(═O)NR.sup.bR.sup.c, OC(═O)NR.sup.bR.sup.e, NR.sup.bC(═O)(O).sub.pR.sup.e, NR.sup.bC(═O)NR.sup.bR.sup.c, C(═S)NR.sup.bR.sup.c, S(O).sub.mR.sup.b, SO.sub.2NR.sup.bR.sup.c, OSO.sub.2R.sup.c, OSO.sub.2NR.sup.bR.sup.c, NR.sup.bSO.sub.2R.sup.c, NR.sup.bSO.sub.2NR.sup.bR.sup.c, SF.sub.5, OCN, SCN, Si(R.sup.d).sub.3, C(═N(O).sub.pR.sup.b) R.sup.b, C(═NNR.sup.bR.sup.c)R.sup.b, C(═NN(C(═O)O.sub.pR.sup.c)R.sup.c)R.sup.b, ON═CR.sup.bR.sup.c, ONR.sup.bR.sup.c, S(═O).sub.o(═NR.sup.b).sub.qR.sup.c, SO.sub.2NR.sup.b(═O)NR.sup.bR.sup.c, P(═X.sup.2)R.sup.bR.sup.c, OP(═X.sup.2)(O.sub.pR.sup.c)R.sup.b, OP(═X.sup.2)(OR.sup.c).sub.2, N═CR.sup.bR.sup.c, NR.sup.bN═CR.sup.bR.sup.c, NR.sup.bNR.sup.bR.sup.c, NR.sup.bC(═S)NR.sup.bR.sup.c, NR.sup.bC(═NR.sup.b)NR.sup.bR.sup.c, NR.sup.bNR.sup.bC(═X.sup.2)NR.sup.bR.sup.c, NR.sup.bNR.sup.bSO.sub.2NR.sup.bR.sup.c, N═S(═O).sub.pR.sup.cR.sup.c, and a three- to six-membered saturated, or partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from the group consisting of N—(R.sup.c).sub.p, O, and S, wherein S may be oxidized, and wherein the aforementioned groups and the carbo- or heterocyclic ring may be partially or fully substituted by R.sup.2aa or two geminally bound groups R.sup.2a together may form a group selected from the group consisting of ═O, ═S, ═CR.sup.bR.sup.c, ═NR.sup.c, ═NOR.sup.c, and ═NNR.sup.cR.sup.c; R.sup.2aa is each independently selected from the group consisting of halogen, 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.6-haloalkoxy, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.3-C.sub.6-cycloalkyl, CN, OR.sup.c, NR.sup.bR.sup.c, NO.sub.2, C(═O)(O).sub.pR.sup.c, OC(═O)(O).sub.pR.sup.e, C(═O)NR.sup.bR.sup.c, OC(═O)NR.sup.bR.sup.e, NR.sup.bC(═O)(O).sub.pR.sup.e, NR.sup.bC(═O)NR.sup.bR.sup.c, C(═S)NR.sup.bR.sup.c, S(O).sub.mR.sup.b, SO.sub.2NR.sup.bR.sup.c, OSO.sub.2R.sup.c, OSO.sub.2NR.sup.bR.sup.c, NR.sup.bSO.sub.2R.sup.c, NR.sup.bSO.sub.2NR.sup.bR.sup.c, SF.sub.5, OCN, SCN, Si(R.sup.d).sub.3, C(═N(O).sub.pR.sup.b)R.sup.b, C(═NNR.sup.bR.sup.c)R.sup.b, C(═NN(C(═O)O.sub.pR.sup.c)R.sup.b)R.sup.b, ON═CR.sup.bR.sup.c, ONR.sup.bR.sup.c, S(═O).sub.o(═NR.sup.b).sub.qR.sup.c, SO.sub.2NR.sup.b(═O)NR.sup.bR.sup.c, P(═X.sup.2)R.sup.bR.sup.c, OP(═X.sup.2)(O.sub.pR.sup.c)R.sup.b, OP(═X.sup.2)(OR.sup.c).sub.2, N═CR.sup.bR.sup.c, NR.sup.bN═CR.sup.bR.sup.c, NR.sup.bNR.sup.bR.sup.c, NR.sup.bC(═S)NR.sup.bR.sup.c, NR.sup.bC(═NR.sup.b)NR.sup.bR.sup.c, NR.sup.bNR.sup.bC(═X.sup.2)NR.sup.bR.sup.c, NR.sup.bNR.sup.b SO.sub.2NR.sup.bR.sup.c, and N═S(═O).sub.pR.sup.cR.sup.c or two geminally bound groups R.sup.2aa together may form a group selected from the group consisting of ═O, ═S,═CR.sup.bR.sup.c, ═NR.sup.c, ═NOR.sup.c, and ═NNR.sup.cR.sup.c; X.sup.2 is independently O or S; R.sup.3 is each independently selected from the group consisting of halogen, 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.6-haloalkoxy, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.3-C.sub.6-cycloalkyl, CN, OR.sup.c, NR.sup.bR.sup.c, NO.sub.2, C(═O)(O).sub.pR.sup.c, OC(═O)(O).sub.pR.sup.e, C(═O)NR.sup.bR.sup.c, OC(═O)NR.sup.bR.sup.e, NR.sup.bC(═O)(O).sub.pR.sup.e, NR.sup.bC(═O)NR.sup.bR.sup.c, (═S)NR.sup.bR.sup.c, S(O).sub.mR.sup.b, SO.sub.2NR.sup.bR.sup.c, OSO.sub.2R.sup.c, OSO.sub.2NR.sup.bR.sup.c, NR.sup.bSO.sub.2R.sup.c, NR.sup.bSO.sub.2NR.sup.bR.sup.c, SF.sub.5, OCN, SCN, Si(R.sup.d).sub.3, C(═N(O).sub.pR.sup.b)R.sup.b, C(═NNR.sup.bR.sup.c)R.sup.b, C(═NN(C(═O)O.sub.pR.sup.c)R.sup.b)R.sup.b, ON═CR.sup.bR.sup.c, ONR.sup.bR.sup.c, S(═O).sub.o(═NR.sup.b).sub.qR.sup.c, SO.sub.2NR.sup.b(═O)NR.sup.bR.sup.c, P(═X.sup.2)R.sup.bR.sup.c, OP(═X.sup.2)(O.sub.pR.sup.c)R.sup.b, OP(═X.sup.2)(OR.sup.c).sub.2, N═CR.sup.bR.sup.c, NR.sup.bN═CR.sup.bR.sup.c, NR.sup.bNR.sup.bR.sup.c, NR.sup.bC(═S)NR.sup.bR.sup.c, NR.sup.bC(═NR.sup.b)NR.sup.bR.sup.c, NR.sup.bNR.sup.bC(═X.sup.2)NR.sup.bR.sup.c, NR.sup.bNR.sup.bSO.sub.2NR.sup.bR.sup.c, and N═S(═O).sub.pR.sup.cR.sup.c or two geminally bound groups R.sup.3 together may form a group selected from the group consisting of ═O, ═S, ═CR.sup.bR.sup.c, ═NR.sup.c, ═NOR.sup.c, and ═NNR.sup.cR.sup.c; and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof.

2. The compound of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof as defined in claim 1, wherein Het is selected from any one of the following ring systems: ##STR00142## ##STR00143## ##STR00144##

3. The compound of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof as defined in claim 1, wherein Het is selected from structures D-2, D-9, D-22, D25, D28, D-29 and D-54: ##STR00145## wherein R.sup.a is selected from the group consisting of halogen, C.sub.1-C.sub.4-haloalkyl, C.sub.1C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio and phenyl, n is 0, 1 or 2, and wherever used in a structure, the following: # denotes the bond to A in formula (I).

4. The compound of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof as defined in claim 3, wherein X, Y are each O; A is CH and the nitrogen of the pyrimidinium ring taken together with the contiguous linking carbon atom and A as depicted in formula (I), form a five or six membered ring, wherein each remaining ring member is selected from 2 and 3 carbon atoms; R.sup.1 is selected from the group consisting of CH.sub.3, CH.sub.2CH.sub.3, isopropyl, cyclopropyl, CH.sub.2CF.sub.3, phenyl, allyl and benzyl; R.sup.2 is phenyl which may be substituted by halogen, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-haloalkoxy or phenyl; Z is a direct bond and Het is selected from the group consisting of D-2, D-9, D-25 or D-56 and R.sup.a is Cl, Br, F, SCH.sub.3, CF.sub.3, OCH.sub.3 or phenyl.

5. The compound of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof as defined in claim 1, wherein A is CH or N, wherein the nitrogen of the pyrimidinium ring taken together with the contiguous linking carbon atom and A as depicted in formula (I), form a five or six membered ring, wherein each remaining ring member is selected from carbon atoms and up to one heteroatom selected from the group consisting of O, S and N(R.sup.c).sub.p, which ring may be substituted by R.sup.a.

6. The compound of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof as defined in claim 1, wherein X and Y are O.

7. The compound of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof as defined in claim 1, wherein Z is a direct bond, and R.sup.2 is a six membered carbo- or heterocyclic ring, which ring may be unsubstituted, partially, or fully substituted by R.sup.2a, and wherein R.sup.2a is selected from the group consisting of halogen, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-haloalkoxy, C(═O)OR.sup.c, C(═O)NR.sup.bR.sup.c, phenyl, and pyridyl, which may be substituted by halogen, C.sub.1-C.sub.6-haloalkyl or C.sub.1-C.sub.6-haloalkoxy.

8. The compound of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof as defined in claim 1, wherein R.sup.1 is selected from the group consisting of C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.4-alkenyl, benzyl and phenyl, which groups may be partially or fully substituted by halogen or C.sub.1-C.sub.4-alkyl.

9. A composition comprising at least one compound of formula (I) as defined in claim 1, and at least one inert liquid and/or solid carrier.

10. An agricultural composition for combating animal pests comprising at least one compound of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof as defined in claim 1, and at least one inert liquid and/or solid acceptable carrier and, if desired, at least one surfactant.

11. A seed treated with the compound of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof as defined in claim 1 in an amount of from 0.1 g to 10 kg per 100 kg of seed.

12. A method for protecting crops, plants, plant propagation material and/or growing plants from attack or infestation by invertebrate pests comprising contacting or treating the crops, plants, plant propagation material and growing plants, or soil, material, surface, space, area or water in which the crops, plants, plant propagation material is stored or the plant is growing with a pesticidally effective amount of at least one compound of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof as defined in claim 1.

13. The method of claim 12, wherein Het is selected from any one of the following ring systems: ##STR00146## ##STR00147## ##STR00148##

14. The method of claim 12, wherein Het is selected from structures D-2, D-9, D-22, D25, D28, D-29 and D-54: ##STR00149## wherein R.sup.a is selected from the group consisting of halogen, C.sub.1-C.sub.4-haloalkyl, C.sub.1C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio and phenyl, n is 0, 1 or 2, and wherever used in a structure, the following: # denotes the bond to A in formula (I).

15. The method of claim 14, wherein X, Y are each O; A is CH and the nitrogen of the pyrimidinium ring taken together with the contiguous linking carbon atom and A as depicted in formula (I), form a five or six membered ring, wherein each remaining ring member is selected from 2 and 3 carbon atoms; le is selected from the group consisting of CH.sub.3, CH.sub.2CH.sub.3, isopropyl, cyclopropyl, CH.sub.2CF.sub.3, phenyl, allyl and benzyl; R.sup.2 is phenyl which may be substituted by halogen, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-haloalkoxy or phenyl; Z is a direct bond and Het is selected from the group consisting of D-2, D-9, D-25 or D-56 and R.sup.a is Cl, Br, F, SCH.sub.3, CF.sub.3, OCH.sub.3 or phenyl.

16. The method of claim 12, wherein A is CH or N, wherein the nitrogen of the pyrimidinium ring taken together with the contiguous linking carbon atom and A as depicted in formula (I), form a five or six membered ring, wherein each remaining ring member is selected from carbon atoms and up to one heteroatom selected from the group consisting of O, S and N(R.sup.c).sub.p, which ring may be substituted by R.sup.a.

17. The method of claim 12, wherein X and Y are O.

18. The method of claim 12, wherein Z is a direct bond, and R.sup.2 is a six membered carbo- or heterocyclic ring, which ring may be unsubstituted, partially, or fully substituted by R.sup.2a, and wherein R.sup.2a is selected from the group consisting of halogen, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-haloalkoxy, C(═O)OR.sup.c, C(═O)NR.sup.bR.sup.c, phenyl, and pyridyl, which may be substituted by halogen, C.sub.1-C.sub.6-haloalkyl or C.sub.1-C.sub.6-haloalkoxy.

19. The method of claim 12, wherein R.sup.1 is selected from the group consisting of C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.4-alkenyl, benzyl and phenyl, which groups may be partially or fully substituted by halogen or C.sub.1-C.sub.4-alkyl.

20. A method for combating, controlling, or protecting against infestation or infection by invertebrates pest, 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 formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof as defined in claim 1.

21. A non-therapeutic method for treating animals infested or infected by parasites or protecting animals against infestation or infection by parasites which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of formula (I) and/or stereoisomers or agriculturally or veterinary acceptable salts or tautomers or N-oxides thereof as defined in claim 1.

22. A method for protecting crops, plants, plant propagation material and/or growing plants from attack or infestation by invertebrate pests comprising contacting or treating the crops, plants, plant propagation material and growing plants, or soil, material, surface, space, area or water in which the crops, plants, plant propagation material is stored or the plant is growing with a pesticidally effective amount of the composition of claim 9.

23. A method for combating, controlling, or protecting against infestation or infection by invertebrates pest, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of the composition of claim 9.

Description

S. SYNTHESIS EXAMPLES

Example.1: Synthesis S1

Synthesis of Example numbered C-3: 6-(6-chloro-3-pyridyl)-1-isopropyl-3-methyl-4-oxo-7,8-dihydro-6H-pyrrolo[1,2-a]pyrimidin-1-ium-2-olate

(1) ##STR00083##

Step 1.1: 6-chloro-3-pyridyl) methanol

(2) To a solution of LiAIH4 (25 g, 0.65 mol) in THF (1500 ml) was added a solution of 6-chloropyridine-3-carboxylic acid (50 g, 0.323 mol) in THF drop-wise at 0° C., and the mixture was stirred for 3 h at 0° C. THF and Na.sub.2SO.sub.4×5H.sub.2O was added slowly. After stirring for 20 min, the mixture was filtered and the filtrate was concentrated to give crude product (26 g, yield: 57.1%).

Step 1.2: 6-chloropyridine-3-carbaldehyde

(3) To a solution of PCC (58 g, 0.27 mol) in DCM (1500 ml) was added the product of the proceeding step (26 g, 0.184 mol) as a solution in DCM drop wise at 0° C. The mixture was then stirred for 2 h at 20° C. It was filtered through diatomaceous earth and the filter contents were washed with DCM. The organic phase was concentrated to give the crude product, which was purified by column chromatography to give the product (15 g, yield: 60.1%).

(4) .sup.1H NMR (400 MHz, CDCl3): δ 10.067 (s, 1H), 8.874 (s, 1H, J=3 Hz), 8.158˜8.138 (d, 1H, J=8 Hz), 7.534˜7.513 (d, 1H, J=8 Hz)

Step 1.3: Methyl 4-(6-chloro-3-pyridyl)-4-oxo-butanoate

(5) To a solution of 6-chloropyridine-3-carbaldehyde (10 g, 70 mmol) in DMF (40 ml) was added NaCN (0.7 g, 14 mmol). The mixture was stirred for 1 h followed by dropwise addition of methyl acrylate (5.2 g, 60 mmol). Stirring was continued for 3 h at room temperature, the solution was poured into water, and extracted with EtOAc. The organic phase was dried, filtered and concentrated to give methyl 4-(6-chloro-3-pyridyl)-4-oxo-butanoate (6.8 g, yield: 42.5%).

(6) .sup.1H NMR (400 MHz, CDCl3): δ 8.971˜8.968 (m, 1H), 8.219˜8.198 (d, 1H, J=8.4 Hz), 7.462˜7.441 (d, 1H, J=8.4 Hz), 3.710 (s, 3H), 3.306˜3.274 (m, 1H) 2.812˜2.760 (m, 2H).

Step 1.4: 5-(6-chloro-3-pyridyl) pyrrolidin-2-one

(7) To a solution of methyl 4-(6-chloro-3-pyridyl)-4-oxo-butanoate (6.7 g, 29.5 mmol) in MeOH (100 ml) was added NH.sub.4OAc (6.8 g, 88.3 mmol) and NaBH3CN (5.6 g, 88.3 mmol), and the mixture was refluxed overnight. The solvent was removed in vacuo, the residue dissolved in DCM, washed with brine, dried, and concentrated to give the crude product. Purification by column chromatography gave the product (3 g, yield: 51.9%).

(8) .sup.1H NMR (400 MHz, CDCl3): δ 8.336˜8.330 (d, 1H, J=2.4 Hz), 7.642˜7.616 (m, 1H), 7.361˜7.340 (d, 1H, J=8.4 Hz), 6.987 (s, 1H), 4.819˜4.782 (m, 1H), 2.634˜2.482 (m, 1H), 2.474˜2.432 (m, 2H), 1.967˜1.935 (m, 1H).

Step 1.5: 5-(6-chloro-3-pyridyl) pyrrolidine-2-thione

(9) To a solution of the compound from the preceding step (2.4 g, 12.24 mmol) in dioxane (150 ml) was added P255 (3.3 g, 14.7 mmol) at RT. The mixture was heated to 110° C. and stirred for 2.0 h. After filtration of the hot mixture, the filtrate was concentrated to give the crude material. Purification by column chromatography yielded the pure product (1.56 g, yield: 60.2%).

Step 1.6: 2-chloro-5-(5-methylsulfanyl-3,4-dihydro-2H-pyrrol-2-yl)pyridine

(10) To a solution of 5-(6-chloro-3-pyridyl) pyrrolidine-2-thione (2 g, 9.4 mmol) in acetone (100 ml) was added K.sub.2CO.sub.3. After stirring at RT for 30 min, iodomethane was added and stirred for additional 3 h at room temperature. After filtration, the filtrate was concentrated to give the crude material. Purification by column chromatography yielded the pure product (2.1 g, yield: 97.6%).

(11) .sup.1H NMR (400 MHz, CDCl3): δ 8.320 (s, 1H), 7.564˜7.544 (d, 1H, J=8.0 Hz), 7.298˜7.278 (d, 1H, J=8.0 Hz), 5.105˜5.068 (m, 1H), 2.856˜2.792 (m, 2H), 2.634˜2.513 (m, 2H), 2.179 (s, 3H), 1.820˜1.255 (m, 1H).

Step 1.7: 2-(6-chloro-3-pyridyl)-N-isopropyl-3,4-dihydro-2H-pyrrol-5-amine

(12) To the product from step 6 (0.25 g, 1.03 mmol) in THF (30 ml) was added isopropyl amine (580 mg, 10.3 mmol) and the mixture was heated in a sealed tube at 130° C. overnight. Cooled to 20° C. the solvent was removed in vacuo. The residue was dissolved in EtOAc (60 mL), washed with water (30 mL), brine, and concentrated to give the product (230 mg, yield: 88.1%).

Step 1.8: 3-(6-chloro-3-pyridyl)-8-(dimethylamino)-5-oxo-6-phenyl-1,2,3,8-tetrahydroindolizin-4-ium-7-olate

(13) The product from step 7 (0.23 g, 0.96 mmol) and bis(2,4,6-trichlorophenyl) 2-phenylpropanedioate (0.62 g, 1.2 mmol) was taken up in toluene (5 ml) with a few drops of DMF. The reaction mixture was heated in a microwave oven at 150° C. for 90 min. After cooling to RT, it was poured into water (10 ml), and extracted with EtOAc (45 mL). The organic phase was dried with Na.sub.2SO.sub.4, and concentrated to give the crude material. Purification by column chromatography yielded the pure product (0.155 g, yield: 57.8%).

(14) .sup.1H NMR (400 MHz, CDCl3): δ 8.400˜8.394 (d, 1H, J=2.4 Hz), 7.8818˜7.791 (m, 1H), 7.470˜7.395 (m, 3H), 7.285˜7.142 (m, 3H), 5.841˜5.807 (m, 1H), 3.771˜3.608 (m, 2H), 2.982˜2.869 (m, 2H), 2.249˜2.192 (m, 1H), 1.722˜1.671 (m, 6H).

Example 2: Synthesis S2

Synthesis of Example numbered C-8: 6-(6-chloro-3-pyridyl)-1-methyl-4-oxo-3-phenyl-6,7,8,9-tetrahydropyrido[1,2-a]pyrimidin-5-ium-2-olate

(15) ##STR00084##

Step 2.1: Methyl 5-(6-chloro-3-pyridyl)-5-oxo-pentanoate

(16) To a mixture of Zn metal (21.7 g, 0.339 mol) and DMI (38.6 g, 0.339 mol) in MeCN (300 mL) was added under an argon atmosphere 0.2 ml of TMSCl at 60° C. stirred for 5 min, followed by addition of methyl 4-iodo butanoate (58 g, 0.254 mol). The mixture was stirred for 2 hours at this temperature, and then cooled to room temperature. This solution was used directly.

(17) To a mixture of 6-chloropyridine-3-carbonyl chloride (14.8 g, 0.085 mol) and Pd(OAc).sub.2 (0.57 g, 0.00254 mol) in MeCN (300 mL) was added under an argon atmosphere the alkyl zinc reagent and stirred at room temperature. After 2 hours, sat.NH.sub.4Cl solution was added to the reaction mixture and it was extracted with EtOAc. The organic phases were combined, washed with brine, dried, filtered and concentrated to give the crude product. Purification by column chromatography yielded the pure product (9.5 g).

(18) .sup.1H NMR (400 MHz, CDCl3): δ d 8.88˜8.89 (d, 1H, J=2 Hz), 8.13˜8.19 (m, 1H), 7.36˜7.40 (d, 1H, J=16 Hz), 4.03˜4.01 (q, 2H), 2.98˜3.02 (t, 2H, J=6.8 Hz) 2.37˜2.407 (t, 2H, J=7.2 Hz), 1.98˜2.05 (m, 2H), 1.15˜1.22 (t, 2H, J=13 Hz).

Step 2.2: 6-(6-chloro-3-pyridyl) piperidin-2-one

(19) To a solution of methyl 5-(6-chloro-3-pyridyl)-5-oxo-pentanoate (9.5 g, 39.4 mmol) in MeOH (150 ml) was added NH.sub.4OAc (6.1 g, 78.8 mmol) and NaBH3CN (5 g, 78.8 mmol), and the mixture refluxed for overnight. Cooled to RT, the solvent was removed in vacuo, the residue dissolved in DCM, washed with brine dried concentrated to give the crude product. Purification by column chromatography yielded the pure product (5 g, yield: 61%).

Step 2.3: 6-(6-chloro-3-pyridyl)piperidine-2-thione

(20) To a solution of 6-(6-chloro-3-pyridyl)piperidin-2-one (2.2 g, 10.4 mmol) in dioxane (150 ml) was added P255 (2.8 g, 12.6 mmol) at 20° C. The mixture was stirred for 2.5 h at 120° C. After filtration of the hot mixture, the filtrate was concentrated to give the crude material. Purification by column chromatography yielded the pure product (1.5 g, yield: 63.5%).

Step 2.4: 2-chloro-5-(6-methylsulfanyl-2,3,4,5-tetrahydropyridin-2-yl)pyridine

(21) To a solution of 6-(6-chloro-3-pyridyl)piperidine-2-thione (1.5 g, 6.64 mmol) in acetone (120 ml) was added K.sub.2CO.sub.3 and stirred for 30 min, then iodo methane (1.42 g, 9.96 mmol) was added and stirred for overnight at 20° C. After filtration, the filtrate was concentrated to give the crude material. Purification by column chromatography yielded the pure product (1.2 g, yield: 75.3%).

Step 2.5: 2-(6-chloro-3-pyridyl)-N-methyl-2,3,4,5-tetrahydropyridin-6-amine

(22) 2-chloro-5-(6-methylsulfanyl-2,3,4,5-tetrahydropyridin-2-yl)pyridine (0.6 g, 2.5 mmol) was taken up in methyl amine (20 mL, 40 mmol), and the mixture was heated in a sealed tube at 80° C. for overnight. Cooled to 20° C. the solvent was removed in vacuo, the residue was dissolved in EtOAc (60 mL) and washed with water (30 mL), and brine. The organic phase was concentrated to give the product (480 mg, crude).

Step 2.6: 6-(6-chloro-3-pyridyl)-1-methyl-4-oxo-3-phenyl-6,7,8,9-tetrahydropyrido[1,2-a]pyrimidin-5-ium-2-olate

(23) The product from the preceding step (0.48 g, crude) and bis(2,4,6-trichlorophenyl) 2-phenylpropanedioate (1.4 g, 2.4 mmol) was taken up in toluene (5 ml) with a few drops of DMF. The reaction mixture was heated in a microwave oven at 150° C. for 90 min. After cooling to RT, it was poured into water (10 ml), and extracted with EtOAc (45 mL). The organic phase was dried with Na.sub.2SO.sub.4, and concentrated to give the crude material. Purification by column chromatography yielded the pure product (0.4 g, yield: 50.7%).

(24) .sup.1H NMR (400 MHz, CDCl3): δ d 8.381˜8.375 (d, 1H, J=2.4 Hz), 7.818˜7.791 (m, 1H), 7.552˜7.485 (m, 3H), 7.207˜7.048 (m, 3H), 5.941˜5.933 (s, 1H), 3.495 (s, 3H), 3.236˜3.174 (m, 2H), 2.179˜2.132 (m, 2H), 1.822˜1.426 (m, 2H).

Example 3: Synthesis S3

Synthesis of Example numbered C-6: 6-(2-chlorothiazol-5-yl)-1-methyl-4-oxo-3-phenyl-3,6,7,8-tetrahydro-2H-pyrrolo[1,2-a]pyrimidin-5-ium-2-olate

(25) ##STR00085##

(26) A mixture of 2-(2-chlorothiazol-5-yl)-N-methyl-3,4-dihydro-2H-pyrrol-5-amine (230 mg, 1.07 mmol) and bis(2,4,6-trichlorophenyl) 2-phenylpropanedioate (632 mg, 1.17 mmol) in toluene (10 ml) in sealed tube was heated at 150° C. for 90 min under microwave irradiation. Cooled to RT, the resulting mixture was concentrated, and the residue was purified by preparative TLC to give 6-(2-chlorothiazol-5-yl)-1-methyl-4-oxo-3-phenyl-3,6,7,8-tetrahydro-2H-pyrrolo[1,2-a]pyrimidin-5-ium-2-olate (90 mg, yield: 23%) as a yellow solid.

(27) .sup.1H NMR (400 MHz, CDCl3): δ d 7.87 (s, 1H), 7.60 (d, 2H, J=7.2 Hz), 7.23 (t, 2H, J=7.6 Hz), 7.08 (t, 1H, J=7.6 Hz), 5.98˜5.95 (m, 1H), 3.67˜3.59 (m, 1H), 3.51˜3.44 (m, 1H), 3.37 (s, 3H), 2.69˜2.67 (m, 1H), 2.60˜2.54 (m, 1H).

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

(29) Conditions:

(30) Analytical HPLC column 1: RP-18 column Chromolith Speed ROD from Merck KgaA, Germany). Elution: acetonitrile+0.1% trifluoroacetic acid (TFA)/water+0.1% trifluoroacetic acid (TFA) in a ratio from 5:95 to 95:5 in 5 minutes at 40° C. r.t.=HPLC retention time (RT) in minutes; m/z of the [M+H]+, [M+Na]+ or [M+K]+peaks.

(31) Analytical HPLC column 2: Phenomenex Kinetex 1.7 μm XB-C18 100A; 50×2.1 mm Elution: A: acetonitrile+0.1% trifluoroacetic acid (TFA)/water+0.1% trifluoroacetic acid (TFA) in a ratio of from 5:95 to 95:5 in 1.5 minutes at 50° C.

(32) MS-method: ESI positive.

(33) .sup.1H-NMR, respectively .sup.13C-NMR: The signals are characterized by chemical shift δ (ppm) vs. tetramethylsilane, respectively CDCl.sub.3 for .sup.13C-NMR, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: m=multiplett, q=quartett, t=triplett, d=doublet and s=singulett. The coupling constant (J) is expressed in Hertz (Hz).

(34) Further compounds examples of the present invention were prepared by analogy to the above described synthetic methods and the hereunder table illustrates, without imposing any limitation thereto, compounds examples of formula (I) including their corresponding characterization data:

(35) TABLE-US-00002 Characterization .sup.1H-NMR and/or HPLC/MS N.sup.o Formula δ (ppm); J (Hz) C-1 CDCl.sub.3; 8.26(s, 1H), 7.54~7.53 (d, 1H), 7.52~7.51 (d, 1H), 7.31~7.26 (t, 2H ), 7.16~7.13 (t, 1H), 5.77~5.74 (d, 1H), 3.47 (s, 3H), 3.33~2.24 (m, 1H), 3.15~3.07 (m, 1H), 2.68~2.58 (m, 1H), 2.13~2.05(m, 1H), C-2 MeOD: 8.408~8.402 (d, 1H, J = 2.4Hz), 7.825~7.798 (m, 1H), 7.470~7.427 (m, 3H), 7.289~7.147 (m, 3H), 5.860~5.827 (m, 1H), 4.272~4.219 (m, 1H), 4.056~4.022 (m, 1H), 3.763~3.310 (m, 2H), 2.959~2.922 (m, 1H), 2.270~2.213 (m, 1H), 1.444~1.408 (m, 1H). C-3 MeOD: 8.400~8.394 (d, 1H, J = 2.4Hz), 7.8818~7.791 (m, 1H), 7.470~7.395 (m, 3H), 7.285~7.142 (m, 3H), 5.841~5.807(m, 1H), 3.771~3.608 (m, 2H), 2.982~2.869 (m, 2H), 2.249~2.192 (m, 1H), 1.722~1.671 (m, 6H) C-4 MeOD: 8.495~8.489 (d, 1H, J = 2.4), 7.921~7.914 (d, 1H, J = 2.8), 7.622~7.594 (m, 4H), 7.494~7.475 (m, 4H), 7.278~7.135 (m, 3H), 5.918~5.884 (m, 1H), 3.341~3.098 (m, 1H), 3.084~3.072 (m, 1H), 2.854~2.802 (m, 1H), 2.168~2.161 (m, 1H) C-5 0 MeOD: 8.412~8.406 (d, 1H, J = 2.4),7.820~7.793 (m, 1H), 7.486~7.436 (m, 3H), 7.293~7.156 (m, 3H), 5.929~5.897 (m, 1H), 5.136~4.886 (m, 2H), 3.796~3.610 (m, 2H), 2.915~2.512 (m, 2H) C-6 DMSO-D.sub.6: 7.87 (s, 1H), 7.60 (d, 2H, J = 7.2), 7.23 (t, 2H, J = 7.6), 7.08 (t, 1H, J = 7.6), 5.98~5.95 (m, 1H), 3.67~3.59 (m, 1H), 3.51~3.44 (m, 1H), 3.37 (s, 3H), 2.69~2.67 (m, 1H), 2.60~2.54 (m, 1H) C-7 CDCl.sub.3: 9.10(s, 1H), 8.60 (s, 2H), 7.63 (d, 2H, J = 7.6), 7.24 (t, 2H, J = 7.8), 7.09 (t, 1H, J = 7.8), 5.72~5.68 (m, 1H), 3.42 (s, 3H), 3.28~3.21 (m, 1H), 3.11~3.08 (m, 1H), 2.62~2.56 (m, 1H), 2.10~2.06 (m, 1H) C-8 DMSO: 8.381~8.375 (d, 1H, J = 2.4), 7.818~7.791 (m, 1H), 7.552~7.485 (m, 3H), 7.207~7.048 (m, 3H), 5.941~5.933 (s, 1H), 3.495 (s, 3H), 3.236~3.174 (m, 2H), 2.179~2.132 (m, 2H), 1.822~1.426 (m, 2H) C-9 DMSO: 8.363~8.357 (d, 1H, J = 2.4), 7.787~7.760 (m, 1H), 7.564~7.460 (m, 3H), 7.207~7.050 (m, 3H), 5.938 (s, 1H), 4.252~4.007 (m, 2H), 3.364~3.155 (m, 2H), 2.239~1.828 (m, 3H), 1.500~1.473 (m, 1H) 1.309~1.274 (m, 3H) C-10 MeOD: 8.261~8.255(d, 1H, J = 2.4), 7.670~7.117 (m, 7H), 6.045 (s, 1H), 3.333~3.222 (m, 2H), 2.288~2.178(m, 3H), 1.932~1.922 (d, 2H, J = 4.0), 1.723~1.657 (m, 6H) C-11 DMSO: 8.511~8.506 (d, 1H, J = 2.0), 7.943~7.040 (m, 12H), 5.976 (s, 1H), 2.583 (s, 2H), 2.235~1.354 (m, 4H) C-12 CDCl.sub.3: 7.66~7.62 (d, 2H), 7.27~7.21 (m, 2H), 7.11~7.08 (t, 1H), 6.34 (s, 1H), 3.47 (s, 3H), 2.90~2.86 (d, 1H), 2.76~2.70 (m, 1H), 2.57 (s, 3H), 2.22~2.20 (d, 1H), 1.94 (s, 3H). C-13 CDCl.sub.3: 7.65~7.59 (d, 2H, J = 7.6), 7.29~7.22 (m, 2H), 7.13~7.10 (t, 1H), 6.31 (m, 1H), 3.52 (s, 3H), 2.99~2.93 (m, 1H), 2.83~2.76 (m, 1H), 2.33~2.30 (m, 1H), 2.02~2.00 (m, 1H) C-14 CDCl.sub.3: 9.13 (s, 1H), 8.51 (s, 2H), 7.65-7.63 (d, 2H, J = 7.6), 7.31~7.27 (t, 2H, J = 7.6), 7.16~7.13 (t, 1H, J = 7.6), 6.10 (m, 1H), 3.56 (s, 3H), 3.00~2.93 (m, 1H), 2.82~2.75 (m, 1H), 2.12~2.10 (m, 2H), 1.92~1.86 (m, 1H), 1.62~1.56 (m, 1H) C-15 00 HPLC/MS RT 1.106 min m/z 462.7 .sup.1H-NMR(CDCl3/ppm) 8.45(s, 1H), 7.90 (s, 1H), 7.70(d, 1H), 7.65(t, 1H), 7.60(d, 2H), 7.40(t, 4H), 7.35(t, 2H), 6.95(s, 1H), 4.80(d, 1H), 4.60(d, 1H), 4.40- 4.25(m, 1H), 4.05-3.95(m, 1H), 1.45(t, 3H) C-16 01 HPLC/MS RT 1.126 min m/z 452.6 .sup.1H-NMR(CDCl3/ppm) 7.95(s, 1 H), 7.75(s, 1H), 7.70- 7.65(m, 1H), 7.60(d, 2H), 7.50- 7.40(m, 4H), 7.30(t, 1H), 7.20(s, 1H), 5.45(dd, 1H), 5.35(dd, 1H), 4.00-3.90(m, 1H), 3.90- 3.80(m, 1H), 1.40(t, 3H) C-17 02 HPLC/MS RT 0.9 min m/z 385.3 .sup.1H-NMR(CDCl3/ppm) 7.75(d, 2H), 7.50(s, 1H), 7.35(t, 2H), 7.20(t, 1H), 6.00(d, 1H), 5.95- 5.80(m, 1H), 5.30(d, 1H), 5.20(d, 1H), 4.60(dd, 1H), 4.45(dd, 1H), 3.40- 3.30(m, 1H), 3.20(q, 1H), 2.62- 2.50(m, 1H), 2.45(q, 1H) C-18 03 H-NMR(CDCl3/ppm/400MHz) racemic 7.62(d, 2H), 7.57(s, 1H), 7.35(t, 2H), 7.20(t, 1H), 6.02(q, 1H), 3.85(q, 1H), 3.60(s, 3H), 2.80- 2.70(m, 1H), 2.60-2.40(m, 1H), 1.59(d, 3H) C-19 04 .sup.1H-NMR(CDCl3/ppm/400MHz) 7.71 (s, 1H), 7.53(d, 2H), 7.42(t, 2H), 7.34(t, 1H), 5.91(dd, 1H), 4.95(t, 1H), 4.81(dd, 1H), 3.36 (s, 3H) C-20 05 HPLC-MS RT 0.969 min m/z 423.8 .sup.1H-NMR(CDCl3/ppm) 8.55(s, 1H), 8.00(s, 1H), 7.85(d, 2H), 7.45(d, 2H), 7.40(d, 1H), 7.05(s, 1H), 5.45(d, 1H), 5.35(d, 1H), 3.45(s, 3H), 1.65(s(breit), 1H) C-21 06 HPLC-MS RT 0.891 min m/z 432.3 H-NMR(CDCl3/ppm) 7.75(d, 2H),7.40- 7.30(m, 5H), 7.23(d, 2H), 7.15(t, 1H), 6.75(s, 1H), 5.75(d, 1H), 5.30(d, 1H), 5.05(d, 1H), 3.20 (s, 3H)3.10-3.00(m, 2H), 2.45- 2.30(m, 1H), 2.15-2.10(m, 1H) C-22 07 .sup.1HNMR(CDCl3/ppm/400MHz) 8.08(s, 1H), 7.98(d, 1H), 7.55(s, 1H),7.48- 7.43(m, 2H), 6.04(d, 1H), 3.46(s, 3H), 3.50- 3.44(m, 1H), 3.32-3.25(m, 1H), 2.71- 2.68(m, 1H), 2.61-2.56(m, 1H) C-23 08 .sup.1H-NMR(CDCl3/ppm/400MHz) 8.29(d, 1H), 7.71(d, 2H), 7.52(d, 1H), 7.44(d, 5H), 7.34- 7.30(m, 2H), 7.18(t, 1H), 5.85(dd, 1H), 3.50(s, 3H), 3.38-3.31(m, 1H), 3.22- 3.19(m, 1H), 2.75-2.69(m, 1H), 2.21- 2.15(m, 1H) C-24 09 HPLC/MS RT 0.846 min m/z 373.8 H-NMR(CDCl3/ppm) 7.70(d, 2H), 7.55(s, 1H), 7.35(d, 2H), 7.2(d, 1H), 6.05(d, 1H), 4.00(q, 2H), 3.44- 3.40(m, 1H), 3.25-3.20(m, 1H), 2.65- 2.60(m, 1H), 2.60-2.50(m, 1H), 1.66(s(breit), 1H), 1.37(d, 3H) C-25 0 First eluting enantiomer (-) HPLC/MS RT 0.98 min m/z 428.6 C-26 HPLC-MS RT 1.079 min m/z 454.6 H-NMR(CDCl3/ppm) 8.40(d, 1H), 7.98(s, 1H), 7.85(t, 1H), 7.70(dd, 1H), 7.40(d, 2H), 7.30(d, 1H)6.85(s, 1H), 4.75 (dd, 1H), 4.45(d, 1H)4.25-4.15(m, 1H), 3.90- 3.80(m, 1H), 1.35(t, 3H) C-27 HPLC/MS RT 1.042 min m/z 442.6 H-NMR(CDCl3/ppm) 8.10(s, 1H), 7.95(d, 1H), 7.55(s, 1H), 7.45(q, 2H), 6.10(d, 1H), 4.15-4.05(m, 1H),4.00- 3.90(m, 1H), 3.60- 3.50(m, 1H), 3.40(q, 1H), 2.85- 2.75(m, 1H), 2.65(q, 1H), 1.40(t, 3H) C-28 Second eluting enantiomer HPLC-MS RT 0.982 min m/z 428.6 C-29 H-NMR(CDCl3/ppm/400MHz) racemic 7.65(d, 2H), 7.55(s, 1H), 7.35(t, 2H), 7.25(t, 1H), 6.05(d, 1H), 3.60-3.45(m, 1H), 3.50(s, 3H), 3.00-2.90(m, 1H), 2.35(d, 1H), 1.55(d, 3H) LC-MS RT 1.073 min m/z 374.2 C-30 HPLC-MS RT 0.891 min m/z 386.5 H-NMR(CDCl3/ppm) 8.45(d, 1H), 7.75(dd, 1H), 7.35(d, 2H), 7.30(t, H), 7.15(t, 1H), 6.95(s, 1H), 4.80(d, 1H), 4.60(d, 1H), 4.35-4.35(m, 1H), 4.05- 3.95(m, 1H), 1.50(t, 3H) C-31 HPLC/MS RT 1.173 min m/z 455.2 H-NMR(CDCl3/ppm) 7.75(s, 2H), 7.55(s, 1H), 7.15(s, 1H), 6.10(d, 1H), 6.00- 5.85(m, 1H), 5.35(d, 1H), 5.25(d, 1H), 4.70- 4.55(m, 2H), 3.60-3.45(m, 1H), 3.40(q, 1H), 2.85- 2.70(m, 1H), 2.65(q, 1H), 1.60(s, 1H) C-32 HPLC/MS RT 1.025 min m/z 437.8 H-NMR(CDCl3/ppm) 8.55(s, 1H), 8.00(s, 1H), 7.90- 7.80(m, 2H), 7.45- 7.35(m, 3H), 7.05(s, 1H), 5.55- 5.45(m, 1H), 5.45-5.40(m, 1H), 4.15- 4.00(m, 1H), 3.90-3.80(m, 1H), 1.45(t, 3H) C-33 HPLC-MS RT 1.006 min m/z 431.8 H-NMR(CDCl3/ppm) 8.55(s, 1H), 7.90(d, 2H), 7.65(d, 1H), 7.60(d, 2H), 7.40(d, 3H), 7.35(d, 2H), 7.30(t, 1H), 7.00(s, 1H), 5.40(d, 1H), 5.30(d, 1H), 3.45(s, 3H) C-34 HPLC/MS RT 1.014 min m/z 436.2 H-NMR(CDCl3/ppm) 7.75(d, 2H), 7.45(s, 1H), 7.40- 7.30(m, 6H), 7.28(d, 1H), 7.20(t, 1H), 5.95(d, 1H), 5.25(d, 1H), 5.05(d, 1H), 3.25-3.05(m, 2H), 2.55-2.40 (m, 1H), 2.35(q, 1H), 1.70(s(breit), 1H) C-35 0 HPLC/MS RT 0.969 min m/z 443.8 H-NMR(CDCl3/ppm) 8.05(s, 1H), 7.95(d, 1H), 7.75(s, 1H), 7.45(d, 2H), 7.20(s, 1H), 5.40(q, 2H), 3.95- 3.85(m, 1H), 3.85-3.70(m, 1H), 1.20(t, 3H) C-36 HPLC-MS RT 0.848 min m/z 369.7 H-NMR(CDCl3/ppm) 8.55(d, 1H), 7.95(dd, 1H), 7.65(d, 2H), 7.35(d, 1H), 7.30(t, 1H), 7.25(s, 3H), 7.20(t, 1H), 7.10 (s, 1H), 5.50(d, 1H), 5.40(d, 1H), 4.10- 3.95(m, 1H), 3.90-3.80(m, 1H), 1.45(t, 3H) C-37 HPLC-MS RT 0.792 min m/z 356.6 H-NMR(CDCl3/ppm) 8.55(d, 1H), 7.90(dd, 1H), 7.65(d, 2H), 7.35 (t, 3H), 7.20(t, 1H), 6.95(s, 1H), 5.30(d, 1H), 5.15(d, 1H), 3.35(s, 3H), 1.65(s(breit), 1H) C-38 H-NMR(CDCl3/ppm/400MHz) 7.76(d, 2H), 7.54(s, 1H), 7.37(t, 2H), 7.21(t, 1H), 5.26(t, 1H), 4.96(q, 1H), 4.53(q, 1H), 3.49(s, 3H) C-39 First Eluting Enantiomer (-) HPLC/MS RT 0.797 min m/z 360.5 C-40 HPLC-MS RT 1.180 min m/z 388.1 H-NMR(CDCl3/ppm/400MHz) 7.70(d, 2H) 7.48(s, 1H), 7.33(t, 2H), 7.19(t, 1H), 5.86(d, 1H), 3.53(t, 3H), 2.57(q, 1H), 2.44 (d, 1H), 1.53(dd, 6H) C-41 HPLC/MS RT 1.096 min m/z 453.3 H-NMR(CDCl3/ppm) 8.10(s, 1H), 7.90(d, 1H), 7.55(s, 1H), 7.45(q, 2H), 6.10(d, 1H), 6.00- 5.80(m, 1H), 5.35(d, 1H), 5.25(d, 1H), 4.65- 4.45(m, 2H), 3.60- 340(m, 1H), 3.35(q, 1H), 2.80- 2.62(m, 1H), 2.60(q, 1H) C-42 HPLC-MS RT 0.801 min m/z 360.5 C-43 HPLC-MS RT 1.079 min m/z 446.7 H-NMR(CDCl3/ppm) 8.55(d, 1H), 7.90(d, 2H), 7.65- 7.60(m, 1H), 7.60(d, 2H), 7.40(d, 3H), 7.35(d, 2H), 7.30(t, 1H), 7.05(s, 1H), 5.40(d, 1H), 5.30(d, 1H), 4.10-3.90(m, 1H), 3.90- 3.80(m, 1H), 1.40(t, 3H) C-44 HPLC-MS RT 1.096 min m/z 437.7 H-NMR(CDCl3/ppm) 8.55(s, 1H), 7.90(dd, 1H), 7.65(s, 2H), 7.45(d, 1H), 7.10(s, 1H), 7.15(t, 1H), 5.55(d, 1H), 5.45(d, 1H), 4.15-4.05(m, 1H), 3.95- 3.85(m, 1H), 1.45(t, 3H) C-45 0 HPLC-MS RT 0.792min m/z 436.1 H-NMR(CDCl3/ppm) 7.99(s, 1H), 7.73- 7.72(m, 1H), 7.64(d, 2H), 7.50(s, 1H), 7.43(t, 4H), 7.32(t, 1H), 6.01 (d, 1H), 3.38(s, 3H), 3.46- 3.33(m, 1H), 3.18-3.11(m, 1H), 2.59- 2.48(m, 2H) C-46 HPLC/MS RT 0.821 min m/z 372.5 H-NMR(CDCl3/ppm/500MHz) 8.45(d, 1H), 7.70(d, 1H), 7.60(d, 2H), 7.30- 7.25(m, 3H), 7.15(t, 1H), 6.90(s, 1H), 4.65(d, 1H), 4.45(d, 1H), 3.55(s, 3H) C-47 HPLC/MS RT 0.842 min m/z 404.5 H-NMR(CDCl3/ppm) 7.65(d, 2H), 7.55(s, 1H), 6.90(d, 2H), 6.10(d, 1H), 4.15-4.05(m, 1H), 4.00- 3.90(m, 1H), 3.80(s, 3H), 3.60- 3.45(m, 1H), 3.35(q, 1H), 2.80- 2.70(m, 1H), 2.65(q, 1H), 1.40(t, 3H) C-48 H-NMR(CDC3/ppm/400MHz) 8.81 (s, 1H), 8.20(s, 1H), 8.00(s, 1H), 7.92(d, 1H), 7.59(d, 1H), 7.55(s, 1H), 7.47(t, 1H), 6.08(d, 1H), 3.52(s, 3H), 3.50-3.47(m, 1H), 3.38- 3.34(m, 1H), 2.74-2.71(m, 1H), 2.68- 2.66(m, 1H) C-49 HPLC/MS RT 1.068 min m/z 450.6 H-NMR(CDCl3/ppm) 7.98(s, 1H), 7.70(s, 1H), 7.60(d, 2H), 7.50(s, 1H), 7.40(d, 3H), 7.39(s, 1H), 7.30(t, 1H), 6.05 (d, 1H), 3.95(q, 2H), 3.50- 3.40(m, 1H), 3.22(q, 1H), 2.70- 2.60(m, 1H), 2.52(t, 1H), 1.65(s(breit), 1H), 1.35(t, 3H) C-50 HPLC-MS RT 1.07 min m/z 428.8 H-NMR(CDCl3/ppm) 7.75(s, 2H), 7.55(s, 1H), 7.20(t, 1H), 6.05(d, 1H), 5.30(s, 1H), 3.55-3.40(m, 3H), 3.25(q, 1H), 2.80- 2.60(m, 1H), 2.60(q, 1H)

(36) The biological activity of the compounds of formula (I) of the present invention can be evaluated in biological tests as described in the following.

(37) General conditions: If not otherwise specified, most test solutions are to be prepared as follows:

(38) 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.

(39) Test solutions are prepared in general at concentrations of 2500 ppm, 1000 ppm, 500 ppm, 300 ppm, 100 ppm and 30 ppm (wt/vol).

(40) Boll Weevil (Anthonomus grandis)

(41) 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.

(42) 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.

(43) 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.

(44) In this test, compounds C-3, C-47, C-29, C-40 and C-44 at 2500 ppm showed over 75% mortality in comparison with untreated controls.

(45) Green Peach Aphid (Myzus persicae)

(46) 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.

(47) 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.

(48) 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.

(49) In this test, compounds C-1, C-2, C-3, C-6, C-8, C-9, C-12, C-13, C-21, C-34, C-45, C-23, C-22, C-24, C-27, C-49, C-47, C-48, C-50, C-29, C-40, C-32, C-43, C-44, C-38, C-17, C-41 and C-31 at 2500 ppm showed over 75% mortality in comparison with untreated controls.

(50) Orchid Thrips (Dichromothrips corbetti)

(51) Dichromothrips corbetti adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions. For testing purposes, the test compound is diluted in a 1:1 mixture of acetone:water (vol:vol), plus 0.01% vol/vol Alkamuls® EL 620 surfactant.

(52) Thrips potency of each compound was evaluated by using a floral-immersion technique. Plastic petri dishes were used as test arenas. All petals of individual, intact orchid flowers were dipped into treatment solution and allowed to dry. Treated flowers were placed into individual petri dishes along with about 20 adult thrips. The petri dishes were then covered with lids. All test arenas were held under continuous light and a temperature of about 28° C. for duration of the assay. After 3 days, the numbers of live thrips were counted on each flower, and along inner walls of each petri dish. The percent mortality was recorded 72 hours after treatment.

(53) In this test, compounds C-1, C-2, C-3, C-6, C-8, C-34, C-45, C-22, C-24, C-27, C-49, C-47, C-28, C-48, C-50, C-29, C-42, C-35 and C-38 at 500 ppm showed over 75% mortality in comparison with untreated controls.

(54) Rice Green Leafhopper (Nephotettix virescens)

(55) Rice seedlings were cleaned and washed 24 hours before spraying. The active compounds were formulated in 50:50 acetone:water (vol:vol), and 0.1% vol/vol surfactant (EL 620) was added. Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants were kept at about 28-29° C. and relative humidity of about 50-60%. Percent mortality was recorded after 72 hours.

(56) In this test, compounds C-1, C-2, C-6, C-8, C-22, C-24, C-47, C-28, C-42 and C-38 at 500 ppm showed over 75% mortality in comparison with untreated controls.

(57) Rice Brown Plant Hopper (Nilaparvata lugens)

(58) Rice seedlings were cleaned and washed 24 hours before spraying. The active compounds were formulated in 50:50 acetone:water (vol:vol) and 0.1% vol/vol surfactant (EL 620) was added. Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants were kept at about 28-29° C. and relative humidity of about 50-60%. Percent mortality was recorded after 72 hours.

(59) In this test, compounds C-1, C-6, C-24, C-28, C-29, C-42 and C-38 at 500 ppm showed over 75% mortality in comparison with untreated controls.

(60) Spider Mite (Tetranychus spp.)

(61) 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. Potted cotton plants at two weeks of age were cleaned, air dried and inoculated with approximately 50 mites of various stages. The potted plants are sprayed after the pest population has been recorded. Percent mortality is recorded 72 hours after treatment. In this test, compounds C-9 and C-42 at 500 ppm showed over 75% mortality in comparison with untreated controls.

(62) Tobacco Budworm (Heliothis virescens)

(63) 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.

(64) In this test, compounds C-1, C-45, C-44 and C-38 at 2500 ppm showed over 75% mortality in comparison with untreated controls.

(65) Vetch Aphid (Megoura viciae)

(66) 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.

(67) 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.

(68) 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.

(69) In this test, compounds C-1, C-2, C-3, C-6, C-8, C-9, C-13, C-34, C-45, C-22, C-24, C-27, C-49, C-47, C-48, C-50, C-29, C-40, C-44, C-38, C-19 and C-31 at 2500 ppm showed over 75% mortality in comparison with untreated controls.