SUBSTITUTED PYRIMIDINIUM COMPOUNDS FOR COMBATING ANIMAL PESTS

Abstract

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), wherein X, Y, Z, R.sup.1, R.sup.2, A and R.sup.3 are defined as in the description.

##STR00001##

Claims

1. A substituted pyrimidinium compound of formula (I) ##STR00038## wherein X, Y are each independently O or S; Z is a direct bond, O, S(O).sub.m, NR.sup.b, C(R.sup.aR.sup.aa)O, C(═X.sup.1), C(═X.sup.1)Y.sup.1, or Y.sup.1C(═X.sup.1); X.sup.1 is O, S, or NR.sup.b; Y.sup.1 is O, S, or 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; R.sup.3 is C.sub.1-C.sub.6-alkyl-C(═N(O).sub.pR.sup.b)R.sup.bi or C.sub.1-C.sub.6-alkyl-C(═NNR.sup.bR.sup.c)R.sup.b1; R.sup.1 is 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, 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 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 with R.sup.a; or R.sup.1 is C(═O)R.sup.b, C(═O)OR.sup.e, NR.sup.bR.sup.c, 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, or N═CR.sup.bR.sup.c; R.sup.a is each independently 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 or a three- to six-membered saturated, or partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from 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 with R.sup.aa, or two geminally bound groups R.sup.a together may form a group selected from ═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 halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy or C.sub.1-C.sub.6-haloalkoxy; R.sup.b is each independently hydrogen, 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-alkylcarbonyl, C.sub.1-C.sub.6-cycloalkylcarbonyl, C.sub.1-C.sub.6-phenylcarbonyl, or a three- to six-membered saturated, or partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from N(R.sup.c).sub.p, O, and S, wherein S may be oxidized, and wherein R.sup.b may be partially or fully substituted with R.sup.ab; R.sup.ab is each independently is each independently halogen, CN, 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, —S—C.sub.1-C.sub.6-alkyl, phenyl or 5-or 6-aromatic heterocyclic ring; wherein R.sup.ab may be partially or fully substituted with R.sup.aa; R.sup.bi is each independently 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 or a three- to six-membered saturated, or partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from 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 with R.sup.aa; R.sup.c is each independently 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, or a three- to six-membered saturated, partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from 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 with 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 N, O, S, NO, SO and SO.sub.2 and wherein the carbo- or heterocyclic ring may be partially or fully substituted with R.sup.4; R.sup.d is each independently 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-cycloalkyl, or C.sub.1-C.sub.6-alkoxyalkyl, wherein the above mentioned groups may be substituted with one or more halogen; R.sup.e is each independently, 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, or a three- to six-membered saturated, partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from 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 with R.sup.aa; n is 0, 1 or 2; m is 0, 1, or 2; p is 0 or 1; R.sup.2 is 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, or 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 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 with R.sup.2a; R.sup.2a is each independently 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, or a three- to six-membered saturated, or partially unsaturated or aromatic carbo- or heterocyclic ring, which may contain 1 to 3 heteroatoms selected from 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 with R.sup.2aa; or two geminally bound groups R.sup.2a together may form a group selected from ═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 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.bSO.sub.2NR.sup.bR.sup.c, or N═S(═O).sub.pR.sup.cR.sup.c, or two geminally bound groups R.sup.2aa together may form a group selected from ═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.4 is each independently 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.bSO.sub.2NR.sup.bR.sup.c, or N═S(═O).sub.pR.sup.cR.sup.c, or two geminally bound groups R.sup.4 together may form a group selected from ═O, ═S, ═CR.sup.bR.sup.c, ═NR.sup.c, ═NOR.sup.c, and ═NNR.sup.cR.sup.c; or a stereoisomer, tautomer, salt, or N-oxide thereof.

2. The compound of formula (I) or a stereoisomer, tautomer, salt, or N-oxide thereof according to claim 1, wherein wherein X and Y are O.

3. The compound of formula (I) or a stereoisomer, tautomer, salt, or N-oxide thereof according to claim 1, wherein R.sup.3 is C.sub.1-C.sub.6-alkyl-C(═N(O).sub.pR.sup.b) R.sup.b1.

4. The compound of formula (I) or a stereoisomer, tautomer, salt, or N-oxide thereof according to claim 1, wherein R.sup.3 is C.sub.1-C.sub.6-alkyl-C(═NNR.sup.bR.sup.c)R.sup.b1.

5. The compound of formula (I) or a stereoisomer, tautomer, salt, or N-oxide thereof according to claim 1, wherein R.sup.b is C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.1-C.sub.6-alkylcarbonyl, C.sub.1-C.sub.6-cycloalkylcarbonyl, C.sub.1-C.sub.6-phenylcarbonyl, tetrahydrofuranyl, tetrahydropyranyl, phenyl, or pyridyl; wherein R.sup.b may be partially or fully substituted with R.sup.ab; R.sup.ab is each independently halogen, CN, 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, —S—C.sub.1-C.sub.6-alkyl, phenyl or 5- or 6-aromatic heterocyclic ring; wherein R.sup.ab may be partially or fully substituted with R.sup.aa; R.sup.aa is each independently halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy or C.sub.1-C.sub.6-haloalkoxy.

6. The compound of formula (I) or a stereoisomer, tautomer, salt, or N-oxide thereof according to 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 O, S and N(R.sup.c).sub.p, which ring may be substituted with R.sup.a.

7. The compound of formula (I) or a stereoisomer, tautomer, salt, or N-oxide thereof according to 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 with R.sup.2a, and wherein R.sup.2a is halogen, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-haloalkoxy, OR.sup.c, C(═O)OR.sup.c, C(═O)NR.sup.bR.sup.c, phenyl, or pyridyl, which may be substituted with halogen, C.sub.1-C.sub.6-haloalkyl or C.sub.1-C.sub.6-haloalkoxy.

8. The compound of formula (I) or a stereoisomer, tautomer, salt, or N-oxide thereof according to claim 1, wherein Z is a direct bond, and R.sup.2 is phenyl, which is optionally substituted with halogen, C.sub.1-C.sub.4-haloalkyl, and/or C.sub.1-C.sub.4-haloalkoxy.

9. The compound of formula (I) or a stereoisomer, tautomer, salt, or N-oxide thereof according to claim 1, wherein R.sup.1 is C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.4-alkenyl, benzyl or phenyl, which groups may be partially or fully substituted with halogen or C.sub.1-C.sub.4-alkyl.

10. The compound of formula (I) or a stereoisomer, tautomer, salt, or N-oxide thereof according to claim 1 is a compound of formula II-4, ##STR00039## wherein X is O; Y is O Z is direct bond; R.sup.1 is hydrogen, C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.8-alkenyl, C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-cycloalkyl or C.sub.5-C.sub.11-cycloalkylcycloalkyl, wherein the C-atoms of the aforementioned groups may be unsubstituted, or partially or fully substituted with halogen; R.sup.2 is phenyl which may be substituted with halogen, C.sub.1-C.sub.6-haloalkyl or C.sub.1-C.sub.6-haloalkoxy; R.sup.3 is C.sub.1-C.sub.6-alkyl-C(═N(O).sub.pR.sup.b) R.sup.b1.

11. 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.

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) or a stereoisomer, tautomer, salt, or N-oxide thereof as defined in claim 1.

13. A method for combating, controlling, preventing or protecting against infestation or infection by invertebrate pest, comprising contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound of formula (I) or a stereoisomer, tautomer, salt, or N-oxide thereof as defined in claim 1.

14. A non-therapeutic method for treating animals infested or infected by parasites or preventing animals of getting infected or infested 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) or a stereoisomer, tautomer, salt, or N-oxide thereof as defined in claim 1.

15. A seed comprising a compound of formula (I) or a stereoisomer, tautomer, salt, or N-oxide thereof as defined in claim 1 in an amount of from 0.1 g to 10 kg per 100 kg of seed.

16. (canceled)

17. (canceled)

Description

EXAMPLES

Synthesis of 3-[(2E)-2-methoxyiminopropyl]-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium-5-olate (C-1)

Step-1: Synthesis of 2-aminopent-4-en-1-ol (2)

[0547] To a suspension of solid LAH (0.099 mol) in THF (50 mL) was added a solution of 2-aminopent-4-enoic acid (8 g) in dry THF (200 mL, LR) was added slowly dropwise at 0° C. over a period of 30 min. The starting material was not soluble in THF, so heated the slurry of compound in THF for addition, the slurry compound is added to the LAH suspension. After complete addition of starting material, the reaction mixture was heated to refluxed for 4 h. Floathing of LAH was observed in the reaction mixture. The reaction mixture cooled to RT and then the reaction mixture was poured slowly into the saturated aqueous solution of sodium sulphate (exothermic reaction) with manual stirring with Teflon rod and diluted with ethyl acetate (200 mL). The white suspension was formed which filtered through celite bed of sintered funnel and cake was washed with hot THF (500 mL) for 1 h, filtrate was concentrated under reduced pressure to get crude brown colour oil. (4 g)

[0548] 1HNMR (d6-CDCl3) 5.72-5.74 (m, 1H), 5.04-4.97 (m, 1H), 3.52 (dd, 1H), 3.26 (m, 1H), 2.85-2.83 (m, 1H), 2.15-2.09 (m, 1H), 1.92-1.85 (m, 1H)

Step-2: 1-[1-(hydroxymethyl) but-3-enyl]-3-methyl-thiourea (3)

[0549] To a stirred solution of 2-aminopent-4-en-1-ol (3 g) in a THF (50 mL) was added MeNCS (1.90 g) at RT under nitrogen and the reaction mixture was stirred at RT for 16 h. The reaction mixture was concentrated under reduced pressure to get crude and crude was purified by column chromatography using 230-400 mesh size silica with 60% ethyl acetate in heptane as an eluent. (2.5 g)

[0550] 1HNMR (d6-CDCl3) 5.85-5.82 (m, 1H), 5.20-5.16 (m, 2H), 4.15-4.11 (m, 1H), 3.83-3.81 (m, 1H), 3.68-3.66 (m, 1H), 3.00 (d, 3H), 2.39-2.36 (m, 2H)

[0551] LCMS (M+1)=175.0

Step-3: 4-allyl-N-methyl-4,5-dihydrothiazol-2-amine (4)

[0552] To a stirred solution of 1-[1-(hydroxymethyl)but-3-enyl]-3-methyl-thiourea (2.7 g) in a dry THF (50 mL, LR) was added CDI (2.77 g) at 0° C. under nitrogen and the reaction mixture was stirred at RT for 2 h. Reaction was monitored by TLC, Desired conversion was observed on TLC. The reaction mixture was concentrated on rotary evaporator and crude was loaded on silica for slurry to perform the purification on combi flash purifier in silica packed column with 50% ethyl acetate in heptane as an eluent. (1.2 g)

[0553] 1HNMR (d6-CDCl3) 5.90-5.86 (m, 1H), 5.16-5.10 (m, 2H), 4.33-4.29 (m, 1H), 3.41-3.37 (m, 1H), 3.10-307 (m, 1H), 2.95 (S, 3H), 2.55-2.52 (m, 1H), 2.35-2.32 (m, 1H)

[0554] LCMS (M+1)=157.0

Step-4: tert-butyl N-(4-allyl-4,5-dihydrothiazol-2-yl)-N-methyl-carbamate (5)

[0555] 1-[2-(methylamino)-4,5-dihydrothiazol-4-yl] propan-2-one (1.2 g) was dissolved in dry DCM (25 mL, LR grade) at 0° C. and triethylamine (1.55 g, 121-44-8), Boc anhydride (1.67 g) were added simultaneously into reaction mixture under nitrogen atmosphere. Then stirred the reaction mixture at RT for overnight. The solvent was removed in vaccuo and crude was purified by column chromatography using 230-400 mesh size silica with 50% ethyl acetate in heptane as an eluent. (1.10 g)

[0556] 1HNMR (d6-CDCl3) 5.86-5.83 (m, 1H), 5.31-5.10 (m, 2H), 4.36-4.32 (m, 1H), 3.40 (s, 3H), 3.34-3.30 (m, 1H), 3.04-2.98 (m, 1H), 2.51-2.32 (m, 2H), 1.55 (s, 9H).

[0557] LCMS (M+1)=257.1

Step-5: tert-butyl N-(4-acetonyl-4,5-dihydrothiazol-2-yl)-N-methyl-carbamate (6)

[0558] To a stirred solution of tert-butyl N-(4-allyl-4,5-dihydrothiazol-2-yl)-N-methyl-carbamate (1 g) in a mixture of ACN:H2O (7:1) was added Pd(II)OAc2 (0.044 g) and DMP (1.98 g) at RT under nitrogen atmosphere and stirred the reaction mixture at 50° C. for 2 h. The desired conversion was observed on TLC. The reaction mixture was filtered through small celite bed and washed with ethyl acetate, filtrate was concentrated under reduced pressure to afford brown coloured crude. Crude was purified by column chromatography using 230-400 mesh size silica with 20% ethyl acetate heptane as an eluent. (0.3 g)

[0559] 1HNMR (d6-CDCl3) 4.57-4.55 (m, 1H),3.40-3.38 (m, 1H), 3.34-3.30 (m, 1H), 3.30 (s, 3H), 2.97-2.95 (m, 1H), 2.75-2.72 (m, 1H), 2.43 (s, 3H), 1.45 (S, 9H).

[0560] LCMS (M+1)=272.4

Step-6: 1-[2-(methylamino)-4,5-dihydrothiazol-4-yl] propan-2-one (7)

[0561] To a stirred solution of tert-butyl N-(4-acetonyl-4,5-dihydrothiazol-2-yl)-N-methyl-carbamate (0.250 g) in dry DCM (10 mL) was added 4M HCl in dioxane at 0° C. and stirred the reaction mixture at RT for overnight. The reaction mixture was concentrated under reduced pressure on Rotary evaporator to get off white solid. Then residue was basified with saturated solution of sodium bicarbonate (20 mL) and diluted with ethyl acetate (20 mL), organic layer separated, and aqueous layer was re-extracted with ethyl acetate (2×10 mL). Organic layer dried over sodium sulphate and concentrated under reduced pressure to get off pale brown colour semi-solid. (0.120 g)

[0562] 1HNMR (d6-CDCl3) 5.60-5.58 (m, 1H), 3.60-3.58 (m, 2H), 3.10-3.08 (m, 1H), 3.05 (d, 3H) 2.94-2.92 (m, 1H), 2.19 (s, 3H).

Step-7: 3-acetonyl-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a] pyrimidin-4-ium-5-olate (8)

[0563] To a stirred solution of starting material (0.120 g, 1.0 eq) in toluene (10 mL) was added activated diester and heated the reaction mixture at 110° C. for 2 h. The reaction was monitored by TLC. The non-polar spot formation was observed. The reaction mixture was concentrated, and crude was purified by column chromatography using 230-400 mesh size silica with 5% MeOH: DCM as an eluent. (0.120 g)

[0564] 1HNMR (d6-CDCl3) 7.66-7.65 (m, 2H), 7.44-7.41 (m, 2H), 7.19-7.17 (m, 1H), 5.62-5.56 (m, 1H), 4.01-3.98 (m, 1H), 3.51 (s, 3H), 3.48-3.46 (m, 2H), 3.09-3.03 (m, 1H), 2.21 (s, 3H).

[0565] LCMS (M+1)=316.5

Step-8: 3-[(2E)-2-methoxyiminopropyl]-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium-5-olate (C-1)

[0566] To a stirred solution of starting material (0.1 g) in pyridine (10 mL) was added methoxylamine hydrochloride and heated the reaction mixture at 70° C. for 2 h. Concentrated the reaction mixture and Crude was purified by prep HPLC to afford off white solid. (0.020 g) 1HNMR (d6-DMSO) 7.62-7.60 (dd, 2H), 7.24-7.21 (dd, 2H), 7.07 (dd, 1H), 5.40-5.38 (m, 1H), 3.99-3.97 (m, 1H), 3.75 (s, 3H), 3.43-341 (m, 1H), 3.29 (s, 3H), 2.73-2.71 (m, 2H), 1.85 (S, 3H).

[0567] LCMS (M+1)=346.1

BIOLOGICAL EXAMPLES

[0568] If not otherwise specified, the test solutions are prepared as follows:

[0569] 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.

[0570] Test solutions are prepared in general at concentrations of 1000 ppm, 500 ppm, 300 ppm, 100 ppm and 30 ppm (wt/vol).

[0571] B.1. Boll weevil (Anthonomus grandis)

[0572] For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 96-wellmicrotiter plates containing an insect diet and 5-10 A. grandis eggs.

[0573] 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.

[0574] 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.

[0575] In this test, the compound C-1 at 800 ppm showed over 75% mortality in comparison with untreated controls.

[0576] B.2. Diamond back moth (Plutella xylostella)

[0577] The active compound is dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water: acetone. Surfactant (Alkamuls® EL 620) is added at a rate of 0.1% (vol/vol). The test solution is prepared at the day of use.

[0578] Leaves of cabbage were dipped in test solution and air-dried. Treated leaves were placed in petri dish enlined with moist filter paper and inoculated with ten 3rd instar larvae. Mortality was recorded 72 hours after treatment. Feeding damages were also recorded using a scale of 0-100%.

[0579] In this test, the compound C-1 at 500 ppm showed over 75% mortality in comparison with untreated controls

[0580] B.3 Silverleaf whitefly (Bemisia argentifolii) (adults)

[0581] The active compounds were formulated in cyclohexanone as a 10,000 ppm solution supplied in tubes. The tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A non-ionic surfactant (Kinetic®) was included in the solution at a volume of 0.01% (v/v).

[0582] Cotton plants at the cotyledon stage (one plant per pot) were sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into a plastic cup and about 10 to 12 whitefly adults (approximately 3-5 days old) were introduced. The insects were collected using an aspirator and a nontoxic Tygon® tubing connected to a barrier pipette tip. The tip, containing the collected insects, was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding. Cups were covered with a reusable screened lid. Test plants were maintained in a growth room at about 25° C. and about 20-40% relative humidity for 3 days, avoiding direct exposure to fluorescent light (24-hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment, compared to untreated control plants.

[0583] In this test, the compound C-1 at 500 ppm showed over 75% mortality in comparison with untreated controls:

[0584] B.4. Southern armyworm (Spodoptera eridania), 2nd instar larvae

[0585] The active compounds were formulated in cyclohexanone as a 10,000 ppm solution supplied in tubes. The tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01% (v/v).

[0586] Lima bean plants (variety Sieva) were grown 2 plants to a pot and selected for treatment at the 1st true leaf stage. Test solutions were sprayed onto the foliage by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into perforated plastic bags with a zip closure. About 10 to 11 armyworm larvae were placed into the bag and the bags zipped closed. Test plants were maintained in a growth room at about 25° C. and about 20-40% relative humidity for 4 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the bags. Mortality and reduced feeding were assessed 4 days after treatment, compared to untreated control plants. In this test, the compound C-1 at 500 ppm showed over 75% mortality in comparison with untreated controls