Substituted pyrimidinium compounds and derivatives for combating animal pests
11542280 · 2023-01-03
Assignee
Inventors
- Joachim Dickhaut (Ludwigshafen, DE)
- Ashokkumar Adisechan (Navi Mumbai, IN)
- Gopal Krishna Datta (Goettingen, DE)
- Olesya Kuzmina (Ludwigshafen, DE)
Cpc classification
A01N2300/00
HUMAN NECESSITIES
A01N43/90
HUMAN NECESSITIES
A01N2300/00
HUMAN NECESSITIES
A01N43/90
HUMAN NECESSITIES
International classification
A01N43/90
HUMAN NECESSITIES
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) ##STR00001##
wherein X, Y, Z, R.sup.1, R.sup.2, A and R.sup.3 are defined as in the description.
Claims
1. A substituted pyrimidinium compound of formula (I) ##STR00058## 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 the group consisting of 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.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-haloalkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.2-C.sub.4-haloalkynyl, C.sub.3-C.sub.7-cycloalkyl, C.sub.3-C.sub.7-halocycloalkyl, C.sub.4-C.sub.8-alkylcycloalkyl, C.sub.4-C.sub.8-haloalkylcycloalkyl, C.sub.4-C.sub.8-cycloalkylalkyl, C.sub.4-C.sub.8-halocycloalkylalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, C.sub.2-C.sub.6-alkylcarbonyl, C.sub.2-C.sub.6-haloalkylcarbonyl, each substituted with at least one substituent selected from 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 R.sup.3 is phenyl optionally substituted with one or more substituents selected from halogen, 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 R.sup.3 is phenyl optionally substituted with one or more substituents selected from C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-haloalkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.2-C.sub.4-haloalkynyl, C.sub.3-C.sub.7-cycloalkyl, C.sub.3-C.sub.7-halocycloalkyl, C.sub.4-C.sub.8-alkylcycloalkyl, C.sub.4-C.sub.8-haloalkylcycloalkyl, C.sub.4-C.sub.8-cycloalkylalkyl, C.sub.4-C.sub.8-halocycloalkylalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, C.sub.2-C.sub.6-alkylcarbonyl, C.sub.2-C.sub.6-haloalkylcarbonyl, which groups may optionally be substituted with halogen, 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)Rb, 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, 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 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 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-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.sub.8-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 Rea; with the proviso that if R.sup.2 is halogen or CN, then Z is a direct bond; 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 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 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.b, 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 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.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 the group consisting of ═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) of claim 1 or a stereoisomer, tautomer, salt, or N-oxide thereof, wherein X and Y are O.
3. The compound of formula (I) of claim 1 or a stereoisomer, tautomer, salt, or N-oxide thereof, wherein R.sup.3 is C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-haloalkyl, each substituted with at least one substituent selected from cyano.
4. The compound of formula (I) of claim 1 or a stereoisomer, tautomer, salt, or N-oxide thereof of, 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 with R.sup.a.
5. The compound of formula (I) of claim 1 or a stereoisomer, tautomer, salt, or N-oxide thereof, 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.
6. The compound of formula (I) of claim 1 or a stereoisomer, tautomer, salt, or N-oxide thereof, 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.
7. The compound of formula (I) of claim 1 or a stereoisomer, tautomer, salt, or N-oxide thereof, 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.
8. The compound of formula (I) of claim 3 or a stereoisomer, tautomer, salt, or N-oxide thereof, 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 CH.sub.3, CH.sub.2CH.sub.3, isopropyl, cyclopropyl, CH.sub.2CF.sub.3, phenyl, allyl or benzyl; R.sup.2 is phenyl which may be substituted with halogen, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-haloalkoxy or phenyl; Z is a direct bond and R.sup.3 is cyanoethyl or cyanomethyl.
9. The compound of formula (I) of claim 3 or a stereoisomer, tautomer, salt, or N-oxide thereof, wherein the cyano is CH.sub.2—CN or CH.sub.2—CH.sub.2—CN.
10. The compound of formula (I) of claim 3 or a stereoisomer, tautomer, salt, or N-oxide thereof, wherein the cyano is CH.sub.2—CN.
11. The compound of formula (I) of claim 2 or a stereoisomer, tautomer, salt, or N-oxide thereof, 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 with R.sup.a.
12. The compound of formula (I) of claim 2 or a stereoisomer, tautomer, salt, or N-oxide thereof, 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.
13. The compound of formula (I) of claim 2 or a stereoisomer, tautomer, salt, or N-oxide thereof, 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.
14. A composition comprising at least one compound of formula (I) of claim 1 and at least one inert liquid and/or solid carrier.
15. A seed comprising a compound of formula (I) of claim 1 or a stereoisomer, tautomer, salt, or N-oxide thereof in an amount of from 0.1 g to 10 kg per 100 kg of seed.
16. 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) of claim 1 or a stereoisomer, tautomer, salt, or N-oxide thereof.
17. A method for combating, controlling, preventing or protecting against infestation or infection by invertebrate 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) of claim 1 or a stereoisomer, tautomer, salt, or N-oxide thereof.
18. 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) of claim 1 or a stereoisomer, tautomer, salt, or N-oxide thereof.
19. A method for combating, controlling, preventing or protecting against infestation or infection by invertebrate 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) or a stereoisomer, tautomer, salt, or N-oxide thereof a composition of claim 14.
20. 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 composition of claim 14.
Description
EXAMPLES
(1) With appropriate modification of the starting materials, the procedures as described in the preparation examples below were used to obtain further compounds of formula I. The compounds obtained in this manner are listed in the table X that follows, together with physical data.
(2) Compounds can be characterized e.g. by coupled High Performance Liquid Chromatography/mass spectrometry (HPLC/MS), or by .sup.1H-NMR and/or by their melting points.
Example-(C-1)
3-(cyanomethyl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium-5-olate
(3) (C-1)
Step 1: 4-amino-2-(tert-butoxycarbonylamino)-4-oxo-butanoic acid
(4) To Compound of DL-Asparagine monohydrate (15.0 gm, 0.114 mol) in 1,4 Dioxane (150 ml) and water (150 ml) was added sodium carbonate (14.44 gm, 0.136 mol) and Di-tert butyl-dicarbonate (31.29 ml, 0.136 ma). Then reaction mass was stirred for 16 hr. at ambient temperature. Progress of reaction was monitored by TLC. After completion of reaction, reaction mass was concentrate under reduced pressure until 1,4-dioxane was evaporated. Then pH adjusted to 2 with 37% HCl to give white solid that was filtered, washed with water and dried under reduced pressure to afford 25.0 g (94.8% yield) of title compound as a solid.
(5) .sup.1H NMR (DMSO-d.sub.6, 500 MHz) δ=12.5 (s, 1H), 7.31 (s, 1H), 6.88 (t, J=14 Hz, 2H), 4.25-4.21 (m, 1H), 2.51-2.40 (m, 2H), 1.38 (s, 1H).
Step 2: ethyl 2-(tert-butoxycarbonylamino)-3-cyano-propanoate
(6) To the product of step-1 (15.0 gm, 0.065 mol) in DCM (150 ml) and Ethanol (15 ml) was added EDC.HCl (37.4 gm, 0.194 mol) and 4-Dimethylaminopyridine (1.57 gm, 0.013 ml) 0° C. after addition Reaction mass was stirred for 16 hr. at ambient temperature. Progress of reaction was monitored by TLC. After completion of reaction, reaction mass was diluted with water (200 ml) and followed by extracting in ethyl acetate (100 ml×3). The combined organic extracts were dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluting in 0-30% ethyl acetate in heptane as a mobile phase) to afford 7.0 gm (44.7% yield) of title compound as a solid.
(7) .sup.1H NMR (DMSO-d.sub.6, 300 MHz) δ=7.65 (d, J=8.4, 1H), 4.35-4.27 (m, 1H), 4.14-4.07 (m, 2H), 2.29-2.80 (m, 2H), 1.36 (s, 10H), 1.18 (t, J=7.2, 3H).
Step 3: tert-butyl N-[1-(cyanomethyl)-2-hydroxy-ethyl]carbamate
(8) To the product of step-2 (1.8 gm, 0.007 mol) in dry THF (15 ml) was added Lithium borohydride 2M (1.85 ml, 0.004 mol) at 0° C. Then reaction mass was heated at 70° C. for 2 hr. Progress of reaction was monitored by TLC. After completion of reaction, reaction mass was cooled to room temp and acidified with 2M KHSO.sub.4 solution to pH 4. After filtration, Filtrate was extracted in ethyl acetate (30 ml×3). The combined organic extracts were dried over Na.sub.2SO.sub.4, filter and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluting in 0-50% ethyl acetate in heptane as a mobile phase) to afford 1.3 gm (87.4% yield) of title compound as a liquid.
(9) .sup.1H NMR (DMSO-d.sub.6, 300 MHz) δ=6.98 (d, J=8.4, 1H), 4.95-4.91 (m, 1H), 3.65-3.67 (m, 1H), 3.43-3.24 (m, 2H), 2.75-2.55 (m, 1H), 1.39 (s, 9H).
Step 4: 3-amino-4-hydroxy-butanenitrile
(10) To the product of step-3 (0.500 gm, 0.002 mol) in Methanol (5 ml) was added 3M Methanolic HCl (5 ml). Reaction mass was stirred for 16 hr. at ambient temperature. Progress of reaction was monitored by TLC. After completion of reaction, reaction mass was concentrated under reduced pressure. diluted with DCM (10 ml) Then added 3M Methanolic ammonia at 0° C. NH.sub.4Cl was formed, Filtered it and filtrate was concentrated under reduced pressure to afford 0.200 gm (80.0% yield) of title compound as a Liquid.
(11) .sup.1H NMR (CDCl.sub.3-d.sub.6, 500 MHz) δ=3.68-3.57 (m, 2H), 3.28-3.23 (m, 1H), 2.58-2.45 (m, 2H). Step 5: 1-[1-(cyanomethyl)-2-hydroxy-ethyl]-3-methyl-thiourea
(12) To the product of step-4 (0.764 gm, 0.008 mol) in dry THF (10 ml) was added Methyl Isothiocyanate (0.837 gm, 0.011 mol) at 0′C. Reaction mass was stirred for 16 hr. at ambient temperature. Progress of reaction was monitored by TLC. After completion of reaction, Reaction mass was concentrated under reduced pressure to afford crude 1.20 gm (90.8% yield) of title compound as a viscous liquid.
(13) LC/MS (method 1): R.sub.t: 0.84 min; MS: m/z=174.2 (M.sup.+1).
Step 6: 2-[(2Z)-2-methyliminothiazolidin-4-yl]acetonitrile
(14) To the product of step-5 (1.20 gm, 0.007 mol) in dry THF (10 ml) was added 1,1′Carbonyldiimidazole (1.68 gm, 0.010 mol) at room temperature. Reaction mass was stirred for 16 hr. at ambient temperature. Progress of reaction was monitored by TLC. After completion of reaction, reaction mass was concentrate under reduced pressure. The crude product was purified by flash chromatography (eluting in 0-80% ethyl acetate in heptane as a mobile phase) to afford 0.500 gm (46.5% yield) of title compound as a solid.
(15) LC/MS (method 1): R.sub.t: 0.48 min; MS: m/z=156.2 (M.sup.+1).
Step 7: 3-(cyanomethyl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium-5-olate (C-1)
(16) To the product of step-6 (0.200 gm, 0.001 mol) in Toluene (5 ml) was heated at 105° C. for 15 min. Then added Activated ester (0.517 gm 0.001 mol) at same temperature. Then reaction mass was heated at 110° C. for 2 hr. Progress of reaction was monitored by TLC. After completion of reaction, reaction mass was cooled to room temperature, concentrated under reduced pressure. The crude product was purified by flash chromatography (eluting in 0-100% ethyl acetate in heptane as a mobile phase) to afford 0.080 gm (20.5% yield) of title compound as a solid.
(17) LC/MS (method 1): R.sub.t: 1.18 min; MS: m/z=300.0 (M.sup.+1).
(18) .sup.1H NMR (DMSO-d.sub.6, 500 MHz) δ=7.62 (dd J=1.5, 7 Hz, 2H). 7.45 (dd, J=7.5, 7.5 Hz, 2H), 7.09 (dd, J=7.5, 7 Hz, 1H), 4.41-4.39 (m, 1H), 4.10-4.08 (m, 1H), 3.62-3.59 (m, 1H), 3.41 (s, 3H), 3.31-3.21 (m, 1H), 3.19-3.15 (m, 1H),
(19) Examples of compound of formula I given in table Z were prepared using the method analogous to preparation of the above examples or by derivatization of the above examples or intermediates thereof, or using the method analogous to the methods mentioned in the general procedure.
(20) TABLE-US-00038 TABLE Z Example Structure .sup.1H NMR C-1
(21) Biological Tests
(22) The biological activity of the compounds of formula (I) of the present invention can be evaluated in biological tests as described in the following.
(23) General conditions: If not otherwise specified, the test solutions are prepared as follows:
(24) 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.
(25) Test solutions are prepared in general at different concentrations (wt/vol).
(26) Orchid Thrips (Dichromothrips corbetti)
(27) Dichromothrips corbetti adults used for bioassay are 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.
(28) Thrips potency of each compound is evaluated by using a floral-immersion technique. Plastic petri dishes are used as test arenas. All petals of individual, intact orchid flowers are dipped into treatment solution and allowed to dry. Treated flowers are placed into individual petri dishes along with about 20 adult thrips. The petri dishes v then covered with lids. All test arenas are held under continuous light and a temperature of about 28° C. for duration of the assay. After 3 days, the numbers of live thrips are counted on each flower, and along inner walls of each petri dish. The percent mortality is recorded 72 hours after treatment.
(29) In this test, compound C1 at 500 ppm showed over 75% mortality in comparison with untreated controls
(30) Rice Green Leafhopper (Nephotettix virescens)
(31) Rice seedlings are cleaned and washed 24 hours before spraying. The active compounds are formulated in 50:50 acetone:water (vol:vol), and 0.1% vol/vol surfactant (EL 620) is added. Potted rice seedlings are sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants are kept at about 28-29° C. and relative humidity of about 50-60%. Percent mortality is recorded after 72 hours.
(32) In this test, compound C1 at 500 ppm showed over 75% mortality in comparison with untreated controls
(33) Rice Brown Plant Hopper (Nilaparvata lugens)
(34) Rice seedlings are cleaned and washed 24 hours before spraying. The active compounds are formulated in 50:50 acetone:water (vol:vol) and 0.1% vol/vol surfactant (EL 620) is added. Potted rice seedlings are sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants are kept at about 28-29° C. and relative humidity of about 50-60%. Percent mortality is recorded after 72 hours.
(35) In this test, compound C1 at 500 ppm showed over 75% mortality in comparison with untreated controls