NOVEL HETEROARYL-SUBSTITUTED PYRAZINE DERIVATIVES AS PESTICIDES

Abstract

The present invention relates to novel heteroaryl-substituted pyrazine derivatives of the general formula (I), in which the structural elements R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 have the meaning given in the description, to formulations and compositions comprising such compounds and for their use in the control of animal pests including arthropods and insects in plant protection and to their use for control of ectoparasites on animals.

##STR00001##

Claims

1. A compound of formula (I) ##STR00100## in which R.sup.1 is hydrogen; in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.2-C.sub.6haloalkynyl; or phenyl-C.sub.1-C.sub.6alkyl, in which phenyl is optionally substituted with 1 to 5 substituents, each independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —CONH.sub.2, —CSNH.sub.2, —NO.sub.2, —Si(CH.sub.3).sub.3, —SF.sub.5, —NH.sub.2, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycanocycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3cyanoalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.3haloalkoxy, C.sub.1-C.sub.3cyanoalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.1-C.sub.3haloalkylthio, C.sub.1-C.sub.3haloalkylsulfinyl, C.sub.1-C.sub.3haloalkylsulfonyl, C.sub.1-C.sub.3cyanoalkylthio, C.sub.1-C.sub.3cyanoalkylsulfinyl, C.sub.1-C.sub.3-cyanoalkylsulfonyl; or heterocyclyl-C.sub.1-C.sub.6alkyl, wherein the heterocyclyl is selected from the group consisting of saturated and partially unsaturated 3- to 10-membered heterocyclyl, 5-membered heteroaryl, 6-membered heteroaryl, 9-membered heteroaryl and 10-membered heteroaryl and the heterocyclyl is optionally substituted with 1 to 5 substituents, each independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —CONH.sub.2, —CSNH.sub.2, —NO.sub.2, —Si(CH.sub.3).sub.3, —SF.sub.5, —NH.sub.2, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycanocycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3cyanoalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.3haloalkoxy, C.sub.1-C.sub.3cyanoalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.1-C.sub.3haloalkylthio, C.sub.1-C.sub.3haloalkylsulfinyl, C.sub.1-C.sub.3haloalkylsulfonyl, C.sub.1-C.sub.3cyanoalkylthio, C.sub.1-C.sub.3cyanoalkylsulfinyl, C.sub.1-C.sub.3cyanoalkylsulfonyl R.sup.2 is phenyl or a 5- or 6-membered heteroaryl, each of which is optionally substituted with 1, 2 or 3 substituents independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —NO.sub.2, —NH.sub.2, —SF.sub.5; and in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkoxy, C.sub.1-C.sub.6haloalkoxy, hydroxy-C.sub.1-C.sub.6alkyl, —CO.sub.2C.sub.1-C.sub.6alkyl, —NH(C.sub.1-C.sub.6alkyl), —N(C.sub.1-C.sub.6alkyl).sub.2, S—C.sub.1-C.sub.6alkylsulfinimidoyl, S—C.sub.3-C.sub.6cycloalkylsulfinimidoyl, S—C.sub.2-C.sub.6alkenylsulfinimidoyl, S—C.sub.2-C.sub.6alkinylsulfinimidoyl, S-phenylsulfinimidoyl, S-heterocyclylsulfinimidoyl, S-heteroarylsulfinimidoyl, S—C.sub.1-C.sub.6alkylsulfonimidoyl, S—C.sub.3-C.sub.6cycloalkylsulfonimidoyl, S—C.sub.2-C.sub.6alkenylsulfonimidoyl, S—C.sub.2-C.sub.6alkinylsulfonimidoyl, S-phenylsulfonimidoyl, S-heterocyclylsulfonimidoyl, S-heteroarylsulfonimidoyl, —C(═NOC.sub.1—C.sub.6alkyl)H, —C(═NOC.sub.1—C.sub.6alkyl)-C.sub.1-C.sub.6alkyl, (C.sub.1-C.sub.6alkyl).sub.3-silyl; and the substructures S1-S9, in which the bond to the phenyl or 5- or 6-membered heteroaryl is marked with a # and Z is CO or CS and Y is independently selected from CO or SO.sub.2; ##STR00101## R.sup.21 is hydrogen or in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, —C.sub.1-C.sub.6alkyl-C.sub.3-C.sub.6cycloalkyl, phenyl, heteroaryl and heterocyclyl; R.sup.22 is hydrogen or in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, —C.sub.1-C.sub.6alkyl-C.sub.3-C.sub.6cycloalkyl and C.sub.3-C.sub.6cycloalkyl; R.sup.23 is independently selected from in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl and phenyl; R.sup.24 is in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, phenyl, heteroaryl and heterocyclyl; or R.sup.21 and R.sup.22 together with the nitrogen atom to which they are attached, represent a monocyclic or polycyclic optionally substituted 3- to 12-membered saturated or unsaturated heterocyclyl which may contain further heteroatoms; and 3- to 6-membered heterocyclyl or a 5- to 6-membered heteroaryl each containing 1 or 2 heteroatoms selected from the group consisting of N, O, and S, wherein the 3- to 6-membered heterocyclyl or the 5- to 6-membered heteroaryl substituent may optionally carry 1, 2, 3 or 4 substituents independently selected from the group consisting of halogen, hydroxy, CN, —COOH, —CONH.sub.2, —CSNH.sub.2, —NO.sub.2, —Si(CH.sub.3).sub.3, SF.sub.5, —NH.sub.2, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycanocycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3cyanoalkyl, C.sub.3-C.sub.6cyanocycloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.3haloalkoxy, C.sub.1-C.sub.3cyanoalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.1-C.sub.3haloalkylthio, C.sub.1-C.sub.3haloalkylsulfinyl, C.sub.1-C.sub.3haloalkylsulfonyl, C.sub.1-C.sub.3cyanoalkylthio, C.sub.1-C.sub.3cyanoalkylsulfinyl, C.sub.1-C.sub.3cyanoalkylsulfonyl; R.sup.3 is hydrogen or C.sub.1-C.sub.6alkyl optionally substituted with 1 to 3 substituents selected from halogen, C.sub.3-C.sub.6-cycloalkyl and C.sub.1-C.sub.6-alkoxy; R.sup.4 is a monocyclic 5-membered heteroaryl, containing 3 or 4 heteroatoms selected from the group consisting of N, O, and S, and optionally substituted by 1 or 2 substituents independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —NO.sub.2, —NH.sub.2, —SF.sub.5; and in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6alkyl-C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkoxy, C.sub.1-C.sub.6haloalkoxy, hydroxy-C.sub.1-C.sub.6alkyl, —NH(C.sub.1-C.sub.6alkyl), —NH(C.sub.1-C.sub.6alkyl-C.sub.3-C.sub.6cycloalkyl), —N(C.sub.1-C.sub.6alkyl).sub.2, —N(C.sub.1-C.sub.6alkyl)(C.sub.1-C.sub.6alkyl-C.sub.3-C.sub.6cycloalkyl), —CO.sub.2C.sub.1-C.sub.6alkyl, S—C.sub.1-C.sub.6alkylsulfinimidoyl, S—C.sub.3-C.sub.6cycloalkylsulfinimidoyl, S—C.sub.2-C.sub.6alkenylsulfinimidoyl, S—C.sub.2-C.sub.6alkinylsulfinimidoyl, S-phenylsulfinimidoyl, S-heterocyclylsulfinimidoyl, S-heteroarylsulfinimidoyl, S—C.sub.1-C.sub.6alkylsulfonimidoyl, S—C.sub.3-C.sub.6cycloalkylsulfonimidoyl, S—C.sub.2-C.sub.6alkenylsulfonimidoyl, S—C.sub.2-C.sub.6alkinylsulfonimidoyl, S-phenylsulfonimidoyl, S-heterocyclylsulfonimidoyl, S-heteroarylsulfonimidoyl, —C(═NOC.sub.1—C.sub.6alkyl)H, —C(═NOC.sub.1—C.sub.6alkyl)-C.sub.1-C.sub.6alkyl; and 3- to 6-membered heterocyclyl containing 1 or 2 heteroatoms selected from the group consisting of N, O, and S, wherein the 3- to 6-membered heterocyclyl substituent may optionally carry 1, 2, 3 or 4 substituents independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —CONH.sub.2, —CSNH.sub.2, —NO.sub.2, —Si(CH.sub.3).sub.3, —SF.sub.5, —NH.sub.2, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycanocycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3cyanoalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.3haloalkoxy, C.sub.1-C.sub.3cyanoalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.1-C.sub.3haloalkylthio, C.sub.1-C.sub.3haloalkylsulfinyl, C.sub.1-C.sub.3haloalkylsulfonyl, C.sub.1-C.sub.3cyanoalkylthio, C.sub.1-C.sub.3cyanoalkylsulfinyl, C.sub.1-C.sub.3cyanoalkylsulfonyl; and the following substructures S10-S18, in which the bond to the monocyclic 5-membered heteroaryl is marked with a # and Z is CO or CS and Y is independently selected from CO or SO.sub.2: ##STR00102## R.sup.41 is hydrogen or in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, —C.sub.1-C.sub.6alkyl-C.sub.3-C.sub.6cycloalkyl, phenyl, heteroaryl and heterocyclyl; R.sup.42 is hydrogen or in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl and C.sub.3-C.sub.6cycloalkyl; R.sup.43 is independently selected from in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl and phenyl; R.sup.44 is in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, phenyl, heteroaryl and heterocyclyl; or R.sup.41 and R.sup.42 together with the nitrogen atom to which they are attached, represent a monocyclic or polycyclic optionally substituted 3- to 12-membered saturated or unsaturated heterocyclyl which may contain further heteroatoms; R.sup.5 is hydrogen, halogen, —CN, —NH.sub.2, or in each case optionally substituted C.sub.1-C.sub.3-alkyl, C.sub.3-C.sub.4-cycloalkyl, C.sub.1-C.sub.3alkoxy, —CO.sub.2(C.sub.1-C.sub.3alkyl), —CH—(C.sub.1-C.sub.3alkoxy).sub.2, —CONH(C.sub.1-C.sub.4alkyl), —CON(C.sub.1-C.sub.4alkyl).sub.2, —NHCO—C.sub.1-C.sub.4alkyl, —N(C.sub.1-C.sub.4alkyl)CO—C.sub.1-C.sub.4alkyl, —C(═NOC.sub.1—C.sub.4alkyl)H, or —C(═NOC.sub.1—C.sub.4alkyl)-C.sub.1-C.sub.4alkyl, —NH(C.sub.1-C.sub.3alkyl), —N(C.sub.1-C.sub.3alkyl).sub.2, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.3-C.sub.6cycloalkylthio, C.sub.3-C.sub.6cycloalkylsulfinyl, C.sub.3-C.sub.6cycloalkylsulfonyl; R.sup.6 is hydrogen, halogen, —CN, —NH.sub.2, or in each case optionally substituted C.sub.1-C.sub.3-alkyl, C.sub.3-C.sub.4cycloalkyl, C.sub.1-C.sub.3alkoxy, —CO.sub.2(C.sub.1-C.sub.3alkyl), —CH—(C.sub.1-C.sub.3alkoxy).sub.2, —CONH(C.sub.1-C.sub.4alkyl), —CON(C.sub.1-C.sub.4alkyl).sub.2, —NHCO—C.sub.1-C.sub.4alkyl, —N(C.sub.1-C.sub.4alkyl)CO—C.sub.1-C.sub.4alkyl, —C(═NOC.sub.1—C.sub.4alkyl)H, or —C(═NOC.sub.1—C.sub.4alkyl)-C.sub.1-C.sub.4alkyl, —NH(C.sub.1-C.sub.3alkyl), —N(C.sub.1-C.sub.3alkyl).sub.2, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.3-C.sub.6cycloalkylthio, C.sub.3-C.sub.6cycloalkylsulfinyl, C.sub.3-C.sub.6cycloalkylsulfonyl; And/or a salt and/or N-oxide thereof.

2. The compound according to claim 1, in which R.sup.1 is hydrogen; or in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkylthioC.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkylsulfinylC.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkylsulfonylC.sub.1-C.sub.6alkyl, wherein the aforementioned optionally substituted radicals are optionally substituted with up to 3 substituents independently selected from the group consisting of halogen, hydroxy, —CN, —NO.sub.2, —Si(CH.sub.3).sub.3, —NH.sub.2 and C.sub.1-C.sub.6alkyl; or phenyl-C.sub.1-C.sub.6alkyl, in which phenyl is optionally substituted with 1 to 5 substituents, each independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —CONH.sub.2, —CSNH.sub.2, —NO.sub.2, —Si(CH.sub.3).sub.3, —SF.sub.5, —NH.sub.2, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cyanocycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3cyanoalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.3haloalkoxy, C.sub.1-C.sub.3cyanoalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.1-C.sub.3haloalkylthio, C.sub.1-C.sub.3haloalkylsulfinyl, C.sub.1-C.sub.3haloalkylsulfonyl, C.sub.1-C.sub.3cyanoalkylthio, C.sub.1-C.sub.3cyanoalkylsulfinyl, C.sub.1-C.sub.3cyanoalkylsulfonyl; or heterocyclyl-C.sub.1-C.sub.3alkyl, wherein the heterocyclyl is selected from the group consisting of tetrahydropyranyl, tetrahydrofuranyl, oxetanyl and azetidinyl, or heteroaryl, wherein the heteroaryl is selected from the group consisting of pyridyl, pyrimidinyl, pyrazyl, pyridazinyl, thiophenyl, furanyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, and oxazolyl, and wherein the heteroaryl or the heterocyclyl is optionally substituted with 1 to 3 substituents, each independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —CONH.sub.2, —CSNH.sub.2, —NO.sub.2, —Si(CH.sub.3).sub.3, SF.sub.5, —NH.sub.2, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycanocycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3cyanoalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.3haloalkoxy, C.sub.1-C.sub.3cyanoalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.1-C.sub.3haloalkylthio, C.sub.1-C.sub.3haloalkylsulfinyl, C.sub.1-C.sub.3haloalkylsulfonyl, C.sub.1-C.sub.3cyanoalkylthio, C.sub.1-C.sub.3cyanoalkylsulfinyl, C.sub.1-C.sub.3cyanoalkylsulfonyl; R.sup.2 is selected from the group consisting of phenyl, pyridine, pyrimidine, pyrazine, pyridazine, pyrazole, pyrrole, thiazole, oxazole and thiophene, each of which is optionally substituted by 1, 2 or 3 substituents independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —NO.sub.2, —NH.sub.2, —SF.sub.5; and in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.3-C.sub.6cycloalkoxy, C.sub.1-C.sub.3haloalkoxy, hydroxy-C.sub.1-C.sub.4alkyl, —CO.sub.2C.sub.1-C.sub.4alkyl, —NH(C.sub.1-C.sub.4alkyl), —N(C.sub.1-C.sub.4alkyl).sub.2, —C(═NOC.sub.1—C.sub.4alkyl)H, —C(═NOC.sub.1—C.sub.4alkyl)-C.sub.1-C.sub.4alkyl and (C.sub.1-C.sub.4alkyl).sub.3-silyl, wherein the aforementioned optionally substituted radicals are optionally substituted with up to 3 substituents independently selected from the group consisting of halogen, hydroxy, oxo (═O), —CN, —NO.sub.2, —Si(CH.sub.3).sub.3, —NH.sub.2, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.3-C.sub.4cycloalkyl, C.sub.3-C.sub.4-halocycloalkyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.3-C.sub.4cycloalkylsulfonyl, C.sub.1-C.sub.3haloalkylthio and C.sub.1-C.sub.3haloalkylsulfonyl; and the substructures S1, S4, S7, S8 and S9, in which the bond to the aforementioned phenyl, pyridine, pyrimidine, pyrazine, pyridazine, pyrazole, pyrrole, thiazole, oxazole or thiophene is marked with a # and Z is CO or CS; ##STR00103## R.sup.21 is hydrogen or in each case optionally substituted C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6cycloalkyl, —C.sub.1-C.sub.4alkyl-C.sub.3-C.sub.6cycloalkyl and 3- to 6-membered heterocyclyl. R.sup.22 is hydrogen or in each case optionally substituted C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, —C.sub.1-C.sub.4alkyl-C.sub.3-C.sub.6cycloalkyl and C.sub.3-C.sub.6cycloalkyl. R.sup.24 is in each case optionally substituted C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6cycloalkyl, phenyl, heteroaryl and 3- to 6-membered heterocyclyl. wherein the aforementioned optionally substituted radicals in the definitions of R.sup.21, R.sup.22 and R.sup.24 are optionally substituted with up to 3 substituents independently selected from the group consisting of halogen, hydroxy, —CN, —NO.sub.2, —Si(CH.sub.3).sub.3, —NH.sub.2, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.3-C.sub.4cycloalkyl, C.sub.3-C.sub.4halocycloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.3alkylsulfonyl, C.sub.3-C.sub.4cycloalkylsulfonyl, C.sub.1-C.sub.3haloalkylthio and C.sub.1-C.sub.3haloalkylsulfonyl; or R.sup.21 and R.sup.22 together with the nitrogen atom to which they are attached, represent a 4- to 12-membered saturated or unsaturated heterocyclyl which may contain up to two further heteroatoms selected from the group of oxygen, nitrogen and sulfur and which is optionally substituted with one to three substituents selected from the group consisting of halogen, ═O (oxo), ═S (thiono), hydroxy, —CN, —NO.sub.2, —SF.sub.5, and —NH.sub.2; and C.sub.1-C.sub.4alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.3-C.sub.6cycloalkylsulfanyl, C.sub.3-C.sub.6cycloalkylsulfinyl, C.sub.3-C.sub.6cycloalkylsulfonyl, C.sub.1-C.sub.4haloalkylthio, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl; and 3- to 6-membered heterocyclyl or a 5- to 6-membered heteroaryl each containing 1 or 2 heteroatoms selected from the group consisting of N, O, and S, wherein the 3- to 6-membered heterocyclyl or the 5- to 6-membered heteroaryl substituent may optionally carry 1, 2 or 3 substituents independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —CONH.sub.2, —CSNH.sub.2, —NO.sub.2, —Si(CH.sub.3).sub.3, —SF.sub.5, —NH.sub.2, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3cyanoalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.3haloalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.1-C.sub.3haloalkylthio, C.sub.1-C.sub.3haloalkylsulfinyl, C.sub.1-C.sub.3haloalkylsulfonyl; R.sup.3 is hydrogen or C.sub.1-C.sub.6alkyl optionally substituted with halogen, cyano, C.sub.3-C.sub.6cycloalkyl or C.sub.1-C.sub.4alkoxy; R.sup.4 is selected from the group consisting of triazole, oxadiazole, thiadiazole and tetrazole, where any oxadiazole, thiadiazole and tetrazole is optionally substituted by 1 substituent, a triazole is optionally substituted with 1 or 2 substituents, independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —NO.sub.2, —NH.sub.2, —SF.sub.5; and in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.3-C.sub.6cycloalkoxy, C.sub.1-C.sub.3haloalkoxy, hydroxy-C.sub.1-C.sub.4alkyl, —CO.sub.2C.sub.1-C.sub.4alkyl, —NH(C.sub.1-C.sub.4alkyl), —N(C.sub.1-C.sub.4alkyl).sub.2, —C(═NOC.sub.1—C.sub.4alkyl)H, —C(═NOC.sub.1—C.sub.4alkyl)-C.sub.1-C.sub.4alkyl and (C.sub.1-C.sub.4alkyl).sub.3-silyl, wherein the aforementioned optionally substituted radicals are optionally substituted with up to 3 substituents independently selected from the group consisting of halogen, hydroxy, oxo (═O), —CN, —NO.sub.2, —Si(CH.sub.3).sub.3, —NH.sub.2, —CONH.sub.2, —CONH(C.sub.1-C.sub.4alkyl), —CON(C.sub.1-C.sub.4alkyl).sub.2, —COOC.sub.1-C.sub.4alkyl, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.3-C.sub.4cycloalkyl, C.sub.3-C.sub.4halocycloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.3alkylsulfonyl, C.sub.3-C.sub.4cycloalkylsulfonyl, C.sub.1-C.sub.3haloalkylthio and C.sub.1-C.sub.3haloalkylsulfonyl; and the substructures S10, S11, S13, S14, S16, S17 and S18, in which the bond to the aforementioned triazole, oxadiazole, thiadiazole and tetrazole is marked with a # and Z is CO or CS; ##STR00104## R.sup.41 is hydrogen or in each case optionally substituted C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6cycloalkyl, —C.sub.1-C.sub.4alkyl-C.sub.3-C.sub.6cycloalkyl and 3- to 6-membered heterocyclyl. R.sup.42 is hydrogen or in each case optionally substituted C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, —C.sub.1-C.sub.4alkyl-C.sub.3-C.sub.6cycloalkyl and C.sub.3-C.sub.6cycloalkyl. R.sup.43 is independently selected from in each case optionally substituted C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl and C.sub.3-C.sub.6cycloalkyl. R.sup.44 is in each case optionally substituted C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.3-C.sub.6cycloalkyl, phenyl, heteroaryl and 3- to 6-membered heterocyclyl. wherein the aforementioned optionally substituted radicals in the definitions of R.sup.41, R.sup.42, R.sup.43 and R.sup.24 are optionally substituted with up to 3 substituents independently selected from the group consisting of halogen, hydroxy, —CN, —NO.sub.2, —Si(CH.sub.3).sub.3, —NH.sub.2, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.3-C.sub.4cycloalkyl, C.sub.3-C.sub.4halocycloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.3alkylsulfonyl, C.sub.3-C.sub.4cycloalkylsulfonyl, C.sub.1-C.sub.3haloalkylthio and C.sub.1-C.sub.3haloalkylsulfonyl; or R.sup.41 and R.sup.42 together with the nitrogen atom to which they are attached, represent a 4- to 12-membered saturated or unsaturated heterocyclyl which may contain up to two further heteroatoms selected from the group of oxygen, nitrogen, sulfur and silicon and which is optionally substituted with one to three substituents selected from the group consisting of halogen, ═O (oxo), ═S (thiono), hydroxy, —CN, —NO.sub.2, —SF.sub.5, and —NH.sub.2; and in each case optionally substituted C.sub.1-C.sub.4alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkoxy, C.sub.1-C.sub.4alkylthio, C.sub.1-C.sub.4alkylsulfinyl, C.sub.1-C.sub.4alkylsulfonyl, C.sub.3-C.sub.6cycloalkylsulfanyl, C.sub.3-C.sub.6cycloalkylsulfinyl, C.sub.3-C.sub.6cycloalkylsulfonyl, C.sub.1-C.sub.4haloalkylthio, C.sub.1-C.sub.4haloalkylsulfinyl, C.sub.1-C.sub.4haloalkylsulfonyl; and 3- to 6-membered heterocyclyl or a 5- to 6-membered heteroaryl each containing 1 or 2 heteroatoms selected from the group consisting of N, O, and S, wherein the 3- to 6-membered heterocyclyl or the 5- to 6-membered heteroaryl substituent may optionally carry 1, 2 or 3 substituents independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —CONH.sub.2, —CSNH.sub.2, —NO.sub.2, —Si(CH.sub.3).sub.3, —SF.sub.5, —NH.sub.2, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3cyanoalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.3haloalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.1-C.sub.3haloalkylthio, C.sub.1-C.sub.3haloalkylsulfinyl, C.sub.1-C.sub.3haloalkylsulfonyl; R.sup.5 is hydrogen, halogen, —CN, NH.sub.2, or in each case optionally substituted C.sub.1-C.sub.3-alkyl, C.sub.3-C.sub.4-cycloalkyl, C.sub.1-C.sub.3alkoxy, —CO.sub.2(C.sub.1-C.sub.3alkyl), —CH—(C.sub.1-C.sub.3alkoxy).sub.2, —CONH(C.sub.1-C.sub.4alkyl), CON(C.sub.1-C.sub.4alkyl).sub.2, —NHCO—C.sub.1-C.sub.4alkyl, —N(C.sub.1-C.sub.4alkyl)CO—C.sub.1-C.sub.4alkyl, —C(═NOC.sub.1—C.sub.4alkyl)H, or —C(═NOC.sub.1—C.sub.4alkyl)-C.sub.1-C.sub.4alkyl, NH(C.sub.1-C.sub.3alkyl), N(C.sub.1-C.sub.3alkyl).sub.2, C.sub.1-C.sub.3alkylthio, C.sub.3-C.sub.6cycloalkylthio, wherein the aforementioned optionally substituted radicals are optionally substituted with up to 3 substituents independently selected from the group consisting of halogen, hydroxy, —CN, —NO.sub.2, —Si(CH.sub.3).sub.3, —NH.sub.2 and C.sub.1-C.sub.3alkyl; R.sup.6 is hydrogen, halogen, —CN, NH.sub.2, or in each case optionally substituted C.sub.1-C.sub.3-alkyl, C.sub.3-C.sub.4-cycloalkyl, C.sub.1-C.sub.3alkoxy, —CO.sub.2(C.sub.1-C.sub.3alkyl), —CH—(C.sub.1-C.sub.3alkoxy).sub.2, —CONH(C.sub.1-C.sub.4alkyl), —CON(C.sub.1-C.sub.4alkyl).sub.2, —NHCO—C.sub.1-C.sub.4alkyl, —N(C.sub.1-C.sub.4alkyl)CO—C.sub.1-C.sub.4alkyl, —C(═NOC.sub.1—C.sub.4alkyl)H, or —C(═NOC.sub.1—C.sub.4alkyl)-C.sub.1-C.sub.4alkyl, NH(C.sub.1-C.sub.3alkyl), N(C.sub.1-C.sub.3alkyl).sub.2, C.sub.1-C.sub.3alkylthio, C.sub.3-C.sub.6cycloalkylthio, wherein the aforementioned optionally substituted radicals are optionally substituted with up to 3 substituents independently selected from the group consisting of halogen, hydroxy, —CN, —NO.sub.2, —Si(CH.sub.3).sub.3, —NH.sub.2 and C.sub.1-C.sub.3alkyl; And/or a salt and/or N-oxide thereof.

3. The compound according to claim 1, in which R.sup.1 is hydrogen; or C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.2-C.sub.6haloalkynyl, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3alkylthioC.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3alkylsulfinylC.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3alkylsulfonylC.sub.1-C.sub.3alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6cyanoalkyl; R.sup.2 is selected from the group consisting of phenyl, pyridine, pyrimidine, pyrazine, and pyridazine, each of which is optionally substituted by a total of 1, 2 or 3 substituents, wherein 1, 2 or 3 of the optional substituents are independently selected from group A consisting of halogen, hydroxy, —CN, —COOH, —NO.sub.2, —NH.sub.2, —SF.sub.5; and C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3cyanoalkyl, C.sub.3-C.sub.4cycloalkyl, C.sub.3-C.sub.4-halocycloalkyl, C.sub.3-C.sub.4cyanocycloalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3haloalkoxy, C.sub.3-C.sub.4cycloalkoxy, C.sub.1-C.sub.3cyanoalkoxy, —CO.sub.2C.sub.1-C.sub.4alkyl and (C.sub.1-C.sub.3alkyl).sub.3-silyl; and optionally 1 of the optional substituents may be selected from group B consisting of the substructures S1, S4, S7, S8 and S9, in which the bond to the phenyl, pyridine, pyrimidine, pyrazine, or pyridazine is marked with a # and Z is CO; ##STR00105## R.sup.21 is hydrogen or in each case optionally substituted C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.3-C.sub.4cycloalkyl. R.sup.22 is hydrogen or in each case optionally substituted C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl and C.sub.3-C.sub.4cycloalkyl. R.sup.24 is in each case optionally substituted C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.3-C.sub.4cycloalkyl and phenyl. wherein the aforementioned optionally substituted radicals in the definitions of R.sup.21, R.sup.22 and R.sup.24 are optionally substituted with up to 3 substituents independently selected from the group consisting of halogen, —CN, —NO.sub.2, —Si(CH.sub.3).sub.3, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl; R.sup.3 is hydrogen or C.sub.1-C.sub.6alkyl; R.sup.4 is selected from the group consisting of ##STR00106## where # designates the attachment to the pyrazine moiety, optionally substituted by 1 substituent R.sup.8 which has the meaning of R.sup.81 when bound to a nitrogen atom and R.sup.82 when bound to a carbon atom of the 5-membered heteroaryl, R.sup.81 is selected from the group consisting of C.sub.1-C.sub.4alkyl, C.sub.3-C.sub.4cycloalkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3cyanoalkyl, —(C.sub.1-C.sub.3alkyl)CONH.sub.2, —(C.sub.1-C.sub.3alkyl)-CONH(C.sub.1-C.sub.4alkyl), —(C.sub.1-C.sub.3alkyl)CON(C.sub.1-C.sub.4alkyl).sub.2, C.sub.3-C.sub.4cyanocycloalkyl, hydroxy-C.sub.1-C.sub.3alkyl, —CO.sub.2C.sub.1-C.sub.4alkyl, —COOC.sub.1-C.sub.4alkyl, —(C.sub.1-C.sub.3alkyl)-COOC.sub.1-C.sub.4alkyl, and 5-membered heteroaryl containing 1 or 2 heteroatoms selected from the group consisting of N, O, and S, wherein the 5-membered heteroaryl substituent may optionally carry 1 or 2 substituents independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —CONH.sub.2, —Si(CH.sub.3).sub.3, —SF.sub.5, —NH.sub.2, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3cyanoalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.3haloalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.1-C.sub.3haloalkylthio, C.sub.1-C.sub.3haloalkylsulfinyl, C.sub.1-C.sub.3haloalkylsulfonyl; R.sup.82 is selected from the group consisting of halogen, hydroxy, —CN, —COOH, —NO.sub.2, —NH.sub.2, —SF.sub.5; and C.sub.1-C.sub.4alkyl, C.sub.3-C.sub.4cycloalkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3cyanoalkyl, —(C.sub.1-C.sub.3alkyl)CONH.sub.2, —(C.sub.1-C.sub.3alkyl)-CONH(C.sub.1-C.sub.4alkyl), —(C.sub.1-C.sub.3alkyl)CON(C.sub.1-C.sub.4alkyl).sub.2, —(C.sub.1-C.sub.3alkyl)-COOC.sub.1-C.sub.4alkyl, C.sub.3-C.sub.4cyanocycloalkyl, C.sub.1-C.sub.3alkoxy, C.sub.3-C.sub.4cycloalkoxy, C.sub.1-C.sub.3haloalkoxy, C.sub.1-C.sub.3cyanoalkoxy, hydroxy-C.sub.1-C.sub.3alkyl, —CO.sub.2C.sub.1-C.sub.4alkyl, —NH(C.sub.1-C.sub.3alkyl), —N(C.sub.1-C.sub.3alkyl).sub.2, —C(═NOC.sub.1—C.sub.3alkyl)H, —C(═NOC.sub.1—C.sub.3alkyl)-C.sub.1-C.sub.3alkyl, and (C.sub.1-C.sub.3alkyl).sub.3-silyl; and the substructures S10, S13, S16, S17 and S18, in which the bond to the ring to which R.sup.8 is attached is marked with a # and Z is CO; ##STR00107## R.sup.41 is hydrogen or in each case optionally substituted C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.3-C.sub.4cycloalkyl, —C.sub.1-C.sub.2alkyl-C.sub.3-C.sub.4cycloalkyl and 3- to 6-membered heterocyclyl containing 1 heteroatoms selected from the group consisting of N, O, and S. R.sup.42 is hydrogen or in each case optionally substituted C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, —C.sub.1-C.sub.2alkyl-C.sub.3-C.sub.4cycloalkyl and C.sub.3-C.sub.4cycloalkyl. R.sup.44 is in each case optionally substituted C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.3-C.sub.4cycloalkyl. wherein the aforementioned optionally substituted radicals defined for R.sup.41, R.sup.42 and R.sup.44 are optionally substituted with up to 2 substituents independently selected from the group consisting of halogen, —CN, —NO.sub.2, —Si(CH.sub.3).sub.3, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkyl; or R.sup.41 and R.sup.42 together with the nitrogen atom to which they are attached, represent a monocyclic 4- to 8-membered saturated heterocyclyl which may contain up to one further heteroatom selected from the group of oxygen, nitrogen, sulfur and silicon and which is optionally substituted with one to three substituents selected from the group consisting of  halogen, ═O (oxo), ═S (thiono), hydroxy, —CN, —NO.sub.2, and —NH.sub.2;  and C.sub.1-C.sub.3alkyl, C.sub.3-C.sub.4cycloalkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3haloalkoxy; and 5-membered heteroaryl containing 1 or 2 nitrogen atoms selected from the group consisting of N, O, and S, wherein the 5-membered heteroaryl substituent may optionally carry 1 or 2 substituents independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —CONH.sub.2, —Si(CH.sub.3).sub.3, —SF.sub.5, —NH.sub.2, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3cyanoalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.3haloalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.1-C.sub.3haloalkylthio, C.sub.1-C.sub.3haloalkylsulfinyl, C.sub.1-C.sub.3haloalkylsulfonyl; R.sup.5 is hydrogen, halogen, —CN, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-haloalkyl, C.sub.3-C.sub.4-cycloalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3haloalkoxy; R.sup.6 is hydrogen, halogen, —CN, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-haloalkyl, C.sub.3-C.sub.4cycloalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3haloalkoxy; And/or a salt and/or N-oxide thereof.

4. The compound according to claim 1, in which R.sup.1 is hydrogen; methyl, ethyl, n-propyl, isopropyl, cyanomethyl, cyclopropylmethyl, methoxymethyl, ethoxymethyl, methylthiomethyl, ethylthiomethyl, methylthioethyl, ethylthioethyl, methylsulfonylethyl, ethylsulfonylethyl; R.sup.2 is selected from the group consisting of phenyl and pyridine each of which is optionally substituted by 1 or 2 substituents independently selected from the group consisting of fluorine, chlorine, bromine, iodine, hydroxy, —CN, —COOH, —CONH.sub.2, —NO.sub.2, —NH.sub.2, —SF.sub.5, methyl, ethyl, n-propyl, isopropyl, butyl, tert-butyl, cyclopropyl, cyclobutyl, 1-cyanocyclopropyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, cyanomethyl, 1-methyl-1-cyanoethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, cyanomethoxy, methylthio, methylsulfinyl, methylsulfonyl, ethylsulfonyl, cyclopropylsulfonyl, difluoromethylthio, trifluoromethylthio, difluoromethylsulfinyl, trifluoromethylsulfinyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, (CH.sub.3).sub.3-silyl, phenylsulfonyl which may carry a fluorine, chlorine or methyl substituent; R.sup.3 is hydrogen, methyl, ethyl, n-propyl, or isopropyl; R.sup.4 is selected from the group consisting of ##STR00108## wherein # designates the attachment to the pyrazine moiety and wherein R.sup.81 is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, difluoromethyl, trifluoromethyl, trifluoroethyl, cyanomethyl, —CH.sub.2CONH.sub.2, —CH.sub.2CONHCH.sub.3, —CH.sub.2CONH(CH.sub.3).sub.2, —COOCH.sub.3, —COOCH.sub.2CH.sub.3, —COOCH(CH.sub.3).sub.2, —COOC(CH.sub.3).sub.3, —CH.sub.2—COOCH.sub.2CH.sub.3; and pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, furanyl, thienyl each of which may optionally be substituted with 1 substituent selected from fluorine, chlorine, bromine, —CN, —COOH, —CONH.sub.2, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, trifluoromethyl, trifluoroethyl, cyanomethyl, methoxy, ethoxy, trifluoromethoxy; R.sup.82 is selected from the group consisting of fluorine, chlorine, bromine, —CN, —COOH, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, cyanomethyl, —CH.sub.2CONH.sub.2, —CH.sub.2CONHCH.sub.3, —CH.sub.2CONH(CH.sub.3).sub.2, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, cyanomethoxy, methylthio, methylsulfinyl, methylsulfonyl, ethylsulfonyl, cyclopropylsulfonyl, difluoromethylthio, trifluoromethylthio, difluoromethylsulfinyl, trifluoromethylsulfinyl, difluoromethylsulfonyl, trifluoromethyl-sulfonyl, —COOCH.sub.3, —COOCH.sub.2CH.sub.3, —CH.sub.2—COOCH.sub.2CH.sub.3, and the substructures S13, in which the bond to the ring to which R.sup.82 is attached is marked with a # and Z is CO; ##STR00109## wherein R.sup.41 is hydrogen, methyl, ethyl, n-propyl, propane-2-yl, butane-2-yl, 2,2,2-trifluoroethyl, 2-trifluoromethoxyethyl, cyanomethyl, cyclopropyl, cyclopropylmethyl, or 2-methyl-n-propyl; R.sup.42 is hydrogen, methyl, ethyl, n-propyl, propane-2-yl, butane-2-yl, 2,2,2-trifluoroethyl, 2-trifluoromethoxyethyl, cyanomethyl, cyclopropyl, cyclopropylmethyl, or 2-methyl-n-propyl; R.sup.41 and R.sup.42 together with the nitrogen atom to which they are attached, represent pyrrolidine, piperidine, azepane, morpholine, oxazepane, azasilolidine, azasilinane, azasilepane each of which is optionally substituted with 1 or 2 methyl groups; and pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, furanyl, thienyl optionally substituted with 1 substituent selected from —CN, COOH, CONH.sub.2, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, trifluoromethyl, trifluoroethyl, cyanomethyl, methoxy, ethoxy, trifluoromethoxy, R.sup.5 is hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, butyl, tert-butyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, cyclopropyl, cyclobutyl; R.sup.6 is hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, butyl, tert-butyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, cyclopropyl, cyclobutyl; And/or a salt and/or N-oxide thereof.

5. The compound according to claim 1, in which R.sup.1 is hydrogen; R.sup.2 is phenyl, optionally substituted by 2 substituents independently selected from the group consisting of fluorine, chlorine, bromine, —CN, SF.sub.5, cyclopropyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methylsulfonyl; R.sup.3 is methyl; R.sup.4 is selected from the group consisting of ##STR00110## wherein R.sup.81 is selected from the group consisting of methyl, —CH.sub.2—CONHCH.sub.3, methylpyrazolyl, —CH.sub.2—COOCH.sub.2CH.sub.3; wherein R.sup.82 is selected from the group consisting of —CN, methyl, ethyl, the substructure S13, in which the bond to the ring to which R.sup.82 is attached is marked with # and Z is CO; ##STR00111## wherein R.sup.41 is hydrogen, methyl, ethyl, R.sup.42 is hydrogen, methyl, ethyl, R.sup.41 and R.sup.42 together with the nitrogen atom to which they are attached, represent 2,6-dimethylmorpholine, R.sup.5 is hydrogen or methyl; R.sup.6 is hydrogen or methyl; And/or a salt and/or N-oxide thereof.

6. The compound according to claim 1, in which R.sup.2 is selected from the group consisting of phenyl, pyridyl, thiophene, pyrazole; And/or a salt and/or N-oxide thereof.

7. The compound according to claim 1, in which R.sup.2 is phenyl; And/or a salt and/or N-oxide thereof.

8. The compound according to claim 1, comprising a structure selected from the group consisting of formulae (I-i)-(I-vii) ##STR00112## ##STR00113## wherein R.sup.8 has the meaning of the substituents on the 5-membered heterocycle as defined for R.sup.4; And/or a salt and/or N-oxide thereof.

9. The compound according to claim 1, comprising a structure selected from the group consisting of formulae (I-viii)-(I-xxi) ##STR00114## ##STR00115## ##STR00116## ##STR00117## wherein R.sup.7 are the same or different and have the meaning of the substituents on the phenyl or 5- or 6-membered heteroaryl as defined for R.sup.2; n is 1 or 2, And/or a salt and/or N-oxide thereof.

10. A formulation comprising at least one compound of claim 1, and which may further comprise at least one further compound selected from extenders, surface-active substances, auxiliaries, excipients, solvents and/or additional pharmaceutically active agents.

11. A composition comprising the compound of claim 1 or a formulation thereof.

12. A method for treating an endoparasite, and ectoparasite, an arthropod, or an insect, comprising contacting a plant or animal in need thereof a compound according to claim 1 or a formulation thereof.

13. The method according to claim 12, wherein the endoparasite, and ectoparasite, an arthropod, or an insect is an animal pest selected from the group consisting of an insect or arachnid.

14. The method according to claim 13, wherein the ectoparasite, arthropod, or insect is a plant pest and the method comprises contacting a seed or a germinating plant with the compound or a formulation thereof.

15. Seed obtained by a method according to claim 14.

16. An intermediate compound according to formula IX-1, X, XIII or XXII ##STR00118## wherein R.sup.1, R.sup.3, R.sup.4, R.sup.5 and R.sup.6. R.sup.1 is hydrogen; in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.2-C.sub.6haloalkynyl; or phenyl-C.sub.1-C.sub.6alkyl, in which phenyl is optionally substituted with 1 to 5 substituents, each independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —CONH.sub.2, —CSNH.sub.2, —NO.sub.2, —Si(CH.sub.3).sub.3, —SF.sub.5, —NH.sub.2, C.sub.1-C.sub.6alkyl, 03-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycanocycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3cyanoalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.3haloalkoxy, C.sub.1-C.sub.3cyanoalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.1-C.sub.3haloalkylthio, C.sub.1-C.sub.3haloalkylsulfinyl, C.sub.1-C.sub.3haloalkylsulfonyl, C.sub.1-C.sub.3cyanoalkylthio, C.sub.1-C.sub.3cyanoalkylsulfinyl, C.sub.1-C.sub.3-cyanoalkylsulfonyl, or heterocyclyl-C.sub.1-C.sub.6alkyl, wherein the heterocyclyl is selected from the group consisting of saturated and partially unsaturated 3- to 10-membered heterocyclyl, 5-membered heteroaryl, 6-membered heteroaryl, 9-membered heteroaryl and 10-membered heteroaryl and the heterocyclyl is optionally substituted with 1 to 5 substituents, each independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —CONH.sub.2, —CSNH.sub.2, —NO.sub.2, —Si(CH.sub.3).sub.3, —SF.sub.5, —NH.sub.2, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycanocycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3cyanoalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.3haloalkoxy, C.sub.1-C.sub.3cyanoalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.1-C.sub.3haloalkylthio, C.sub.1-C.sub.3haloalkylsulfinyl, C.sub.1-C.sub.3haloalkylsulfonyl, C.sub.1-C.sub.3cyanoalkylthio, C.sub.1-C.sub.3cyanoalkylsulfinyl, C.sub.1-C.sub.3cyanoalkylsulfonyl R.sup.2 is phenyl or a 5- or 6-membered heteroaryl, each of which is optionally substituted with 1, 2 or 3 substituents independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —NO.sub.2, —NH.sub.2, —SF.sub.5; and in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkoxy, C.sub.1-C.sub.6haloalkoxy, hydroxy-C.sub.1-C.sub.6alkyl, —CO.sub.2C.sub.1-C.sub.6alkyl, —NH(C.sub.1-C.sub.6alkyl), —N(C.sub.1-C.sub.6alkyl).sub.2, S—C.sub.1-C.sub.6alkylsulfinimidoyl, S—C.sub.3-C.sub.6cycloalkylsulfinimidoyl, S—C.sub.2-C.sub.6alkenylsulfinimidoyl, S—C.sub.2-C.sub.6alkinylsulfinimidoyl, S-phenylsulfinimidoyl, S-heterocyclylsulfinimidoyl, S-heteroarylsulfinimidoyl, S—C.sub.1-C.sub.6alkylsulfonimidoyl, S—C.sub.3-C.sub.6cycloalkylsulfonimidoyl, S—C.sub.2-C.sub.6alkenylsulfonimidoyl, S—C.sub.2-C.sub.6alkinylsulfonimidoyl, S-phenylsulfonimidoyl, S-heterocyclylsulfonimidoyl, S-heteroarylsulfonimidoyl, —C(═NOC.sub.1—C.sub.6alkyl)H, —C(═NOC.sub.1—C.sub.6alkyl)-C.sub.1-C.sub.6alkyl, (C.sub.1-C.sub.6alkyl).sub.3-silyl; and the substructures S1-S9, in which the bond to the phenyl or 5- or 6-membered heteroaryl is marked with a # and Z is CO or CS and Y is independently selected from CO or SO.sub.2; ##STR00119## R.sup.21 is hydrogen or in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, —C.sub.1-C.sub.6alkyl-C.sub.3-C.sub.6cycloalkyl, phenyl, heteroaryl and heterocyclyl; R.sup.22 is hydrogen or in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, —C.sub.1-C.sub.6alkyl-C.sub.3-C.sub.6cycloalkyl and C.sub.3-C.sub.6cycloalkyl; R.sup.23 is independently selected from in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl and phenyl; R.sup.24 is in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, phenyl, heteroaryl and heterocyclyl; or R.sup.21 and R.sup.22 together with the nitrogen atom to which they are attached, represent a monocyclic or polycyclic optionally substituted 3- to 12-membered saturated or unsaturated heterocyclyl which may contain further heteroatoms; and 3- to 6-membered heterocyclyl or a 5- to 6-membered heteroaryl each containing 1 or 2 heteroatoms selected from the group consisting of N, O, and S, wherein the 3- to 6-membered heterocyclyl or the 5- to 6-membered heteroaryl substituent may optionally carry 1, 2, 3 or 4 substituents independently selected from the group consisting of halogen, hydroxy, CN, —COOH, —CONH.sub.2, —CSNH.sub.2, —NO.sub.2, —Si(CH.sub.3).sub.3, SF.sub.5, —NH.sub.2, C.sub.1-C.sub.6alkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycanocycloalkyl, 03-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3cyanoalkyl, C.sub.3-C.sub.6cyanocycloalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.3haloalkoxy, C.sub.1-C.sub.3cyanoalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.1-C.sub.3haloalkylthio, C.sub.1-C.sub.3haloalkylsulfinyl, C.sub.1-C.sub.3haloalkylsulfonyl, C.sub.1-C.sub.3cyanoalkylthio, C.sub.1-C.sub.3cyanoalkylsulfinyl, C.sub.1-C.sub.3cyanoalkylsulfonyl; R.sup.3 is hydrogen or C.sub.1-C.sub.6alkyl optionally substituted with 1 to 3 substituents selected from halogen, C.sub.3-C.sub.6-cycloalkyl and C.sub.1-C.sub.6-alkoxy; R.sup.4 is a monocyclic 5-membered heteroaryl, containing 3 or 4 heteroatoms selected from the group consisting of N, O, and S, and optionally substituted by 1 or 2 substituents independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —NO.sub.2, —NH.sub.2, —SF.sub.5; and in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6alkyl-C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkoxy, C.sub.1-C.sub.6haloalkoxy, hydroxy-C.sub.1-C.sub.6alkyl, —NH(C.sub.1-C.sub.6alkyl), —NH(C.sub.1-C.sub.6alkyl-C.sub.3-C.sub.6cycloalkyl), —N(C.sub.1-C.sub.6alkyl).sub.2, —N(C.sub.1-C.sub.6alkyl)(C.sub.1-C.sub.6alkyl-C.sub.3-C.sub.6cycloalkyl), —CO.sub.2C.sub.1-C.sub.6alkyl, S—C.sub.1-C.sub.6alkylsulfinimidoyl, S—C.sub.3-C.sub.6cycloalkylsulfinimidoyl, S—C.sub.2-C.sub.6alkenylsulfinimidoyl, S—C.sub.2-C.sub.6alkinylsulfinimidoyl, S-phenylsulfinimidoyl, S-heterocyclylsulfinimidoyl, S-heteroarylsulfinimidoyl, S—C.sub.1-C.sub.6alkylsulfonimidoyl, S—C.sub.3-C.sub.6cycloalkylsulfonimidoyl, S-C.sub.2-C.sub.6alkenylsulfonimidoyl, S—C.sub.2-C.sub.6alkinylsulfonimidoyl, S-phenylsulfonimidoyl, S-heterocyclylsulfonimidoyl, S-heteroarylsulfonimidoyl, —C(═NOC.sub.1—C.sub.6alkyl)H, —C(═NOC.sub.1—C.sub.6alkyl)-C.sub.1-C.sub.6alkyl; and 3- to 6-membered heterocyclyl containing 1 or 2 heteroatoms selected from the group consisting of N, O, and S, wherein the 3- to 6-membered heterocyclyl substituent may optionally carry 1, 2, 3 or 4 substituents independently selected from the group consisting of halogen, hydroxy, —CN, —COOH, —CONH.sub.2, —CSNH.sub.2, —NO.sub.2, —Si(CH.sub.3).sub.3, —SF.sub.5, —NH.sub.2, C.sub.1-C.sub.6alkyl, 03-C.sub.6cycloalkyl, C.sub.3-C.sub.6cycanocycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkyl-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.3haloalkyl, C.sub.1-C.sub.3cyanoalkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.3haloalkoxy, C.sub.1-C.sub.3cyanoalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.1-C.sub.3haloalkylthio, C.sub.1-C.sub.3haloalkylsulfinyl, C.sub.1-C.sub.3haloalkylsulfonyl, C.sub.1-C.sub.3cyanoalkylthio, C.sub.1-C.sub.3cyanoalkylsulfinyl, C.sub.1-C.sub.3cyanoalkylsulfonyl; and the following substructures S10-S18, in which the bond to the monocyclic 5-membered heteroaryl is marked with a # and Z is CO or CS and Y is independently selected from CO or SO.sub.2: ##STR00120## R.sup.41 is hydrogen or in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, —C.sub.1-C.sub.6alkyl-C.sub.3-C.sub.6cycloalkyl, phenyl, heteroaryl and heterocyclyl; R.sup.42 is hydrogen or in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl and C.sub.3-C.sub.6cycloalkyl; R.sup.43 is independently selected from in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl and phenyl; R.sup.44 is in each case optionally substituted C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, phenyl, heteroaryl and heterocyclyl; or R.sup.41 and R.sup.42 together with the nitrogen atom to which they are attached, represent a monocyclic or polycyclic optionally substituted 3- to 12-membered saturated or unsaturated heterocyclyl which may contain further heteroatoms; R.sup.5 is hydrogen, halogen, —CN, —NH.sub.2, or in each case optionally substituted C.sub.1-C.sub.3-alkyl, C.sub.3-C.sub.4-cycloalkyl, C.sub.1-C.sub.3alkoxy, —CO.sub.2(C.sub.1-C.sub.3alkyl), —CH—(C.sub.1-C.sub.3alkoxy).sub.2, —CONH(C.sub.1-C.sub.4alkyl), —CON(C.sub.1-C.sub.4alkyl).sub.2, —NHCO—C.sub.1-C.sub.4alkyl, —N(C.sub.1-C.sub.4alkyl)CO—C.sub.1-C.sub.4alkyl, —C(═NOC.sub.1—C.sub.4alkyl)H, or —C(═NOC.sub.1—C.sub.4alkyl)-C.sub.1-C.sub.4alkyl, —NH(C.sub.1-C.sub.3alkyl), —N(C.sub.1-C.sub.3alkyl).sub.2, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.3-C.sub.6cycloalkylthio, C.sub.3-C.sub.6cycloalkylsulfinyl, C.sub.3-C.sub.6cycloalkylsulfonyl; R.sup.6 is hydrogen, halogen, —CN, —NH.sub.2, or in each case optionally substituted C.sub.1-C.sub.3-alkyl, C.sub.3-C.sub.4cycloalkyl, C.sub.1-C.sub.3alkoxy, —CO.sub.2(C.sub.1-C.sub.3alkyl), —CH—(C.sub.1-C.sub.3alkoxy).sub.2, —CONH(C.sub.1-C.sub.4alkyl), —CON(C.sub.1-C.sub.4alkyl).sub.2, —NHCO—C.sub.1-C.sub.4alkyl, —N(C.sub.1-C.sub.4alkyl)CO—C.sub.1-C.sub.4alkyl, —C(═NOC.sub.1—C.sub.4alkyl)H, or —C(═NOC.sub.1—C.sub.4alkyl)-C.sub.1-C.sub.4alkyl, —NH(C.sub.1-C.sub.3alkyl), —N(C.sub.1-C.sub.3alkyl).sub.2, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, C.sub.3-C.sub.6cycloalkylthio, C.sub.3-C.sub.6cycloalkylsulfinyl, C.sub.3-C.sub.6cycloalkylsulfonyl.

Description

PREPARATION EXAMPLES

Analytical Methods

Method 1 (LC-MS)

[0583] Instrument: Agilent MS Quad 6150; HPLC: Agilent 1290; column: Waters Acquity UPLC HSS T3 1.8 μm 50×2.1 mm; Eluent A: 1 L water+0.25 mL 99% formic acid, Eluent B: 1 L acetonitrile+0.25 mL 99% formic acid; gradient: 0.0 min 90% A.fwdarw.0.3 min 90% A.fwdarw.1.7 min 5% A.fwdarw.3.0 min 5% A oven temp: 50° C.; flow: 1.20 mL/min; UV-detection: 205-305 nm.

Method 2 (LC-MS)

[0584] Instrument MS: Thermo Scientific FT-MS; instrument for UHPLC+: Thermo Scientific UltiMate 3000; column: Waters, HSST3, 2.1×75 mm, C18 1.8 μm; eluent A: 1 L water+0.01% formic acid; eluent B: 1 L acetonitrile+0.01% formic acid; gradient: 0.0 min 10% B.fwdarw.2.5 min 95% B.fwdarw.3.5 min 95% B; oven temp: 50° C.; flow: 0.90 mL/min; UV-Detektion: 210 nm/Optimum Integration Path 210-300 nm

Method 3 (LC-MS)

[0585] Instrument: Waters Single Quad MS System; Instrument Waters UPLC Acquity; column: Waters BEH C18 1.7μ 50×2.1 mm; Eluent A: 1 L water+1.0 mL 25% ammonia, Eluent B: 1 L acetonitrile; gradient: 0.0 min 92% A.fwdarw.0.1 min 92% A.fwdarw.1.8 min 5% A.fwdarw.3.5 min 5% A; oven temp.: 50° C.; flow: 0.45 mL/min; UV-detection: 210 nm.

Method 4 (HPLC-MS)

[0586] System MS: Waters TOF instrument; System UPLC: Waters Acquity I-CLASS; Column: Waters Acquity UPLC HSS T3 1.8 μm 50×1 mm; Eluent A: 1 1 Water+0.100 ml 99% ige Formic acid, Eluent B: 1 1 Acetonitrile+0.100 ml 99% ige Formic acid; Gradient: 0.0 min 90% A.fwdarw.1.2 min 5% A.fwdarw.2.0 min 5% A Oven: 50° C.; Flow: 0.40 ml/min; UV-Detection: 210 nm.

Method 5 (HPLC-MS)

[0587] System MS: Waters TOF instrument; System UPLC: Waters Acquity I-CLASS; Column: Waters Acquity UPLC HSS T3 1.8 μm 50×1 mm; Eluent A: 1 1 Water+0.100 ml 99% ige Formic acid, Eluent B: 1 1 Acetonitrile+0.100 ml 99% ige Formic acid; Gradient: 0.0 min 95% A.fwdarw.6.0 min 5% A.fwdarw.7.5 min 5% A Oven: 50° C.; Flow: 0.35 ml/min; UV-Detection: 210 nm.

Method 6 (HPLC-MS)

[0588] Instrument: Waters ACQUITY SQD UPLC System; Column: Waters Acquity UPLC HSS T3 1.8 μm 50×1 mm; Eluent A: 1 1 Water+0.25 ml 99% ige Formic acid, Eluent B: 1 1 Acetonitrile+0.25 ml 99% ige Formic acid; Gradient: 0.0 min 90% A.fwdarw.1.2 min 5% A.fwdarw.2.0 min 5% A Oven: 50° C.; Flow: 0.40 ml/min; UV-Detection: 210 nm.

Method 7 (HPLC-MS)

[0589] Column: Waters CORTECS C18+, 2.7 um 4.6*30 mm, Eluent A: water+0.05% formic acid, Eluent B: acetonitrile with 0.05% formic acid, Gradient: 0.0 min 95% A.fwdarw.4.0 min 5% A.fwdarw.7.0 min 5% A. Oven: 45° C.; Flow: 1.8 mL/min; UV-Detection: 254 and 214 nm.

General Synthetic Methods

General Synthetic Method 1

Mitsunobu Reaction

[0590] A substituted (pyrazin-2-yl)ethan-1-ol (1 equivalent) was dissolved in THF (ca 3.0 mL/mmol), 1H-isoindole-1,3(2H)-dione (1.50 equivalents) and triphenylphosphine (1.50 equivalents) were added. Optionally, polymer bound triphenylphosphine (3 mmol/g loading, 1.5 equivalents) was used. The mixture was cooled to 0° C., then DIAD (1.50 equivalents) was slowly added and the mixture was left stirring until complete conversion was observed by TLC or HPLC analysis. The solvent was then distilled and the crude product was purified by preparative HPLC (RP C-18, water acetonitrile gradient with 0.1% TFA) or by flash chromatography (silica gel, cyclohexane-ethyl acetate gradient) to give the title compound.

General Synthetic Method 2

Hydrazinolysis of Phthalimide Group

[0591] A phthalimide protected amine (1 equivalent) was dissolved in ethanol (ca 10 mL/mmol) and hydrazine hydrate (80% in water, 5 equivalents) was added. The mixture was heated to reflux until conversion was complete by HPLC or TLC, then poured into water and extracted with 3 portions of dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate and evaporated. Optionally, the crude product was purified by flash chromatography (silica gel, cyclohexane-ethyl acetate gradient) to give the pure title compound.

General Synthetic Method 3

Amide Coupling

[0592] An amine (1.0 equivalents), a carboxylic acid (1.0-1.5 equivalents) and DIPEA (3.0 equivalents) were dissolved in DMF or THF (ca 0.17 mmol amine per mL of solvent). The solution was cooled on an ice-water bath to 0° C. and HATU (1.5-2.5 equivalents) was added. The cooling bath was removed and mixture was stirred until complete conversion was detected by TLC or HPLC. Then water was added. In case the product readily precipitated, it was collected on a filter funnel and dried under vacuum. If precipitation did not occur, the mixture was extracted with three portions of ethyl acetate, the combined organic extracts were dried over anhydrous sodium sulfate and evaporated. Crude products from either procedure were purified by preparative HPLC (RP-C18, water-acetonitril gradient with 0.1% TFA) or by flash chromatography (silica gel, cyclohexane-ethyl acetate gradient) if this seemed appropriate.

General Synthetic Method 4

Copper Catalysed Coupling of Azoles

[0593] (rac)-1-(3-Bromopyrazin-2-yl)ethan-1-ol (intermediate 1A, 1 equivalent) was dissolved in toluene (3.0 mL/1.0 mmol of bromopyrazine), an azole (1.5 equivalents), potassium carbonate (2.5 equivalents), copper(I) iodide (0.3 equivalents) and trans-N,N,N′,N′-tetramethylcyclohexane-1,2-diamine (0.3 equivalents) were added. The mixture was heated to reflux over night and then poured into water. It was extracted with three portions of ethyl acetate, the combined organic extracts were washed twice with 20% aqueous ammonia, once with water and eventually once with brine. The organic phase was dried over anhydrous sodium sulfate, evaporated and the residue was purified on silica gel with a gradient of cyclohexane-ethyl acetate. Optionally, the crude product was once more purified by preparative HPLC (RP-C18 column with a water-acetonitrile gradient with 0.1% TFA) to give the title compound.

General Synthetic Method 5

Cleavage of TBDMS Group

[0594] A TBDMS ether (1.0 equivalents) was dissolved in hydrogen chloride (4.0 M solution in 1,4-dioxane, ca 4 mL per mmol of substrate) and the mixture was stirred at room temperature until complete conversion was observed by TLC or HPLC. Volatile components were evaporated and the crude product was purified by preparative HPLC (RP-C18, water-acetonitril gradient with 0.1% TFA) or by flash chromatography (silica gel, cyclohexane-ethyl acetate gradient) if this seemed appropriate.

Intermediate 1A

(rac)-1-(3-Bromopyrazin-2-yl)ethan-1-ol

[0595] ##STR00036##

[0596] A solution of 2,2,6,6-tetramethylpiperidine (21 mL, 120 mmol) in THF (260 mL) was cooled to −78° C. A solution of n-butyllithium (2.5 M in hexanes, 48 mL, 120 mmol) was slowly added and stirring was maintained for 30 min at −78° C. Then, 2-bromopyrazine (8.5 mL, 94 mmol) was added dropwise keeping the temperature at −70° C. Stirring was continued at −78° C. for one hour. Acetaldehyde (11 mL, 190 mmol) was added dropwise, the cooling bath was removed and the mixture was allowed to slowly warm to room temperature. The reaction mixture was poured into water (500 mL), acidified with 1 M hydrochloric acid and extracted with 6 portions of ethyl acetate. The combined organic extracts were dried over anhydrous sodium sulfate, the solvent was carefully distilled (40° C. bath temperature, 140 mbar) on the rotatory evaporator and eventually purified by flash chromatography on silica gel with a gradient of cyclohexane-ethyl acetate to yield 12.6 g (61% of theory) of the title compound.

[0597] LC-MS (Method 2): R.sub.t=0.81 min; MS (ESIpos): m/z=203 [M+H].sup.+

[0598] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.164 (2.79), 1.176 (5.67), 1.187 (2.84), 1.407 (15.63), 1.418 (16.00), 1.907 (0.49), 1.987 (10.52), 4.013 (0.83), 4.025 (2.50), 4.037 (2.49), 4.049 (0.82), 5.076 (0.53), 5.087 (2.14), 5.097 (3.28), 5.108 (2.23), 5.119 (0.58), 5.353 (5.76), 5.363 (5.33), 5.744 (1.31), 8.400 (4.78), 8.404 (4.96), 8.670 (4.87), 8.674 (4.75).

Intermediate 2A

(rac)-2-[1-(3-Bromopyrazin-2-yl)ethyl]-1H-isoindole-1,3(2H)-dione

[0599] ##STR00037##

[0600] According to General synthetic method 1, 12.8 g (98% purity, 77% yield) was obtained from (rac)-1-(3-bromopyrazin-2-yl)ethan-1-ol (intermediate 22A, 10.0 g, 49.3 mmol).

[0601] LC-MS (Method 2): R.sub.t=1.75 min; MS (ESIpos): m/z=332 [M+H].sup.+

[0602] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.179 (0.88), 1.189 (0.84), 1.786 (5.16), 1.798 (5.17), 5.655 (1.17), 5.667 (1.14), 7.867 (16.00), 8.452 (1.85), 8.457 (1.83), 8.708 (2.09), 8.712 (1.94).

Intermediate 3A

(rac)-1-[3-(3-Methyl-1H-1,2,4-triazol-1-yl)pyrazin-2-yl]ethan-1-ol

[0603] ##STR00038##

[0604] (rac)-1-(3-Bromopyrazin-2-yl)ethan-1-ol (intermediate 1A, 2.00 g, 9.85 mmol) was dissolved in toluene (20.0 mL). 5-Methyl-1H-1,2,4-triazole (1.23 g, 14.8 mmol), potassium carbonate (3.40 g, 24.6 mmol) and copper (I) iodide (563 mg, 2.96 mmol) and trans-N,N,N′,N′-tetramethylcyclohexane-1,2-diamine (470 μl, 3.0 mmol) were added. The mixture was heated to reflux over night. Then the solvent was evaporated, the residue was washed with ethyl acetate three times under stirring and then filtered. The combined organic extracts were evaporated and the residue was purified by flash chromatography on silica gel (gradient of cyclohexane-ethyl acetate 2:1—pure ethyl acetate) to give 979 mg (100% purity, 48% yield) of the title compound.

[0605] LC-MS (Method 2): R.sub.t=0.73 min; MS (ESIpos): m/z=206 [M+H].sup.+

[0606] .sup.1H-NMR (400 MHz, DMSO-d6) δ[ppm]: 1.427 (6.11), 1.434 (3.30), 1.442 (6.34), 2.403 (16.00), 5.221 (1.21), 5.227 (1.80), 5.236 (5.02), 5.250 (1.88), 5.265 (1.03), 8.590 (3.08), 8.596 (3.37), 8.824 (3.12), 8.830 (3.17), 9.041 (4.16).

Intermediate 4A

(rac)-2-{1-[3-(3-Methyl-1H-1,2,4-triazol-1-yl)pyrazin-2-yl]ethyl}-1H-isoindole-1,3(2H)-dione

[0607] ##STR00039##

[0608] According to General synthetic method 1, 1.18 g (100% purity, 73% yield) of the title compound was obtained from (rac)-1-[3-(3-methyl-1H-1,2,4-triazol-1-yl)pyrazin-2-yl]ethan-1-ol (intermediate 3A, 985 mg, 4.80 mmol)

[0609] LC-MS (Method 2): R.sub.t=1.43 min; MS (ESIpos): m/z=335 [M+H].sup.+

[0610] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.706 (7.57), 1.717 (7.47), 2.157 (16.00), 6.060 (0.60), 6.072 (1.84), 6.084 (1.82), 6.095 (0.57), 7.782 (2.06), 7.787 (2.70), 7.791 (3.00), 7.796 (4.39), 7.803 (1.28), 7.809 (1.34), 7.816 (4.51), 7.820 (3.08), 7.825 (2.78), 7.830 (2.03), 8.633 (2.91), 8.637 (3.08), 8.829 (3.21), 8.833 (3.08), 8.935 (4.52).

Intermediate 5A

(rac)-1-[3-(3-Methyl-1H-1,2,4-triazol-1-yl)pyrazin-2-yl]ethan-1-amine

[0611] ##STR00040##

[0612] According to General synthetic method 2, 363 mg (100% purity, 99% yield) of the title compound was obtained from 2-{(rac)-1-[3-(3-methyl-1H-1,2,4-triazol-1-yl)pyrazin-2-yl]ethyl}-1H-isoindole-1,3(2H)-dione (intermediate 4A, 600 mg, 1.79 mmol).

[0613] LC-MS (Method 3): R.sub.t=0.84 min; MS (ESIpos): m/z=205 [M+H].sup.+

[0614] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.309 (7.83), 1.319 (7.80), 2.404 (16.00), 4.410 (0.58), 4.421 (1.79), 4.432 (1.77), 4.443 (0.55), 8.529 (2.69), 8.533 (2.79), 8.797 (2.69), 8.801 (2.62), 9.023 (3.91).

Intermediate 6A

(rac)-1-[3-(1H-1,2,4-Triazol-1-yl)pyrazin-2-yl]ethan-1-ol

[0615] ##STR00041##

[0616] (rac)-1-(3-Bromopyrazin-2-yl)ethan-1-ol (intermediate 1A, 2.00 g, 9.85 mmol) was dissolved in toluene (20.0 mL). 1H-1,2,4-triazole (1.02 g, 14.8 mmol), potassium carbonate (3.40 g, 24.6 mmol) and copper (I) iodide (563 mg, 2.96 mmol) and trans-N,N,N′,N′-tetramethylcyclohexane-1,2-diamine (470 μl, 3.0 mmol) were added. The mixture was heated to reflux for 6 h. As conversion was not complete at this point, two more portions of 1H-1,2,4-triazole (340 mg, 4.93 mmol) potassium carbonate (1.36 g, 9.85 mmol) and copper (I) iodide (188 mg, 985 μmol) and trans-N,N,N′,N′-tetramethylcyclohexane-1,2-diamine (160 μl, 990 μmol) were added. After each addition, the mixture was again heated to reflux over night. Then the solvent was evaporated, the residue was washed with ethyl acetate three times under stirring and then filtered. The combined organic extracts were evaporated and the residue was purified by flash chromatography on silica gel (gradient of cyclohexane-ethyl acetate 2:1—pure ethyl acetate) to give 590 mg (100% purity, 31% yield) of the title compound.

[0617] LC-MS (Method 2): R.sub.t=0.60 min; MS (ESIpos): m/z=192 [M+H].sup.+

[0618] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.161 (0.52), 1.173 (1.04), 1.185 (0.52), 1.403 (1.99), 1.414 (2.08), 1.433 (16.00), 1.443 (15.83), 1.985 (2.04), 4.023 (0.49), 4.036 (0.49), 5.165 (0.52), 5.176 (2.20), 5.186 (3.80), 5.196 (3.22), 5.207 (8.27), 5.217 (3.27), 5.534 (0.65), 5.542 (0.62), 8.354 (8.74), 8.519 (0.55), 8.619 (5.65), 8.623 (5.95), 8.753 (0.54), 8.756 (0.55), 8.862 (5.71), 8.866 (5.71), 9.183 (9.16).

Intermediate 7A

(rac)-2-{1-[3-(1H-1,2,4-Triazol-1-yl)pyrazin-2-yl]ethyl}-1H-isoindole-1,3(2H)-dione

[0619] ##STR00042##

[0620] According to General synthetic method 1, 872 mg (100% purity, 89% yield) of the title compound was obtained from (rac)-1-[3-(1H-1,2,4-triazol-1-yl)pyrazin-2-yl]ethan-1-ol (intermediate 6A, 585 mg, 3.06 mmol).

[0621] LC-MS (Method 2): R.sub.t=1.39 min; MS (ESIpos): m/z=321 [M+H].sup.+

[0622] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.696 (15.97), 1.708 (16.00), 6.125 (1.22), 6.137 (3.91), 6.149 (3.88), 6.160 (1.21), 7.790 (3.71), 7.796 (5.41), 7.798 (5.91), 7.804 (8.94), 7.810 (2.41), 7.815 (2.53), 7.822 (9.09), 7.827 (5.97), 7.830 (5.58), 7.836 (3.72), 8.233 (9.65), 8.662 (6.00), 8.666 (6.45), 8.831 (6.43), 8.835 (6.16), 9.165 (9.75).

Intermediate 8A

(rac)-1-[3-(1H-1,2,4-Triazol-1-yl)pyrazin-2-yl]ethan-1-amine

[0623] ##STR00043##

[0624] According to General synthetic method 2, 226 mg (100% purity, 98% yield) of the title compound was obtained from 2-{(rac)-1-[3-(1H-1,2,4-triazol-1-yl)pyrazin-2-yl]ethyl}-1H-isoindole-1,3(2H)-dione (390 mg, 1.22 mmol).

[0625] LC-MS (Method 3): R.sub.t=0.76 min; MS (ESIpos): m/z=191 [M+H].sup.+

Intermediate 9A

(rac)-2-{1-[3-(1-Methyl-1H-1,2,3-triazol-4-yl)pyrazin-2-yl]ethyl}-1H-isoindole-1,3(2H)-dione

[0626] ##STR00044##

[0627] Solution A: In a flame-dried 25 mL three-necked round bottom flask, 4-bromo-1-methyl-1H-1,2,3-triazole (1.50 g, 9.26 mmol) is dissolved in THF (2.0 mL). The solution is cooled to −30° C. and isopropylmagnesium chloride×lithium chloride (8.5 mL, 1.3 M in THF, 11 mmol) was slowly added. Stirring was continued for 5 min, then a solution of zinc dichloride (5.80 mL, 1.9 M in methyl-THF, 11 mmol) was added at such a rate that the temperature did not exceed −20° C. This solution was used for the cross coupling reaction.

[0628] 2-[(rac)-1-(3-Bromopyrazin-2-yl)ethyl]-1H-isoindole-1,3(2H)-dione (intermediate 2A, 1.20 g, 3.61 mmol) and solution A were mixed in an argon-flushed microwave reactor vial. 1,1-Bis(diphenylphosphino)-ferrocenedichloropalladium(II) (295 mg, 361 μmol) was added, the vial was crimp-capped and heated to 110° C. for 2.5 h. After cooling, the mixture was directly loaded upon a silica gel column and flash-chromatographed using a gradient of ethyl acetate and 0-20% methanol. Eventually, the material was purified using preparative HPLC (RP-C18, water-acetonitrile gradient with 0.1% TFA) to give 335 mg (100% purity, 28% yield) of the title compound.

[0629] LC-MS (Method 2): R.sub.t=1.34 min; MS (ESIpos): m/z=335 [M+H].sup.+

[0630] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.862 (7.69), 1.874 (7.72), 2.072 (0.80), 2.574 (0.77), 2.577 (0.80), 3.350 (2.85), 4.116 (8.24), 4.118 (16.00), 6.543 (0.58), 6.555 (1.83), 6.567 (1.80), 6.579 (0.54), 7.830 (11.98), 7.832 (14.48), 7.838 (1.08), 8.516 (3.32), 8.520 (3.06), 8.611 (3.31), 8.615 (2.68), 8.660 (5.04).

Intermediate 10A

(rac)-1-[3-(1-Methyl-1H-1,2,3-triazol-4-yl)pyrazin-2-yl]ethan-1-amine

[0631] ##STR00045##

[0632] 2-{(rac)-1-[3-(1-Methyl-1H-1,2,3-triazol-4-yl)pyrazin-2-yl]ethyl}-1H-isoindole-1,3(2H)-dione (intermediate 9A, 400 mg, 1.20 mmol) was suspended in ethanol (14.0 mL). hydrazine hydrate (360 μl, 80% aqueous solution, 6.0 mmol) was added and the mixture was heated to reflux for 10 min. The solvent was distilled. The residue was taken up into ethyl acetate and filtered. The filtrate was evaporated to give 265 mg (98% purity, 106% yield) of the title compound.

[0633] LC-MS (Method 3): R.sub.t=0.82 min; MS (ESIpos): m/z=205 [M+H].sup.+

[0634] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.341 (7.89), 1.352 (7.97), 1.987 (0.61), 4.149 (16.00), 4.180 (0.57), 5.006 (0.58), 5.017 (1.82), 5.028 (1.83), 5.039 (0.63), 8.561 (2.58), 8.565 (3.17), 8.601 (3.17), 8.605 (2.91), 8.613 (5.13).

Intermediate 11A

(rac)-1-{3-[(Trimethylsilyl)ethynyl]pyrazin-2-yl}ethan-1-ol

[0635] ##STR00046##

[0636] (rac)-1-(3-Bromopyrazin-2-yl)ethan-1-ol (intermediate 1A, 1.00 g, 4.93 mmol), copper(I) iodide (46.9 mg, 246 μmol) and triethylamine (2.4 mL, 17 mmol) were dissolved in THF (10.0 mL) in a microwave reactor vial. Argon was bubbled through the solution for 10 min. Then ethynyl(trimethyl)silane (1.7 mL, 12 mmol) and Bis(triphenylphosphin)palladium(II)chloride (69.1 mg, 98.5 μmol) were added, the vial was crimp-capped and heated to 70° C. for 6 h in a single mode microwave device. The mixture was diluted with water and ethyl acetate and filtered over diatomaceous earth. The layers were separated, the aqueous phase was extracted twice with ethyl acetate. The combined organic extracts were evaporated and purified by chromatography on silica gel with a gradient of cyclohexane-ethyl acetate to give 766 mg (100% purity, 71% yield) of the title compound.

[0637] LC-MS (Method 2): R.sub.t=1.67 min; MS (ESIpos): m/z=221 [M+H].sup.+

[0638] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 0.252 (1.09), 0.280 (16.00), 0.284 (1.53), 1.396 (2.50), 1.406 (2.46), 5.195 (0.55), 5.227 (1.14), 5.237 (0.64), 8.531 (0.85), 8.535 (1.00), 8.610 (0.89), 8.615 (0.88).

Intermediate 12A

(rac)-1-(3-Ethynylpyrazin-2-yl)ethan-1-ol

[0639] ##STR00047##

[0640] (rac)-1-{3-[(Trimethylsilyl)ethynyl]pyrazin-2-yl}ethan-1-ol (intermediate 11A, 680 mg, 3.09 mmol) was dissolved in THF (15.0 mL). Potassium carbonate (4.26 g, 30.9 mmol) and methanol (5.0 mL) were added and the mixture was stirred at room temperature for 1 h. Then it was filtered, the filter cake was washed with ethyl acetate, the combined filtrates were washed with conc ammonium chloride and with brine and were evaporated. The crude product was chromatographed (silica gel, cyclohexane/ethyl acetate gradient) to give 280 mg (100% purity, 61% yield) of the title compound.

[0641] LC-MS (Method 2): R.sub.t=0.63 min; MS (ESIpos): m/z=149 [M+H].sup.+

[0642] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.176 (0.49), 1.402 (16.00), 1.412 (15.92), 1.988 (0.93), 4.754 (9.38), 5.181 (0.58), 5.192 (2.29), 5.202 (3.59), 5.213 (2.58), 5.223 (0.71), 5.269 (6.23), 5.279 (4.71), 8.553 (4.87), 8.557 (5.78), 8.634 (5.35), 8.638 (5.13).

Intermediate 13A

(rac)-2-[1-(3-Ethynylpyrazin-2-yl)ethyl]-1H-isoindole-1,3(2H)-dione

[0643] ##STR00048##

[0644] (rac)-1-(3-Ethynylpyrazin-2-yl)ethan-1-ol (intermediate 12A, 280 mg, 1.89 mmol) was dissolved in THF (5.0 mL). 1H-Isoindole-1,3(2H)-dione (417 mg, 2.83 mmol) and triphenylphosphine (743 mg, 2.83 mmol) were added, the mixture was cooled to 0° C. and DIAD (2.8 ml, 1.0 M, 2.8 mmol) was slowly added. The mixture was stirred for 1 h, then it was poured into water, extracted with three portions of ethyl acetate. The combined organic extracts were evaporated and the crude products was purified by chromatography on silica gel (cyclohexane-ethyl acetate gradient) and eventually by preparative HPLC (RP-C18, water-acetonitrile gradient with 0.1% TFA). 415 mg (100% purity, 79% yield) of the title compound were obtained.

[0645] LC-MS (Method 2): R.sub.t=1.51 min; MS (ESIpos): m/z=278 [M+H].sup.+

[0646] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.796 (6.82), 1.808 (6.73), 4.722 (4.87), 5.736 (0.47), 5.749 (1.51), 5.760 (1.49), 5.772 (0.43), 7.862 (16.00), 8.593 (2.30), 8.597 (2.67), 8.643 (2.78), 8.648 (2.42).

Intermediate 14A

(rac)-2-[1-{3-[1-(1-Methyl-1-pyrazol-3-yl)-1H-1,2,3-triazol-4-yl]pyrazin-2-yl}ethyl]-1H-isoindole-1,3(2H)-dione

[0647] ##STR00049##

[0648] 2-[(rac)-1-(3-Ethynylpyrazin-2-yl)ethyl]-1H-isoindole-1,3(2H)-dione (intermediate 13A, 135 mg, 487 μmol) was dissolved in a mixture of tert-butanol and water (1:1, 3.0 mL), (1 3-azido-1-methyl-1H-pyrazole (60.0 mg, 487 μmol) was added followed by sodium L(+) ascorbate (1.0 M in water, 24 μL, 24 μmol) and copper(II) sulfate pentahydrate (1.0 M in water, 24 μL, 24 μmol). The mixture was stirred at room temperature over night. Then, ice-water was added, the precipitate was collected by suction and washed with water and ethyl acetate. The product was dried under vacuum, 177 mg (98% purity, 89% yield) of the title compound were obtained.

[0649] LC-MS (Method 2): R.sub.t=1.59 min; MS (ESIpos): m/z=401 [M+H].sup.+

[0650] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.111 (1.41), 1.873 (7.64), 1.885 (7.64), 3.934 (16.00), 6.493 (0.67), 6.504 (1.96), 6.516 (1.96), 6.528 (0.67), 6.732 (3.59), 7.815 (14.33), 7.933 (3.61), 8.603 (3.46), 8.671 (2.86), 8.981 (4.93).

Intermediate 15A

(rac)-2-(4-{3-[1-(1,3-Dioxo-1,3-dihydro-2H-isoindol-2-yl)ethyl]pyrazin-2-yl}-1H-1,2,3-triazol-1-yl)-N-methylacetamide

[0651] ##STR00050##

[0652] 2-[(rac)-1-(3-Ethynylpyrazin-2-yl)ethyl]-1H-isoindole-1,3(2H)-dione (intermediate 13A, 146 mg, 526 μmol) was dissolved in a mixture of tert-butanol and water (1:1, 3.0 mL). 2-Azido-N-methylacetamide (60.0 mg, 526 μmol) was added followed by sodium L(+) ascorbate (1.0 M in water, 26 μL, 26 μmol) and copper(II) sulfate pentahydrate (1.0 M in water, 26 μl, 24 μmol). The mixture was stirred at room temperature over night. Then, ice-water was added, the precipitate was collected by suction and washed with water and ethyl acetate. The product was dried under vacuum, 190 mg (100% purity, 92% yield) of the title compound were obtained.

[0653] LC-MS (Method 2): R.sub.t=1.19 min; MS (ESIpos): m/z=392 [M+H].sup.+

[0654] 1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.113 (2.73), 1.875 (6.24), 1.887 (6.13), 2.663 (6.98), 2.670 (6.82), 5.174 (7.47), 6.577 (0.59), 6.588 (1.60), 6.600 (1.57), 6.612 (0.56), 7.838 (16.00), 7.860 (0.69), 8.255 (1.34), 8.517 (2.72), 8.624 (2.13), 8.673 (3.90).

Intermediate 16A

(rac)-1-{3-[1-(1-Methyl-1H-pyrazol-3-yl)-1H-1,2,3-triazol-4-yl]pyrazin-2-yl}ethan-1-amine

[0655] ##STR00051##

[0656] 2-[(rac)-1-{3-[1-(1-Methyl-1H-pyrazol-3-yl)-1H-1,2,3-triazol-4-yl]pyrazin-2-yl}ethyl]-1H-isoindole-1,3(2H)-dione (intermediate 14A, 170 mg, 425 μmol) was suspended in ethanol (5.0 mL). Hydrazine hydrate (80% aqueous solution, 130 μl, 2.1 mmol) was added and the mixture was heated to reflux for 30 min. Then the solvent was distilled, the residue was triturated with ethyl acetate and filtered each time. The combined filtrates were evaporated to give 102 mg (100% purity, 89% yield) of the title compound.

[0657] LC-MS (Method 2): R.sub.t=0.60 min; MS (ESIpos): m/z=271 [M+H].sup.+

[0658] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.367 (7.72), 1.378 (8.25), 1.989 (0.77), 2.096 (0.62), 3.945 (16.00), 4.945 (1.06), 6.784 (4.17), 7.952 (4.16), 8.610 (3.34), 8.662 (2.38), 8.959 (4.75).

Intermediate 17A

(rac)-2-(4-{3-[1-Aminoethyl]pyrazin-2-yl}-1H-1,2,3-triazol-1-yl)-N-methylacetamide

[0659] ##STR00052##

[0660] 2-(4-{3-[(rac)-1-(1,3-Dioxo-1,3-dihydro-2H-isoindol-2-yl)ethyl]pyrazin-2-yl}-1H-1,2,3-triazol-1-yl)-N-methylacetamide (intermediate 15A, 190 mg, 485 μmol) was suspended in ethanol (5.7 mL). Hydrazine hydrate (80% aqueous solution, 150 μl, 2.4 mmol) was added and the mixture was heated to reflux for 1 h. Then the solvent was distilled, the residue was triturated with ethyl acetate and filtered each time. The combined filtrates were evaporated to give 110 mg (80% purity, 69% yield) of the title compound.

[0661] LC-MS (Method 3): R.sub.t=0.74 min; MS (ESIpos): m/z=262 [M+H].sup.+

[0662] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.045 (0.62), 1.057 (1.23), 1.069 (0.63), 1.346 (11.57), 1.357 (11.44), 2.664 (13.63), 2.671 (13.41), 3.437 (0.70), 3.448 (0.70), 5.005 (1.10), 5.152 (2.59), 5.189 (16.00), 7.840 (0.47), 7.845 (0.50), 7.850 (0.52), 7.855 (0.55), 8.055 (0.57), 8.061 (0.54), 8.065 (0.54), 8.070 (0.53), 8.267 (1.52), 8.567 (4.12), 8.599 (10.66), 8.605 (4.35).

Intermediate 18A

2-Chloro-3-(1-ethoxyvinyl)pyrazine

[0663] ##STR00053##

[0664] To a solution of 2,3-dichloropyrazine (2.00 g, 13.4 mmol) in toluene (100 mL) was added tributyl(1-ethoxyethenyl) stannane (5.30 g, 14.7 mmol) followed by Bis(triphenylphosphine) palladium (II) chloride (0.20 g, 0.30 mmol). The mixture was stirred at 100° C. under argon atmosphere for 15 hours. It was cooled to room temperature and filtered. The filtrate was concentrated and purified by column chromatography (silica gel, 100-200 mesh; EA-Hexane, 1:3) to afford product (1.50 g, 57%) as light yellow solid.

[0665] LC-MS (method 7): R.sub.t=1.48 min; MS (ESIpos): m/z=185, 187 [M+H].sup.+

Intermediate 19A

1-(3-Chloropyrazin-2-yl)ethanone

[0666] ##STR00054##

[0667] To a solution of 2-chloro-3-(1-ethoxyethenyl) pyrazine (intermediate 18A, 1.50 g, 8.10 mmol) in THF (20 mL) was added 2 N HCl (5 mL). The mixture was stirred at 50° C. for 2 hours. After completion of reaction, the mixture was concentrated, and pH was adjusted to 8 using sodium hydrogen carbonate. Then it was extracted with ethyl acetate (two portions of 50 mL). The organic layer was washed with water, dried over sodium sulfate and evaporated under reduced pressure. The residue was purified by column chromatography (silica gel, 100-200 mesh; EA-Hexanes, 1:5) to afford product (1.0 g, 75%) as white solid.

[0668] .sup.1H NMR (400 MHz, MeOD) δ 7.61-7.57 (m, 2H), 2.50 (s, 3H).

Intermediate 20A

1-[3-(2H-1,2,3-Triazol-2-yl)pyrazin-2-yl]ethanone

[0669] ##STR00055##

[0670] To a solution of 1-(3-chloropyrazin-2-yl) ethanone (intermediate 19A, 1.0 g, 6.4 mmol) in DMF (20 mL) was added 1H-1,2,3-triazole (0.9 g, 12.8 mmol) followed by potassium carbonate (1.80 g, 12.8 mmol). The mixture was stirred at 100° C. for 3 hours. The mixture was diluted with water (50 mL) and extracted with ethyl acetate (two portions of 30 mL), The organic layer was washed with water, dried over sodium sulfate, and evaporated under reduced pressure. The residue was purified by column chromatography (silica gel, methanol-DCM, 1:5) to afford product (0.5 g, 40%) as white solid.

[0671] LC-MS (method 7): R.sub.t=1.21 min; MS (ESIpos): m/z=190 [M+H].sup.+

Intermediate 21A

(rac)-1-[3-(2H-1,2,3-Triazol-2-yl)pyrazin-2-yl]ethanamine

[0672] ##STR00056##

[0673] To a solution of 1-[3-(1,2,3-triazol-2-yl) pyrazin-2-yl]ethanone (intermediate 20A, 500 mg, 2.6 mmol) in methanol (30 mL), ammonium acetate (400 mg, 5.3 mmol) was added followed by sodium cyanoborohydride (330 mg, 5.3 mmol). The mixture was stirred at 50° C. for 15 hours. After completion of reaction, the mixture was concentrated and diluted with water (30 mL), then extracted with ethyl acetate (three portions of 30 mL). The organic layer was washed with water, dried over sodium sulfate and evaporated under reduced pressure. The residue was purified by column chromatography (silica gel, 100-200 mesh; MeOH-DCM, 1:10) to afford product (0.3 g, 54%) as white solid.

[0674] .sup.1H NMR (300 MHz, CD.sub.3OD) δ 8.84 (d, J=2.5 Hz, 1H), 8.68 (d, J=2.4 Hz, 1H), 8.18 (s, 2H), 5.35-5.28 (m, 1H), 1.63 (d, J=6.7 Hz, 3H).

Intermediate 22A

(rac)-Methyl 1-{3-[1-hydroxyethyl]pyrazin-2-yl}-1H-1,2,4-triazole-3-carboxylate

[0675] ##STR00057##

[0676] (rac)-1-(3-Bromopyrazin-2-yl)ethan-1-ol (5.00 g, 24.6 mmol) was dissolved in DMF (30.0 mL), methyl 1H-1,2,4-triazole-5-carboxylate (6.26 g, 49.3 mmol), potassium carbonate (10.2 g, 73.9 mmol) and copper(I) iodide (1.41 g, 7.39 mmol) and trans-cyclohexane,1,2-diamine (1.2 mL, 7.4 mmol) were added and the mixture was heated to 90° C. for 20 min. The mixture was diluted with ethyl acetate and filtered. The filtrate was charged onto diatomaceous earth, evaporated and eventually chromatographed over silica gel with a gradient of cyclohexane/ethyl acetate to give 2.50 g (97% purity, 40% yield) of the title compound.

[0677] LC-MS (Method 2): R.sub.t=0.75 min; MS (ESIpos): m/z=250 [M+H].sup.+

[0678] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.444 (7.54), 1.455 (7.45), 2.733 (4.63), 2.891 (5.35), 3.923 (16.00), 5.133 (1.07), 5.144 (1.66), 5.155 (1.14), 5.265 (2.98), 5.275 (2.52), 5.746 (0.82), 7.953 (0.74), 8.669 (2.75), 8.673 (2.90), 8.919 (2.74), 8.923 (2.72), 9.309 (4.95).

Intermediate 23A

(rac)-Methyl 1-{3-[1-{[tert-butyl(dimethyl)silyl]oxy}ethyl]pyrazin-2-yl}-1H-1,2,4-triazole-3-carboxylate

[0679] ##STR00058##

[0680] (rac)-Methyl 1-{3-[1-hydroxyethyl]pyrazin-2-yl}-1H-1,2,4-triazole-3-carboxylate (intermediate 22A, 1.27 g, 5.10 mmol) was dissolved in DMF (2.0 mL), 1H-imidazole (659 mg, 9.68 mmol; CAS-RN:288-32-4) and tert-butyl(chloro)dimethylsilane (1.08 g, 7.13 mmol; CAS-RN:18162-48-6) were added and the mixture was stirred at room temperature over night. The mixture was diluted with brine and extracted with three portions of ethyl acetate. The combined organic extracts were evaporated and purified chromatographically on silica gel with an cyclohexane/ethyl acetate gradient to yield 1.30 g (100% purity, 70% yield) of the title compound.

[0681] LC-MS (Method 2): R.sub.t=2.12 min; MS (ESIpos): m/z=364 [M+H].sup.+

[0682] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: −0.123 (5.35), 0.088 (0.47), 0.802 (16.00), 1.601 (2.47), 1.612 (2.44), 2.630 (3.03), 4.013 (5.60), 5.578 (0.62), 5.589 (0.61), 8.786 (1.02), 8.790 (1.03), 9.036 (1.03), 9.040 (0.98), 9.478 (1.80).

Intermediate 24A

(rac)-1-{3-[1-{[tert-Butyl(dimethyl)silyl]oxy}ethyl]pyrazin-2-yl}-1H-1,2,4-triazole-3-carboxylic acid

[0683] ##STR00059##

[0684] (rac)-Methyl 1-{3-[1-{[tert-butyl(dimethyl)silyl]oxy}ethyl]pyrazin-2-yl}-1H-1,2,4-triazole-3-carboxylate (intermediate 23A, 755 mg, 2.08 mmol) was dissolved in pyridine (5.00 mL), lithium iodide (2.78 g, 20.8 mmol) was added and the mixture was heated to 120° C. for 1 h. The mixture was diluted with n-butanol and then poured into water. The aqueous phase was saturated with ammonium chloride, the phases were separated and the aqueous phase was extracted another two times with n-butanol. The organic phases were combined and evaporated. The residue was triturated with acetonitrile, filtered and washed twice with acetonitrile. The combined filtrates were eventually purified by preparative HPLC (RP-C18, water-acetonitrile gradient with 0.1% ammonia) to give 650 mg (100% purity, 90% yield) of the title compound.

[0685] LC-MS (Method 2): R.sub.t=1.64 min; MS (ESIpos): m/z=350 [M+H].sup.+

[0686] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: −0.159 (5.27), 0.824 (1.19), 0.829 (16.00), 1.634 (2.33), 1.644 (2.32), 2.661 (2.81), 5.765 (0.58), 5.776 (0.57), 8.751 (0.99), 8.755 (1.05), 8.991 (0.98), 8.995 (0.96), 9.185 (1.30).

Intermediate 25A

(rac)-1-{3-[1-{[tert-Butyl(dimethyl)silyl]oxy}ethyl]pyrazin-2-yl}-N-ethyl-N-methyl-1H-1,2,4-triazole-3-carboxamide

[0687] ##STR00060##

[0688] (rac)-1-{3-[1-{[tert-Butyl(dimethyl)silyl]oxy}ethyl]pyrazin-2-yl}-1H-1,2,4-triazole-3-carboxylic acid (450 mg, 1.29 mmol) was dissolved in DMF (7.50 mL), N-methylethanamine (170 μl, 1.9 mmol) and DIPEA (670 μl, 3.9 mmol) were added and the mixture was cooled to 0° C. on an ice bath. HATU (734 mg, 1.93 mmol) was added and the reaction was left stirring for 30 min. The mixture was then poured into water, brine was added and it was extracted with three portions of ethyl acetate. The combined organic extracts were dried over anhydrous sodium sulfate, evaporated and eventually chromatographed (HPLC RP-C18, water-acetonitrile gradient with 0.1% ammonia) to yield 500 mg (71% purity, 71% yield) of the title compound.

[0689] LC-MS (Method 2): R.sub.t=2.04 min; MS (ESIpos): m/z=391 [M+H].sup.+

[0690] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: −0.096 (4.80), −0.074 (3.06), 0.024 (3.05), 0.146 (1.68), 0.860 (1.27), 0.865 (16.00), 0.869 (10.90), 1.289 (0.84), 1.298 (1.34), 1.301 (1.94), 1.309 (2.52), 1.313 (1.22), 1.321 (1.12), 1.658 (1.52), 1.663 (2.34), 1.668 (1.65), 1.674 (2.23), 2.687 (5.39), 3.167 (4.89), 3.232 (3.38), 3.592 (0.82), 3.604 (0.80), 3.660 (0.63), 3.672 (0.61), 5.605 (0.55), 5.616 (0.55), 8.826 (0.64), 8.830 (1.57), 8.834 (1.02), 9.074 (0.61), 9.078 (0.65), 9.082 (0.98), 9.086 (0.91), 9.487 (1.09), 9.502 (1.71).

Intermediate 26A

(rac)-N-Ethyl-1-[3-(1-hydroxyethyl)pyrazin-2-yl]-N-methyl-1H-1,2,4-triazole-3-carboxamide

[0691] ##STR00061##

[0692] (rac)-1-{3-[1-{[tert-Butyl(dimethyl)silyl]oxy}ethyl]pyrazin-2-yl}-N-ethyl-N-methyl-1H-1,2,4-triazole-3-carboxamide (intermediate 25A, 249 mg, 319 μmol) was dissolved in 1,4-dioxane (2.0 mL), hydrogen chloride (4 M in 1,4-dioxane, 1.5 mL, 6.0 mmol) was added at room temperature and the mixture was stirred for 3 h. The mixture was evaporated and the residue was chromatographed (HPLC RP-C18, water-acetonitrile gradient with 0.1% ammonia) to yield 160 mg (100% purity, 91% yield) of the title compound.

[0693] LC-MS (Method 2): R.sub.t=0.81 min; MS (ESIpos): m/z=277 [M+H].sup.+

[0694] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.145 (2.74), 1.153 (4.09), 1.157 (6.04), 1.165 (8.20), 1.169 (3.40), 1.177 (3.76), 1.236 (0.67), 1.443 (8.41), 1.446 (6.43), 1.453 (8.43), 1.457 (6.08), 2.086 (1.23), 3.017 (16.00), 3.090 (10.90), 3.423 (0.85), 3.435 (2.23), 3.436 (2.22), 3.448 (2.24), 3.460 (0.83), 3.497 (0.82), 3.509 (2.48), 3.520 (2.43), 3.532 (0.78), 5.170 (0.76), 5.181 (1.32), 5.184 (1.29), 5.195 (1.97), 5.205 (1.44), 5.216 (0.43), 5.229 (3.60), 5.240 (2.25), 5.244 (2.29), 5.254 (1.58), 5.746 (1.96), 8.650 (5.16), 8.654 (5.46), 8.894 (4.52), 8.897 (4.52), 9.256 (3.36), 9.264 (5.24).

Intermediate 27A

(rac)-1-{3-[1-(1,3-Dioxo-1,3-dihydro-2H-isoindol-2-yl)ethyl]pyrazin-2-yl}-N-ethyl-N-methyl-1H-1,2,4-triazole-3-carboxamide

[0695] ##STR00062##

[0696] N-Ethyl-1-{3-[1-hydroxyethyl]pyrazin-2-yl}-N-methyl-1H-1,2,4-triazole-3-carboxamide (intermediate 26A, 155 mg, 561 μmol) μmol) was dissolved in THF (3.3 mL). 1H-isoindole-1,3(2H)-dione (124 mg, 841 μmol) and triphenylphosphine (polymer bound, 3 mmol/g, 221 mg, 841 μmol) were added, the mixture was cooled to 0° C. and DIAD (820 μl, 1.0 M, 660 μmol) was slowly added. Stirring was continued for 1 h at room temperature. Then the mixture was poured into water, extracted with 3 portions of ethyl acetate, the combined extracts were dried over anhydrous sodium sulfate, evaporated and eventually purified chromatographically (silica gel, cyclohexane/ethyl acetate gradient) to yield 204 mg (93% purity, 83% yield) of the title compound.

[0697] LC-MS (Method 2): R.sub.t=1.40 min; MS (ESIpos): m/z=406 [M+H].sup.+

[0698] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.093 (1.00), 1.105 (2.86), 1.117 (2.57), 1.129 (0.79), 1.718 (2.07), 1.723 (1.58), 1.730 (2.10), 1.734 (1.47), 1.988 (0.45), 2.070 (0.73), 2.935 (3.25), 2.967 (4.35), 3.293 (14.73), 3.297 (16.00), 3.307 (0.58), 3.319 (0.49), 3.323 (0.49), 3.334 (0.43), 6.105 (0.46), 6.117 (0.45), 7.625 (0.46), 7.772 (0.42), 7.777 (0.51), 7.781 (0.55), 7.786 (0.84), 7.790 (0.64), 7.795 (0.72), 7.799 (0.68), 7.804 (1.15), 7.814 (0.86), 7.819 (0.70), 7.824 (1.55), 7.829 (1.03), 7.833 (0.67), 7.839 (0.52), 8.689 (0.80), 8.693 (1.20), 8.698 (0.57), 8.857 (0.85), 8.861 (0.80), 8.885 (0.60), 8.888 (0.56), 9.257 (1.01), 9.285 (1.45).

Intermediate 28A

(rac)-1-{3-[1-Aminoethyl]pyrazin-2-yl}-N-ethyl-N-methyl-1H-1,2,4-triazole-3-carboxamide

[0699] ##STR00063##

[0700] (rac)-1-{3-[1-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)ethyl]pyrazin-2-yl}-N-ethyl-N-methyl-1H-1,2,4-triazole-3-carboxamide (intermediate 27A, 200 mg, 493 μmol) and hydrazine hydrate (120 μl, 2.5 mmol) were dissolved in ethanol (2.0 mL), the mixture was heated to 80° C. for 1 h, the solvent was distilled the residue was taken up into acetonitrile and purified by preparative HPLC (RP-C18, water-acetonitrile gradient with 0.1% ammonia) to give 122 mg (100% purity, 90% yield) of the title compound.

[0701] LC-MS (Method 2): R.sub.t=0.49 min; MS (ESIpos): m/z=276 [M+H].sup.+

[0702] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.147 (2.63), 1.158 (6.18), 1.168 (8.35), 1.179 (3.74), 1.322 (9.12), 1.333 (9.18), 1.979 (1.93), 2.070 (1.00), 3.019 (16.00), 3.092 (10.60), 3.418 (1.14), 3.430 (3.40), 3.442 (3.37), 3.453 (1.09), 3.499 (0.80), 3.511 (2.44), 3.523 (2.39), 3.535 (0.77), 4.348 (1.18), 4.352 (0.72), 4.359 (1.30), 4.363 (1.89), 4.374 (1.79), 4.385 (0.55), 5.745 (4.91), 8.590 (5.09), 8.594 (5.27), 8.871 (4.93), 8.875 (4.89), 9.277 (6.38).

[0703] The following intermediates were synthesized according to General Synthetic Method 3:

TABLE-US-00001 Structure IUPAC-Name LC-MS (method): Retention time; Mass found Intermediate .sup.1H-NMR 29A [00064] (rac)-1-{3-[1-{[tert-Butyl(dimethyl)silyl]oxy}ethyl] pyrazin-2-yl}-1H-1,2,4-triazole-3-carboxamide LC-MS (Method 2): R.sub.t = 1.67 min; MS (ESIpos): m/z = 349 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 0.251 (0.61), 0.952 (16.00), 1.787 (2.32), 1.797 (2.30), 2.792 (3.26), 5.789 (0.59), 5.799 (0.59), 8.936 (1.02), 8.940 (1.06), 9.180 (1.01), 9.184 (0.98), 9.573 (1.94). 30A [00065] (rac)-(1-{3-[1-{[tert-Butyl(dimethyl)silyl]oxy}ethyl] pyrazin-2-yl}-1H-1,2,4-triazol-3-yl)[(cis)-2,6- dimethylmorpholin-4-yl]methanone LC-MS (Method 2): R.sub.t = 2.17 min; MS (ESIpos): m/z = 447 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: −0.233 (9.71), −0.140 (4.23), −0.133 (4.29), 0.713 (16.00), 0.716 (15.92), 1.050 (2.21), 1.054 (2.30), 1.060 (2.35), 1.064 (2.12), 1.166 (3.52), 1.177 (3.49), 1.526 (2.72), 1.535 (2.70), 2.559 (0.70), 2.562 (0.68), 2.581 (0.57), 2.874 (0.59), 2.896 (0.58), 3.559 (0.48), 3.569 (0.70), 3.576 (0.71), 3.998 (0.66), 4.020 (0.64), 4.400 (0.64), 4.422 (0.63), 5.483 (0.50), 5.494 (0.56), 5.499 (0.55), 5.509 (0.48), 8.686 (1.68), 8.929 (1.82), 8.933 (1.74), 9.372 (3.81).

[0704] The following intermediates were synthesized according to General Synthetic Method 5:

TABLE-US-00002 Structure IUPAC-Name LC-MS (method): Retention time; Mass found Intermediate .sup.1H-NMR 31A [00066] (rac)-1-{3-[1-hydroxyethyl]pyrazin-2-yl}-1H- 1,2,4-triazole-3-carboxamide LC-MS (Method 3): R.sub.t = 0.61 min; MS (ESIpos): m/z = 235 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.444 (16.00), 1.454 (15.72), 5.190 (0.62), 5.201 (2.24), 5.211 (3.42), 5.221 (2.42), 5.231 (0.68), 5.276 (5.10), 5.287 (3.82), 7.287 (6.18), 7.760 (2.97), 8.009 (2.93), 8.653 (6.57), 8.657 (6.65), 8.897 (6.59), 8.901 (6.40), 9.253 (10.40). 32A [00067] (rac)-[(cis)-2,6-Dimethylmorpholin-4-yl](1-{3-[1- hydroxyethyl]pyrazin-2-yl}-1H-1,2,4-triazol-3-yl) methanone LC-MS (Method 2): R.sub.t = 0.95 min; MS (ESIpos): m/z = 333 [M + H].sup.+ .sup.1H-NMR (400 MHz, DMSO-d6) δ [ppm]: 1.049 (8.77), 1.064 (12.49), 1.076 (9.26), 1.160 (15.71), 1.175 (16.00), 1.449 (9.09), 1.459 (10.19), 1.465 (10.38), 1.475 (9.48), 1.908 (0.50), 2.586 (2.08), 2.832 (1.43), 2.837 (1.45), 2.864 (2.88), 2.892 (1.67), 2.897 (1.64), 3.567 (2.74), 3.584 (3.26), 3.593 (2.90), 3.601 (2.23), 3.608 (1.97), 4.029 (1.59), 4.046 (1.56), 4.062 (1.55), 4.079 (1.48), 4.386 (2.76), 4.419 (2.68), 5.171 (1.33), 5.187 (2.25), 5.197 (1.60), 5.202 (1.89), 5.213 (2.32), 5.228 (1.77), 5.244 (0.67), 5.253 (4.37), 5.260 (4.04), 5.268 (2.38), 5.276 (2.68), 5.753 (4.33), 8.654 (7.94), 8.660 (8.64), 8.894 (6.02), 8.897 (5.98), 9.294 (6.57), 9.301 (6.92).

[0705] The following intermediates were synthesized according to General Synthetic Method 1:

TABLE-US-00003 Structure IUPAC-Name LC-MS (method): Retention time; Mass found Intermediate .sup.1H-NMR 33A [00068] (rac)-2-[1-(3-{3-[(cis)-2,6-Dimethylmorpholine-4- carbonyl]-1H-1,2,4-triazol-1-yl} pyrazin-2-yl)ethyl]-1H-isoindole-1,3(2H)-dione LC-MS (Method 2): R.sub.t = 1.52 min; MS (ESIpos): m/z = 462 [M + H].sup.+ .sup.1H-NMR (400 MHz, DMSO-d6) δ [ppm]: 0.146 (0.40), 0.980 (3.32), 0.996 (3.40), 1.033 (3.09), 1.048 (3.16), 1.153 (5.94), 1.168 (6.12), 1.718 (3.13), 1.734 (5.50), 1.751 (2.95), 1.988 (0.50), 2.367 (0.43), 2.454 (0.52), 2.610 (0.52), 2.642 (0.60), 2.669 (0.84), 2.710 (0.47), 2.817 (0.44), 2.844 (0.54), 2.849 (0.53), 2.876 (0.49), 3.553 (0.77), 3.563 (0.77), 3.580 (0.62), 3.838 (0.62), 3.871 (0.60), 3.953 (0.58), 3.986 (0.55), 4.333 (1.10), 4.366 (1.06), 5.753 (1.99), 6.022 (0.81), 6.039 (0.92), 6.053 (0.86), 6.070 (0.75), 7.530 (3.25), 7.535 (3.48), 7.549 (10.42), 7.557 (8.53), 7.566 (11.03), 7.573 (9.54), 7.597 (12.90), 7.614 (11.59), 7.625 (16.00), 7.644 (8.72), 7.771 (0.85), 7.779 (1.70), 7.785 (2.07), 7.792 (2.94), 7.799 (2.28), 7.810 (1.03), 7.820 (2.21), 7.827 (3.09), 7.834 (2.27), 7.840 (1.78), 7.847 (1.01), 8.699 (2.31), 8.705 (2.46), 8.882 (1.37), 8.889 (2.48), 8.896 (1.43), 9.284 (2.17), 9.293 (2.03). 34A [00069] (rac)-1-{3-[1-(1,3-Dioxo-1,3-dihydro-2H-isoindol-2-yl) ethyl]pyrazin-2-yl}-1H-1,2,4-triazole-3-carboxamide LC-MS (Method 2): R.sub.t = 1.07 min; MS (ESIpos): m/z = 364 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.725 (16.00), 1.736 (15.92), 1.900 (0.46), 1.907 (0.60), 1.912 (0.42), 2.731 (9.16), 2.890 (9.85), 3.258 (0.91), 6.095 (1.25), 6.107 (4.14), 6.119 (4.03), 6.130 (1.16), 7.691 (3.62), 7.725 (3.65), 7.766 (4.94), 7.771 (5.82), 7.774 (6.22), 7.780 (8.74), 7.787 (1.71), 7.801 (1.98), 7.808 (9.07), 7.813 (6.32), 7.817 (5.44), 7.823 (4.57), 7.952 (1.59), 8.693 (6.56), 8.697 (6.58), 8.884 (7.00), 8.888 (6.42), 9.244 (12.17).

[0706] The following intermediates were synthesized according to General Synthetic Method 2:

TABLE-US-00004 Structure IUPAC-Name LC-MS (method): Retention time; Mass found Intermediate .sup.1H-NMR 35A [00070] (rac)-1-{3-[1-Aminoethyl]pyrazin-2-yl}-1H-1,2,4- triazole-3-carboxamide LC-MS (Method 3): R.sub.t = 0.68 min; MS (ESIpos): m/z = 234 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.137 (0.65), 1.325 (2.69), 1.331 (16.00), 1.335 (3.48), 1.342 (15.75), 1.545 (1.82), 1.557 (1.81), 1.631 (0.72), 1.767 (0.72), 1.896 (0.81), 2.732 (0.71), 2.831 (1.31), 2.871 (0.89), 2.892 (1.25), 3.171 (15.36), 3.285 (0.55), 3.395 (0.78), 4.380 (1.18), 4.391 (3.49), 4.402 (3.44), 4.413 (1.13), 4.418 (0.50), 5.746 (0.85), 7.197 (0.52), 7.299 (0.55), 7.441 (0.50), 7.558 (0.47), 7.742 (0.44), 7.773 (2.24), 7.869 (0.81), 7.874 (0.76), 7.878 (0.78), 7.884 (0.90), 7.990 (2.24), 8.065 (1.13), 8.070 (0.80), 8.075 (0.72), 8.080 (0.71), 8.600 (7.46), 8.604 (6.82), 8.850 (0.44), 8.854 (1.01), 8.858 (0.69), 8.881 (6.66), 8.885 (5.85), 9.270 (11.26), 9.308 (0.63), 9.322 (1.22). 36A [00071] (rac)-(1-{3-[1-Aminoethyl]pyrazin-2-yl}-1H-1,2,4-triazol- 3-yl)[(cis)-2,6-dimethylmorpholin-4-yl]methanone LC-MS (Method 2): R.sub.t = 0.63 min; MS (ESIpos): m/z = 332 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d.sub.6) δ [ppm]: 1.059 (9.43), 1.065 (10.61), 1.070 (10.50), 1.076 (8.87), 1.164 (16.00), 1.175 (15.77), 1.330 (9.28), 1.337 (10.55), 1.341 (10.30), 1.348 (8.68), 2.046 (1.35), 2.559 (3.19), 2.579 (1.99), 2.857 (2.47), 2.875 (3.10), 2.879 (2.88), 2.897 (2.58), 3.578 (2.86), 3.590 (3.68), 3.601 (2.70), 3.606 (2.46), 4.021 (1.61), 4.043 (2.76), 4.069 (1.54), 4.359 (0.71), 4.371 (2.10), 4.382 (2.43), 4.389 (3.76), 4.393 (3.93), 4.400 (3.30), 4.415 (2.84), 5.744 (4.09), 8.590 (7.76), 8.594 (7.71), 8.870 (7.90), 8.874 (7.47), 9.310 (6.73), 9.314 (6.57).

EXAMPLES

Example I-1

(rac)-3-Chloro-5-(methylsulfonyl)-N-{1-[3-(2H-1,2,3-triazol-2-yl)pyrazin-2-yl]ethyl}benzamide

[0707] ##STR00072##

[0708] To a solution of 1-1-[3-(1,2,3-triazol-2-yl) pyrazin-2-yl] ethanamine (intermediate 21A, 150 mg, 0.8 mmol) in DCM (20 mL) was added DIPEA (300 mg, 2.4 mmol) followed by 3-chloro-5-methanesulfonylbenzoyl chloride (300 mg, 1.2 mmol) at 0° C. The mixture was stirred at room temperature for 3 hours. The mixture was quenched by MeOH (1 mL) then washed with water (20 mL). The organic layer was dried over Na.sub.2SO.sub.4 and evaporated under reduced pressure. The residue was purified by column chromatography (silica gel, 100-200 mesh; EA-Hexane, 1:1) to afford product (0.15 g, 44%) as white solid.

[0709] LC-MS (Method 7): R.sub.t=1.40 min; MS (ESIpos): m/z=407 [M+H].sup.+

[0710] .sup.1H-NMR (400 MHz, CDCl.sub.3) δ [ppm]: 1.60 (d, 3H), 6.19 (m, 1H), 7.69 (m, 1H), 8.05 (s, 2H), 8.61 (s, 1H), 8.62 (s, 1H), 8.71 (s, 1H), 8.72 (s, 1H).

Example I-2

3,5-Dibromo-N-{(rac)-1-[3-(3-methyl-1H-1,2,4-triazol-1-yl)pyrazin-2-yl]ethyl}benzamide

[0711] ##STR00073##

[0712] (rac)-1-[3-(3-Methyl-1H-1,2,4-triazol-1-yl)pyrazin-2-yl]ethan-1-amine (intermediate 5A, 50.0 mg, 245 μmol) and DIPEA (130 μl, 730 μmol) were dissolved in DMF (2.0 mL). The mixture was cooled to 0° C. and HATU (140 mg, 367 μmol) was added. The cooling bath was removed and stirring was maintained for 1 h. The reaction mixture was diluted with water. The product precipitated and was collected on a filter funnel and dried under vacuum. The crude product was triturated twice with a small amount of acetonitrile and dried again to give 88.0 mg (98% purity, 76% yield) of the title compound.

[0713] LC-MS (Method 2): R.sub.t=1.87 min; MS (ESIpos): m/z=465 [M+H].sup.+

[0714] .sup.1H-NMR (400 MHz, DMSO-d6) δ[ppm]: 1.577 (6.97), 1.595 (6.97), 2.391 (16.00), 2.889 (0.43), 5.616 (1.17), 5.633 (1.75), 5.650 (1.17), 7.980 (5.88), 7.985 (8.32), 8.000 (2.54), 8.004 (3.02), 8.008 (1.70), 8.564 (3.22), 8.570 (3.42), 8.781 (3.32), 8.787 (3.25), 9.103 (4.13), 9.149 (1.75), 9.166 (1.72).

TABLE-US-00005 Structure IUPAC-Name LC-MS (method): Retention time; Mass found Example .sup.1H-NMR I-3 [00074] (rac)-N-{1-[3-(3-Methyl-1H-1,2,4-triazol-1-yl)pyrazin-2-yl] ethyl}-3,5-bis(trifluoromethyl)benzamide LC-MS (Method 2): R.sub.t = 1.92 min; MS (ESIpos): m/z = 445 [M + H].sup.+ 1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.633 (7.17), 1.644 (7.11), 2.385 (16.00), 5.701 (1.19), 5.712 (1.79), 5.724 (1.16), 8.278 (3.11), 8.455 (7.38), 8.576 (3.13), 8.580 (3.30), 8.791 (3.16), 8.795 (3.14), 9.100 (4.65), 9.442 (1.81), 9.453 (1.75). I-4 [00075] (rac)-3-Chloro-5-(methanesulfonyl)-N-{1-[3-(3-methyl- 1H-1,2,4-triazol-1-yl)pyrazin-2-yl]ethyl}benzamide LC-MS (Method 2): R.sub.t = 1.33 min; MS (ESIpos): m/z = 421 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.614 (6.62), 1.625 (6.56), 2.397 (15.42), 3.308 (16.00), 3.358 (0.48), 5.676 (1.10), 5.687 (1.67), 5.698 (1.09), 8.110 (1.75), 8.113 (2.92), 8.116 (1.92), 8.186 (2.04), 8.189 (3.11), 8.192 (2.02), 8.273 (3.43), 8.572 (2.98), 8.576 (3.09), 8.791 (3.03), 8.795 (2.95), 9.100 (4.50), 9.319 (1.66), 9.330 (1.61). I-5 [00076] (rac)-N-(1-[3-(1H-1,2,4-Triazol-1-yl)pyrazin-2-yl]ethyl)-3,5- bis(trifluoromethyl)benzamide LC-MS (Method 2): R.sub.t = 1.86 min; MS (ESIpos): m/z = 431 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.217 (0.78), 1.228 (0.95), 1.234 (0.88), 1.246 (0.75), 1.640 (16.00), 1.651 (15.83), 2.732 (0.80), 2.890 (0.87), 5.629 (0.67), 5.641 (2.65), 5.652 (3.99), 5.663 (2.63), 5.675 (0.65), 8.276 (6.29), 8.387 (11.68), 8.461 (15.11), 8.611 (6.98), 8.615 (7.16), 8.834 (7.15), 8.838 (6.94), 9.278 (11.74), 9.483 (3.78), 9.494 (3.67). I-6 [00077] (rac)-3-Chloro-5-(methanesulfonyl)-N-{1-[3-(1H-1,2,4- triazol-1-yl)pyrazin-2-yl]ethyl}benzamide LC-MS (Method 2): R.sub.t = 1.26 min; MS (ESIpos): m/z = 407 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.621 (8.15), 1.632 (7.83), 3.307 (16.00), 5.627 (2.14), 8.112 (3.82), 8.196 (4.30), 8.278 (4.44), 8.390 (4.08), 8.610 (4.27), 8.837 (4.29), 9.276 (3.95), 9.358 (2.68). I-7 [00078] (rac)-3,5-Dibromo-N-{1-[3-(1H-1,2,4-triazol-1-yl)pyrazin- 2-yl]ethyl}benzamide LC-MS (Method 2): R.sub.t = 1.81 min; MS (ESIpos): m/z = 451 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.589 (10.26), 1.600 (10.21), 5.559 (0.45), 5.571 (1.69), 5.582 (2.53), 5.593 (1.66), 5.605 (0.42), 7.992 (16.00), 8.382 (7.32), 8.600 (4.42), 8.604 (4.59), 8.825 (4.55), 8.829 (4.44), 9.164 (2.43), 9.175 (2.41), 9.265 (7.14). I-8 [00079] (rac)-3-Chloro-N-{1-[3-(1H-1,2,4-triazol-1-yl)pyrazin- 2-yl]ethyl}-5-(trifluoromethoxy)benzamide LC-MS (Method 2): R.sub.t = 1.84 min; MS (ESIpos): m/z = 413 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.206 (0.49), 1.222 (0.64), 1.233 (0.51), 1.605 (16.00), 1.617 (15.68), 5.577 (0.65), 5.589 (2.61), 5.600 (3.86), 5.611 (2.50), 5.623 (0.59), 7.724 (5.88), 7.740 (5.30), 7.964 (4.22), 7.967 (7.32), 8.382 (11.59), 8.604 (6.70), 8.608 (7.21), 8.828 (6.96), 8.832 (6.77), 9.229 (3.60), 9.239 (3.51), 9.271 (11.39). I-9 [00080] (rac)-3-Chloro-N-{1-[3-(3-methyl-1H-1,2,4-triazol-1- yl)pyrazin-2-yl]ethyl}-5-(trifluoromethoxy)benzamide LC-MS (Method 2): R.sub.t = 1.92 min; MS (ESIpos): m/z = 427 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.598 (6.77), 1.610 (6.68), 2.388 (16.00), 5.655 (1.12), 5.666 (1.66), 5.677 (1.08), 7.722 (2.40), 7.739 (2.18), 7.958 (2.12), 7.960 (3.12), 7.963 (1.86), 8.570 (3.09), 8.574 (3.16), 8.786 (3.14), 8.790 (2.95), 9.097 (4.72), 9.193 (1.54), 9.204 (1.49). I-10 [00081] (rac)-N-{1-[3-(1-Methyl-1H-1,2,3-triazol-4-yl)pyrazin- 2-yl]ethyl}-3,5-bis(trifluoromethyl)benz amide LC-MS (Method 2): R.sub.t = 1.87 min; MS (ESIpos): m/z = 445 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.630 (7.23), 1.642 (7.16), 4.177 (16.00), 6.264 (1.22), 6.276 (1.83), 6.287 (1.21), 8.283 (3.19), 8.524 (7.48), 8.580 (2.66), 8.583 (4.32), 8.591 (4.29), 8.595 (2.61), 8.691 (5.26), 9.471 (1.83), 9.482 (1.80). I-11 [00082] (rac)-3-Chloro-N-{1-[3-(1-methyl-1H-1,2,3-triazol-4-yl) pyrazin-2-yl]ethyl}-5-(trifluoromethoxy)benzamide LC-MS (Method 1): R.sub.t = 1.30 min; MS (ESIpos): m/z = 427 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.594 (7.04), 1.605 (6.98), 4.172 (16.00), 6.203 (1.19), 6.215 (1.82), 6.226 (1.18), 7.742 (2.46), 7.776 (2.74), 8.029 (3.44), 8.573 (2.20), 8.577 (4.44), 8.583 (4.45), 8.587 (2.28), 8.680 (5.31), 9.202 (1.69), 9.214 (1.66). I-12 [00083] (rac)-N-1-{3-[1-(1-Methyl-1H-pyrazol-3-yl)-1H-1,2,3- triazol-4-yl]pyrazin-2-yl}ethyl]-3,5-bis(trifluoromethyl) benzamide LC-MS (Method 2): R.sub.t = 2.04 min; MS (ESIpos): m/z = 511 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.663 (6.59), 1.675 (6.52), 3.951 (16.00), 6.219 (1.15), 6.231 (1.74), 6.242 (1.12), 6.786 (2.86), 6.790 (3.01), 7.957 (2.84), 7.961 (2.85), 8.276 (2.80), 8.517 (6.62), 8.649 (10.49), 9.026 (5.28), 9.502 (1.72), 9.513 (1.68). I-13 [00084] (rac)-N-[1-(3-{1-[2-(Methylamino)-2-oxoethyl]-1H-1,2,3- triazol-4-yl}pyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl) benzamide LC-MS (Method 2): R.sub.t = 1.69 min; MS (ESIpos): m/z = 502 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.629 (13.14), 1.641 (13.00), 2.070 (3.35), 2.678 (15.63), 2.686 (15.44), 5.216 (16.00), 6.288 (0.53), 6.299 (2.24), 6.310 (3.43), 6.322 (2.22), 6.333 (0.53), 8.284 (6.73), 8.293 (2.09), 8.533 (11.89), 8.583 (5.11), 8.587 (7.77), 8.601 (7.89), 8.605 (5.42), 8.684 (12.43), 9.475 (3.30), 9.486 (3.18). I-14 [00085] (rac)-3-Chloro-5-(methanesulfonyl)-N-{1-[3-(1-methyl- 1H-1,2,3-triazol-4-yl)pyrazin-2-yl]ethyl}benzamide LC-MS (Method 2): R.sub.t = 1.26 min; MS (ESIpos): m/z = 421 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.608 (6.39), 1.619 (6.35), 3.319 (16.00), 3.369 (0.45), 4.174 (15.01), 6.236 (1.08), 6.248 (1.66), 6.259 (1.08), 8.113 (1.73), 8.116 (2.91), 8.119 (1.86), 8.246 (2.09), 8.249 (3.13), 8.252 (2.04), 8.326 (2.22), 8.328 (3.37), 8.331 (2.07), 8.581 (1.79), 8.585 (4.70), 8.588 (4.87), 8.592 (1.84), 8.684 (4.98), 9.317 (1.57), 9.329 (1.55). I-15 [00086] (rac)-3,5-Dibromo-N-{1-[3-(1-methyl-1H-1,2,3-triazol- 4-yl)pyrazin-2-yl]ethyl}benzamide LC-MS (Method 2): R.sub.t = 1.84 min; MS (ESIpos): m/z = 465 [M + H].sup.+ .sup.1H-NMR (500 MHz, DMSO-d6) δ [ppm]: 1.580 (6.35), 1.594 (6.41), 4.174 (16.00), 6.177 (1.10), 6.191 (1.73), 6.205 (1.09), 8.010 (1.59), 8.013 (3.14), 8.016 (2.04), 8.051 (7.57), 8.055 (6.46), 8.574 (1.78), 8.578 (5.06), 8.583 (5.20), 8.588 (1.84), 8.692 (5.85), 9.170 (1.58), 9.183 (1.54). I-16 [00087] (rac)-3-Chloro-5-(methanesulfonyl)-N-[1-{3-[1-(1- methyl-1H-pyrazol-3-yl)-1H-l,2,3-triazol-4-yl]pyrazin- 2-yl}ethyl]benzamide LC-MS (Method 2): R.sub.t = 1.47 min; MS (ESIpos): m/z = 487 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.645 (6.23), 1.656 (6.17), 3.314 (16.00), 3.325 (4.94), 3.341 (4.73), 3.954 (15.25), 6.197 (1.07), 6.208 (1.63), 6.220 (1.06), 6.792 (2.32), 6.793 (3.08), 6.796 (2.68), 6.797 (2.74), 7.958 (2.91), 7.962 (2.54), 8.113 (2.94), 8.248 (3.13), 8.332 (3.22), 8.334 (3.38), 8.651 (7.27), 8.657 (1.20), 9.026 (4.28), 9.028 (5.10), 9.361 (1.72), 9.372 (1.67). I-17 [00088] (rac)-3-Chloro-5-(methanesulfonyl)-N-[1-(3-{1-[2- (methylamino)-2-oxoethyl]-1H-1,2,3-triazol-4- yl}pyrazin-2-yl)ethyl]benzamide LC-MS (Method 4): R.sub.t = 0.65 min; MS (ESIpos): m/z = 478 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.610 (7.40), 1.621 (7.19), 2.677 (9.39), 2.684 (7.98), 3.315 (9.31), 3.320 (16.00), 5.213 (8.80), 6.273 (1.39), 6.285 (1.94), 6.296 (1.30), 8.115 (3.61), 8.258 (4.18), 8.283 (1.97), 8.338 (4.25), 8.341 (3.98), 8.591 (4.24), 8.600 (4.41), 8.675 (2.70), 8.680 (4.98), 9.324 (2.28), 9.334 (2.17). I-18 [00089] (rac)-3-Bromo-5-cyano-N-{1-[3-(3-methyl-1H-1,2,4- triazol-1-yl)pyrazin-2-yl]ethyl}benzamide LC-MS (Method 4): R.sub.t = 0.82 min; MS (ESIpos): m/z = 412 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.594 (6.79), 1.605 (6.74), 2.393 (16.00), 5.662 (1.14), 5.673 (1.71), 5.684 (1.11), 8.222 (3.50), 8.271 (2.00), 8.274 (3.34), 8.277 (2.21), 8.305 (2.09), 8.308 (2.92), 8.569 (3.01), 8.573 (3.21), 8.784 (3.09), 8.788 (3.09), 9.096 (4.66), 9.192 (1.62), 9.202 (1.57). I-19 [00090] (rac)-3-Chloro-5-cyano-N-{1-[3-(3-methyl-1H-1,2,4- triazol-1-yl)pyrazin-2-yl]ethyl}benzamide LC-MS (Method 2): R.sub.t = 1.48 min; MS (ESIpos): m/z = 368 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.595 (5.05), 1.607 (4.99), 2.393 (11.20), 3.288 (16.00), 3.290 (12.33), 3.294 (12.35), 5.667 (0.86), 5.678 (1.26), 5.689 (0.82), 8.134 (1.85), 8.137 (2.57), 8.140 (1.45), 8.192 (1.92), 8.195 (5.68), 8.198 (3.92), 8.569 (2.51), 8.573 (2.19), 8.784 (2.52), 8.788 (2.05), 9.097 (3.35), 9.191 (1.29), 9.202 (1.24). I-20 [00091] (rac)-3-Fluoro-N-{1-[3-(3-methyl-1H-1,2,4-triazol-1-yl) pyrazin-2-yl]ethyl}-5-(pentafluoro-lambda.sup.6-sulfanyl) benzamide LC-MS (Method 2): R.sub.t = 1.80 min; MS (ESIpos): m/z = 453 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.618 (6.63), 1.629 (6.57), 2.387 (16.00), 5.679 (1.09), 5.690 (1.63), 5.701 (1.07), 7.984 (1.16), 8.000 (1.11), 8.100 (0.77), 8.103 (1.35), 8.107 (0.88), 8.114 (0.79), 8.117 (1.31), 8.121 (0.81), 8.159 (2.14), 8.161 (2.74), 8.574 (3.18), 8.578 (3.26), 8.788 (3.20), 8.792 (3.08), 9.101 (4.73), 9.333 (1.47), 9.344(1.43).

Example I-21

(rac)-1-(3-{1-[3,5-Bis(trifluoromethyl)benzamido]ethyl}pyrazin-2-yl)-N-ethyl-N-methyl-1H-1,2,4-triazole-3-carboxamide

[0715] ##STR00092##

[0716] (rac)-1-{3-[1-Aminoethyl]pyrazin-2-yl}-N-ethyl-N-methyl-1H-1,2,4-triazole-3-carboxamide (70.0 mg, 254 μmol) was dissolved in DMF (2.1 mL). 3,5-Bis(trifluoromethyl)benzoic acid (98.4 mg, 381 μmol) and DIPEA (180 μl, 1.0 mmol) were added. The mixture was cooled to 0° C., HATU (193 mg, 509 μmol) was added and stirring was maintained over night. The reaction mixture was directly charged upon a preparative HPLC device and chromatographed (RP-C18, water-acetonitrile gradient with 0.1% ammonia). 107 mg (100% purity, 82% yield) of the title compound were isolated.

[0717] LC-MS (Method 2): R.sub.t=1.85 mi; MS (ESIpos): m/z=516 [M+H].sup.+

[0718] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.133 (2.72), 1.145 (9.16), 1.157 (10.61), 1.168 (3.84), 1.638 (10.73), 1.650 (10.59), 3.016 (16.00), 3.074 (10.75), 3.406 (0.85), 3.418 (1.90), 3.426 (1.96), 3.429 (1.95), 3.437 (1.84), 3.449 (0.80), 3.490 (0.83), 3.502 (2.41), 3.514 (2.36), 3.525 (0.76), 5.627 (0.71), 5.638 (1.09), 5.649 (0.87), 5.657 (1.22), 5.668 (1.70), 5.679 (1.09), 8.282 (4.82), 8.467 (9.67), 8.654 (5.05), 8.657 (5.05), 8.884 (5.13), 8.887 (4.93), 9.370 (3.69), 9.376 (5.53), 9.507 (1.34), 9.515 (2.50), 9.525 (1.80).

TABLE-US-00006 Structure IUPAC-Name LC-MS (method): Retention time; Mass found Example .sup.1H-NMR I-22 [00093] (rac)-1-(3-{1-[3,5-Bis(trifluoromethyl)benzamido]ethyl} pyrazin-2-yl)-1H-1,2,4-triazole-3-carboxamide LC-MS (Method 2): R.sub.t = 1.60 min; MS (ESIpos): m/z = 474 [M + H].sup.+ .sup.1H-NMR (400 MHz, DMSO-d6) δ [ppm]: −0.149 (0.88), 0.146 (0.86), 1.157 (0.75), 1.175 (1.49), 1.193 (0.83), 1.656 (15.74), 1.673 (16.00), 1.989 (2.81), 2.368 (1.07), 2.711 (1.09), 2.732 (0.85), 2.892 (0.96), 4.021 (0.69), 4.039 (0.68), 5.609 (0.60), 5.626 (2.68), 5.642 (4.11), 5.659 (2.73), 5.676 (0.65), 7.818 (4.51), 7.977 (4.63), 8.293 (6.65), 8.454 (15.88), 8.650 (7.91), 8.656 (8.59), 8.887 (8.16), 8.893 (8.05), 9.380 (12.45), 9.518 (4.30), 9.534 (4.24). I-23 [00094] (rac)-N-[1-(3-{3-[(cis)-2,6-Dimethylmorpholine-4- carbonyl]-1H-1,2,4-triazol-1-yl}pyrazin-2-yl)ethyl]- 3,5-bis(trifluoromethyl)benzamide LC-MS (Method 2): R.sub.t = 1.95 min; MS (ESIpos): m/z = 572 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 0.999 (11.23), 1.002 (11.89), 1.009 (11.65), 1.013 (11.15), 1.160 (13.70), 1.170 (13.47), 1.640 (8.60), 1.651 (16.00), 1.662 (8.57), 2.523 (1.74), 2.562 (1.65), 2.571 (1.61), 2.808 (1.42), 2.826 (2.94), 2.848 (2.92), 2.867 (1.52), 3.262 (0.69), 3.547 (1.34), 3.556 (2.77), 3.560 (3.09), 3.567 (3.39), 3.571 (3.70), 3.574 (3.34), 3.584 (2.83), 3.588 (2.46), 3.594 (1.27), 3.598 (1.14), 4.001 (1.75), 4.023 (1.72), 4.046 (1.70), 4.068 (1.65), 4.393 (3.40), 4.415 (3.35), 5.668 (1.43), 5.679 (2.43), 5.691 (2.63), 5.703 (2.44), 5.715 (1.46), 8.285 (7.53), 8.458 (15.89), 8.661 (5.06), 8.664 (8.13), 8.667 (5.12), 8.893 (7.64), 8.897 (7.37), 9.389 (7.18), 9.404 (7.47), 9.503 (2.25), 9.514 (2.24), 9.534 (2.36), 9.545 (2.24). I-24 [00095] (rac)-1-(3-{1-[3-Chloro-5-(trifluoromethoxy)benzamido] ethyl}pyrazin-2-yl)-N-ethyl-N-methyl-1H-1,2,4-triazole- 3-carboxamide LC-MS (Method 2): R.sub.t = 1.85 min; MS (ESIpos): m/z = 498 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.138 (4.99), 1.149 (10.12), 1.161 (5.06), 1.600 (9.97), 1.611 (9.92), 3.014 (16.00), 3.069 (10.81), 3.257 (0.45), 3.398 (0.88), 3.410 (1.99), 3.416 (1.98), 3.421 (1.97), 3.428 (1.95), 3.440 (0.84), 3.489 (0.87), 3.501 (2.46), 3.513 (2.39), 3.525 (0.81), 5.569 (0.76), 5.581 (1.15), 5.592 (0.92), 5.599 (1.29), 5.610 (1.77), 5.621 (1.16), 7.725 (4.49), 7.740 (4.50), 7.967 (3.95), 7.969 (4.19), 8.642 (5.08), 8.646 (5.41), 8.873 (5.34), 8.876 (5.37), 9.250 (1.49), 9.258 (2.48), 9.267 (1.97), 9.357 (3.74), 9.363 (5.73). I-25 [00096] (rac)-1-(3-{1-[3-Chloro-5-(methanesulfonyl)benzamido] ethyl}pyrazin-2-yl)-N-ethyl-N-methyl-1H-1,2,4-triazole- 3-carboxamide LC-MS (Method 2): R.sub.t = 1.33 min; MS (ESIpos): m/z = 492 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.035 (0.57), 1.045 (0.57), 1.139 (1.09), 1.151 (3.59), 1.162 (4.12), 1.174 (1.51), 1.617 (3.91), 1.628 (3.88), 2.012 (1.77), 3.018 (6.22), 3.069 (1.24), 3.081 (4.22), 3.289 (16.00), 3.304 (10.88), 3.422 (0.76), 3.432 (0.94), 3.443 (0.76), 3.505 (0.96), 3.517 (0.93), 5.611 (0.43), 5.630 (0.50), 5.641 (0.68), 5.652 (0.44), 8.113 (2.23), 8.199 (1.68), 8.202 (1.60), 8.276 (1.99), 8.278 (1.95), 8.648 (2.08), 8.652 (1.96), 8.881 (2.19), 8.885 (1.92), 9.363 (1.46), 9.370 (2.26), 9.381 (0.55), 9.390 (1.11), 9.401 (0.75). I-26 [00097] (rac)-1-{3-[1-(3-Chloro-5-cyanobenzamido)ethyl]pyrazin- 2-yl}-N-ethyl-N-methyl-1H-1,2,4-triazole-3-carboxamide LC-MS (Method 2): R.sub.t = 1.49 min; MS (ESIpos): m/z = 439 [M + H].sup.+ .sup.1H-NMR (600 MHz, DMSO-d6) δ [ppm]: 1.138 (2.99), 1.146 (4.96), 1.150 (6.49), 1.158 (8.61), 1.169 (3.88), 1.598 (9.83), 1.610 (9.66), 2.011 (0.72), 2.070 (1.58), 3.016 (16.00), 3.077 (10.82), 3.257 (0.45), 3.324 (0.63), 3.405 (0.89), 3.417 (1.95), 3.426 (2.09), 3.437 (1.87), 3.449 (0.81), 3.491 (0.88), 3.503 (2.50), 3.515 (2.41), 3.527 (0.80), 3.652 (0.82), 5.583 (0.76), 5.594 (1.15), 5.605 (0.93), 5.614 (1.29), 5.625 (1.74), 5.636 (1.12), 8.142 (4.63), 8.200 (9.32), 8.645 (4.90), 8.649 (4.96), 8.873 (5.22), 8.877 (4.92), 9.248 (1.44), 9.256 (2.50), 9.266 (1.88), 9.355 (3.63), 9.361 (5.42).

Example I-27

(rac)-N-{1-[3-(3-Cyano-1H-1,2,4-triazol-1-yl)pyrazin-2-yl]ethyl}-3,5-bis(trifluoromethyl)benzamide

[0719] ##STR00098##

[0720] (rac)-1-(3-{1-[3,5-Bis(trifluoromethyl)benzamido]ethyl}pyrazin-2-yl)-1H-1,2,4-triazole-3-carboxamide (example I-22, 100 mg, 211 μmol) was dissolved in THF (3.0 mL). Burgess' reagent (carbomethoxysulfamoyltriethylammoniumhydroxid, CAS-RN 29684-56-8, 151 mg, 634 μmol) was added and the resulting suspension was stirred at ambient temperature for 2 h. Then another portion of Burgess' reagent (50.3 mg, 211 μmol) was added and stirring was maintained over night. The reaction mixture was diluted with water and DMF (10.0 mL), charged in 2 portions onto a preparative HPLC device and chromatographed (RP-C18, water-acetonitrile gradient with 0.1% ammonia) to give 43.0 mg (100% purity, 45% yield) of the title compound.

[0721] LC-MS (Method 2): R.sub.t=2.05 min; MS (ESIpos): m/z=456 [M+H].sup.+

[0722] .sup.1H-NMR (600 MHz, DMSO-d6) δ[ppm]: 1.235 (0.81), 1.652 (16.00), 1.663 (15.90), 2.086 (0.43), 3.257 (0.52), 3.260 (0.45), 5.447 (0.66), 5.459 (2.65), 5.470 (3.90), 5.481 (2.56), 5.492 (0.59), 8.291 (6.19), 8.421 (14.63), 8.704 (7.71), 8.708 (7.55), 8.971 (7.70), 8.975 (7.18), 9.461 (3.81), 9.472 (3.68), 9.634 (13.18).

Example I-28

(rac)-Ethyl [4-(3-{1-[3,5-bis(trifluoromethyl)benzamido]ethyl}pyrazin-2-yl)-1H-1,2,3-triazol-1-yl]acetate

[0723] ##STR00099##

[0724] This compound was prepared in analogy to examples I-13 and I-17.

[0725] .sup.1H-NMR (600 MHz, d6-DMSO) δ (ppm)=1.25 (t, 3H), 1.63 (d, 3H), 48.58-8.61 (m, 2H), 8.76 (s, 1H). 22 (q, 2H), 5.53 (s, 2H), 6.28 (m, 1H), 8.30 (s, 1H), 8.54 (s, 1H), 8.59-8.62 (m, 2H), 8.72 (s, 1H), 9.51 (m, 1H).

Biological Examples

[0726] Rhipicephalus (Boophilus) microplus—In-Vitro Contact Tests Larval Cattle Tick (Strain Parkhurst, Resistant Against Synthetic Pyrethroids)

[0727] 9 mg compound is solved in 1 mL acetone and diluted with acetone to the desired concentration. 250 μL of the test solution is filled in 25 mL glass test tubes and homogeneously distributed on the inner walls by rotation and tilting on a shaking device (2 h at 30 rpm). With a compound concentration of 900 ppm, an inner surface of 44.7 cm.sup.2 and a homogeneous distribution, a dose of 5 pg/cm.sup.2 is achieved.

[0728] After the solvent has evaporated, each test tube is filled with 20-50 cattle tick larvae (Rhipicephalus microplus), closed with a perforated lid and incubated in a horizontal position at 85% relative humidity and 27° C. in an incubator. After 48 hours efficacy is determined. The larvae are patted on the ground of the tubes and negative geotactic behavior is recorded. Larvae that climb back to the top of the vial in a manner comparable to untreated control larvae are marked as alive, larvae not climbing back up comparable to untreated control larvae but are moving uncoordinatedly or only twitching their legs are marked as moribund, tick larvae remaining on the bottom and not moving at all are counted as dead.

[0729] A compound shows a good efficacy against Rhipicephalus microplus, if at a compound concentration of 5 μg/cm.sup.2 an efficacy of at least 80% is monitored. An efficacy of 100% means all larvae are dead or moribund; 0% means no larvae are dead or moribund.

[0730] In this test, for example, the following compounds from the preparation examples showed good activity of 100% at an application rate of 5 μg/cm.sup.2 (=500 g/ha): I-10, I-21, I-27, I-28.

[0731] In this test, for example, the following compounds from the preparation examples showed good activity of 90% at an application rate of 5 μg/cm.sup.2 (=500 g/ha): I-1, I-12.

Ctenocephalides felis—In-Vitro Contact Tests Adult Cat Flea

[0732] 9 mg compound is solved in 1 mL acetone and diluted with acetone to the desired concentration. 250 μL of the test solution is filled in 25 mL glass test tubes and homogeneously distributed on the inner walls by rotation and tilting on a shaking device (2 h at 30 rpm). With a compound concentration of 900 ppm, an inner surface of 44.7 cm.sup.2 and a homogeneous distribution, a dose of 5 μg/cm.sup.2 is achieved.

[0733] After the solvent has evaporated, each test tube is filled with 5-10 adult cat fleas (Ctenocephalides felis), closed with a perforated lid and incubated in a lying position at room temperature and relative humidity. After 48 hours efficacy is determined. The fleas are patted on the ground of the tubes and are incubated on a heating plate at 45-50° C. for at most 5 minutes. Immotile or uncoordinated moving fleas, which are not able to escape the heat by climbing upwards, are marked as dead or moribund.

[0734] A compound shows a good efficacy against Ctenocephalides felis, if at a compound concentration of 5 μg/cm.sup.2 an efficacy of at least 80% is monitored. An efficacy of 100% means all fleas are dead or moribund; 0% means no fleas are dead or moribund.

[0735] In this test, for example, the following compounds from the preparation examples showed good activity of 100% at an application rate of 5 μg/cm.sup.2 (=500 g/ha): I-28.

[0736] In this test, for example, the following compounds from the preparation examples showed good activity of 80% at an application rate of 1 μg/cm.sup.2 (=100 g/ha): I-21.

Rhipicephalus sanguineus—In-Vitro Contact Tests with Adult Brown Dog Ticks

[0737] 9 mg compound is solved in 1 mL acetone and diluted with acetone to the desired concentration. 250 μL of the test solution is filled in 25 mL glass test tubes and homogeneously distributed on the inner walls by rotation and tilting on a shaking device (2 h at 30 rpm). With a compound concentration of 900 ppm, an inner surface of 44.7 cm.sup.2 and a homogeneous distribution, a dose of 5 μg/cm.sup.2 is achieved.

[0738] After the solvent has evaporated, each test tube is filled with 5-10 adult brown dog ticks (Rhipicephalus sanguineus), closed with a perforated lid and incubated in a lying position at room temperature and relative humidity. After 48 hours efficacy is determined. The ticks are patted on the ground of the tubes and are incubated on a heating plate at 45-50° C. for at most 5 minutes. Immotile or uncoordinated moving ticks, which are not able to escape the heat by climbing upwards, are marked as dead or moribund.

[0739] A compound shows a good efficacy against Rhipicephalus sanguineus, if at a compound concentration of 5 μg/cm.sup.2 an efficacy of at least 80% is monitored. An efficacy of 100% means all ticks are dead or moribund; 0% means no ticks are dead or moribund.

[0740] In this test, for example, the following compounds from the preparation examples showed good activity of 100% at an application rate of 5 μg/cm.sup.2 (=500 g/ha): I-1.

[0741] In this test, for example, the following compounds from the preparation examples showed good activity of 80% at an application rate of 1 μg/cm.sup.2 (=100 g/ha): I-21

Diabrotica balteata—Spray Test

[0742] Solvent: 78.0 parts by weight of acetone [0743] 1.5 parts by weight of dimethylformamide

[0744] Emulsifier: alkylarylpolyglycol ether

[0745] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water, containing an emulsifier concentration of 1000 ppm, to the desired concentration. Further test concentrations are prepared by dilution with emulsifier containing water.

[0746] Soaked wheat seeds (Triticum aestivum) are placed in a multiple well plate filled with agar and some water and are incubated for 1 day to germinate (5 seeds per well). The germinated wheat seeds are sprayed with a test solution containing the desired concentration of the active ingredient. Afterwards each unit is infected with 10-20 larvae of the banded cucumber beetle (Diabrotica balteata).

[0747] After 7 days efficacy in % is determined. 100% means all the seedlings have grown up like in the untreated, uninfected control; 0% means none of the seedlings have grown.

[0748] In this test, for example, the following compounds from the preparation examples showed good activity of 100% at an application rate of 500 g/ha (=160 μg/well): I-1, I-28.

[0749] In this test, for example, the following compounds from the preparation examples showed good activity of 100% at an application rate of 100 g/ha (=32 μg/well): I-1, I-2, I-4, I-5, I-6, I-7, I-9, I-10, I-11, I-15.

[0750] In this test, for example, the following compounds from the preparation examples showed good activity of 80% at an application rate of 100 g/ha (=32 μg/well): I-20.

Myzus persicae—Oral Test

[0751] Solvent: 100 parts by weight acetone

[0752] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water to the desired concentration.

[0753] 50 μL compound solution is filled in microtiter plates and 150 μL IPL41 insect medium (33%+15% sugar) is added to obtain a total volume of 200 μL per well. Afterwards the plates are sealed with parafilm through which a mixed population of the green peach aphid (Myzus persicae) can suck on the compound preparation.

[0754] After 5 days mortality in % is determined. 100% means all aphids have been killed and 0% means none of the aphids have been killed.

[0755] In this test, for example, the following compounds from the preparation examples showed good activity of 100% at an application rate of 20 ppm: I-1.

Nezara viridula—Spray Test

[0756] Solvent: 78.0 parts by weight of acetone [0757] 1.5 parts by weight of dimethylformamide

[0758] Emulsifier: alkylarylpolyglycol ether

[0759] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water, containing an emulsifier concentration of 1000 ppm, to the desired concentration. Further test concentrations are prepared by dilution with emulsifier containing water.

[0760] Barley plants (Hordeum vulgare) are sprayed with a test solution containing the desired concentration of the active ingredient and are infested with larvae of the southern green stink bug (Nezara viridula).

[0761] After 4 days mortality in % is determined. 100% means all the stink bugs have been killed; 0% means none of the stink bugs have been killed.

[0762] In this test, for example, the following compounds from the preparation examples showed good activity of 100% at an application rate of 500 g/ha: I-1.

[0763] In this test, for example, the following compounds from the preparation examples showed good activity of 90% at an application rate of 500 g/ha: I-6.

[0764] In this test, for example, the following compounds from the preparation examples showed good activity of 70% at an application rate of 500 g/ha: I-4.

Nilaparvata lugens—Spray Test

[0765] Solvent: 78.0 parts by weight of acetone [0766] 1.5 parts by weight of dimethylformamide

[0767] Emulsifier: alkylarylpolyglycol ether

[0768] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvents and is diluted with water, containing an emulsifier concentration of 1000 ppm, to the desired concentration. Further test concentrations are prepared by dilution with emulsifier containing water.

[0769] Rice plants (Oryza sativa) are sprayed with a preparation of the active ingredient of the desired concentration and the plants are infested with the brown planthopper (Nilaparvata lugens).

[0770] After 4 days mortality in % is determined. 100% means all planthoppers have been killed and 0% means none of the planthoppers have been killed.

[0771] In this test, for example, the following compounds from the preparation examples showed good activity of 100% at an application rate of 500 g/ha: I-5, I-6.

[0772] In this test, for example, the following compounds from the preparation examples showed good activity of 90% at an application rate of 500 g/ha: I-3.

Spodoptera frugiperda—Spray Test

[0773] Solvent: 78.0 parts by weight acetone [0774] 1.5 parts by weight dimethylformamide

[0775] Emulsifier: alkylarylpolyglycol ether

[0776] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvents and is diluted with water, containing an emulsifier concentration of 1000 ppm, to the desired concentration. Further test concentrations are prepared by dilution with emulsifier containing water.

[0777] Maize (Zea mays) leaf sections are sprayed with a preparation of the active ingredient of the desired concentration. Once dry, the leaf sections are infested with fall armyworm larvae (Spodoptera frugiperda).

[0778] After 7 days mortality in % is determined. 100% means all caterpillars have been killed and 0% means none of the caterpillars have been killed.

[0779] In this test, for example, the following compounds from the preparation examples showed good activity of 100% at an application rate of 100 g/ha: I-3, I-9, I-12, I-20, I-25.

[0780] In this test, for example, the following compounds from the preparation examples showed good activity of 83% at an application rate of 20 g/ha: I-5.