Bicyclic compounds

Abstract

The present invention relates to compounds of formula I, ##STR00001##
wherein the variables are defined as given in the description and claims. The invention further relates to uses, processes and composition for compounds I.

Claims

1. A compound of formula (I) selected from the group consisting of a compound of formula (I-A) or (I-B): ##STR00057## wherein X is O or S; R.sup.x, R.sup.y independently of each other are selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, which are unsubstituted or substituted by halogen; C(O)—OR.sup.a, NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylen-NR.sup.bR.sup.c, O—C.sub.1-C.sub.6-alkylen-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylen-CN, NH—C.sub.1-C.sub.6-alkylen-NR.sup.bR.sup.c, C(O)—NR.sup.bR.sup.c, C(O)—R.sup.d, SO.sub.2NR.sup.bR.sup.c, S(═O).sub.mR.sup.c; phenyl and benzyl, wherein the phenyl ring is unsubstituted or substituted by radicals R.sup.f; R.sup.1 is partially or fully halogenated C.sub.1-C.sub.6-alkyl, partially or fully halogenated C.sub.1-C.sub.6-alkoxy, partially or fully halogenated C.sub.2-C.sub.6-alkenyl, partially or fully halogenated C.sub.2-C.sub.6-alkynyl, partially or fully halogenated C.sub.3-C.sub.6-cycloalkyl, partially or fully halogenated C.sub.3-C.sub.6-cycloalkoxy, partially or fully halogenated C.sub.1-C.sub.6-sulfenyl, partially or fully halogenated C.sub.1-C.sub.6-sulfinyl, or partially or fully halogenated C.sub.1-C.sub.6-sulfonyl; R.sup.2, R.sup.3, R.sup.4 independently of each other are selected from the group consisting of H, halogen, N.sub.3, CN, NO.sub.2, —SCN, —SF.sub.5, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, tri-C.sub.1-C.sub.6-alkylsilyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxyx-C.sub.1-C.sub.4-alkyl, which are unsubstituted or substituted by halogen, C(O)—OR.sup.a, NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylen-NR.sup.bR.sup.c, O—C.sub.1-C.sub.6-alkylen-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylen-CN, NH—C.sub.1-C.sub.6-alkylen-NR.sup.bR.sup.c, C(O)—NR.sup.bR.sup.c, C(O)—R.sup.d, SO.sub.2NR.sup.bR.sup.c and S(═O).sub.mR.sup.c, phenyl which is unsubstituted or substituted by radicals R.sup.f, phenoxy which is unsubstituted or substituted by radicals R.sup.f, phenylcarbonyl which is unsubstituted or substituted by radicals R.sup.f, phenylthio which is unsubstituted or substituted by radicals R.sup.f, or benzyl which is unsubstituted or substituted by radicals R.sup.f; Ar is phenyl or 5- or 6-membered heteroaryl, which are unsubstituted or substituted by radicals R.sup.Ar, which are identical or different, wherein R.sup.Ar independently of each other, are selected from the group consisting of halogen, N.sub.3, OH, CN, NO.sub.2, —SCN, —SF.sub.5, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, tri-C.sub.1-C.sub.6-alkylsilyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, which are unsubstituted or substituted by halogen, C(O)—OR.sup.a, NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylen-NR.sup.bR.sup.c, O—C.sub.1-C.sub.6-alkylen-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylen-CN, NH—C.sub.1-C.sub.6-alkylen-NR.sup.bR.sup.c, C(O)—NR.sup.bR.sup.c, C(O)—R.sup.d, SO.sub.2NR.sup.bR.sup.c and S(═O).sub.mR.sup.e, phenyl which is unsubstituted or substituted by radicals R.sup.f, phenoxy which is unsubstituted or substituted by radicals R.sup.f, phenylcarbonyl which is unsubstituted or substituted by radicals R.sup.f, phenylthio which is unsubstituted or substituted by radicals R.sup.f, or benzyl which is unsubstituted or substituted by radicals R.sup.f; each R.sup.a is selected from H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, which are unsubstituted or substituted by halogen, C.sub.1-C.sub.6-alkylen-NR.sup.bR.sup.c, C.sub.1-C.sub.6-alkylen-CN, phenyl and benzyl, wherein the phenyl ring is unsubstituted or substituted by radicals R.sup.f; each R.sup.b is selected from H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, which are unsubstituted or substituted by halogen, C.sub.1-C.sub.6-alkylen-CN, phenyl and benzyl, wherein the phenyl is unsubstituted or substituted by radicals R.sup.f; each R.sup.c is selected from H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, which are unsubstituted or substituted by halogen, C.sub.1-C.sub.6-alkylen-CN, phenyl and benzyl, wherein the phenyl ring is unsubstituted or substituted by radicals R.sup.f; each moiety NR.sup.bR.sup.c may also form an N-bound, saturated 5- to 8-membered heterocycle, which in addition to the nitrogen atom may have 1 or 2 further heteroatoms or heteroatom moieties selected from O, S(═O).sub.m and N—R′, wherein R′ is H or C.sub.1-C.sub.6-alkyl and wherein the N-bound heterocycle is unsubstituted or substituted by radicals selected from halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy and C.sub.1-C.sub.4-haloalkoxy; each R.sup.d is selected from H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, which are unsubstituted or substituted by halogen, phenyl and benzyl, wherein the phenyl ring is unsubstituted or substituted by radicals R.sup.f; each R.sup.e is selected from C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, which are unsubstituted or substituted by halogen, phenyl and benzyl, wherein the phenyl ring is unsubstituted or substituted by R.sup.f; each R.sup.f is selected from halogen, N.sub.3, OH, CN, NO.sub.2, SCN, SF.sub.5, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6 alkynyl, C.sub.1-C.sub.6 alkoxy-C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.6 alkoxy-C.sub.1-C.sub.4 alkoxy, C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6 cycloalkoxy, C.sub.3-C.sub.6 cycloalkyl-C.sub.1-C.sub.4 alkyl, C.sub.3-C.sub.6 cycloalkoxy-C.sub.1-C.sub.4 alkyl, which are unsubstituted or substituted by halogen; m is 0, 1 or 2; and the N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof.

2. The compound of formula (I-A) according to claim 1, wherein R.sup.x is selected from C.sub.1-C.sub.3 alkyl, C.sub.2-C.sub.3 alkenyl, C.sub.2-C.sub.3 alkynyl, C.sub.3-C.sub.6 cycloalkyl, and C.sub.1-C.sub.3 haloalkyl; R.sup.1 is selected from partially or fully halogenated C.sub.1-C.sub.6 alkyl, partially or fully halogenated C.sub.1-C.sub.6 sulfenyl, partially or fully halogenated C.sub.1-C.sub.6 sulfinyl, and partially or fully halogenated C.sub.1-C.sub.6 sulfonyl; R.sup.2 is selected from H, CH.sub.3, C.sub.2H.sub.5, n-propyl, isopropyl, cyclopropyl, allyl and propargyl; R.sup.4 is selected from H, CH.sub.3, C.sub.2H.sub.5, n-propyl, isopropyl, cyclopropyl, allyl and propargyl; Ar is a phenyl or 5- or 6-membered heteroaryl substituted with R.sup.Ar, R.sup.Ar is selected from halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, S(═O).sub.mR.sup.e, phenyl, phenoxy, phenylcarbonyl, phenylthio and benzyl, wherein the phenyl ring is unsubstituted or substituted by radicals R.sup.f; R.sup.e is selected from C.sub.1-C.sub.3 alkyl, C.sub.3-C.sub.6 cycloalkyl, C.sub.1-C.sub.3 haloalkyl, and C.sub.3-C.sub.6 halocycloalkyl; R.sup.f is selected from Cl, F, Br, OCH.sub.3, OC.sub.2H.sub.5, SCH.sub.3, SC.sub.2H.sub.5, CN, CH.sub.3, C.sub.2H.sub.5, n-propyl, isopropyl, cyclopropyl, allyl, propargyl, CF.sub.3, CHF.sub.2, and CF.sub.2CF.sub.3.

3. The compound of formula (I-A) according to claim 1, wherein R.sup.x is CH.sub.3 or C.sub.2H.sub.5; R.sup.1 is selected from CF.sub.3, CF.sub.2CF.sub.3, CF(CF.sub.3).sub.2, SCF.sub.3, OCF.sub.3, OCHF.sub.2, S(═O)CF.sub.3, and S(═O).sub.2CF.sub.3; R.sup.2 is selected from H, CH.sub.3, and C.sub.2H.sub.5; R.sup.4 is selected from H, CH.sub.3, and C.sub.2H.sub.5; Ar is a phenyl or 5- or 6-membered heteroaryl substituted with S(═O).sub.mR.sup.e at the ortho position to bond connecting to 9-membered heteroaryl of compound of formula (I), and optionally further substituted with 1 or 2 R.sup.Ar.

4. The compound of formula (I-B) according to claim 1, wherein R.sup.y is selected from C.sub.1-C.sub.3 alkyl, C.sub.2-C.sub.3 alkenyl, C.sub.2-C.sub.3 alkynyl, C.sub.3-C.sub.6 cycloalkyl, and C.sub.1-C.sub.3 haloalkyl; R.sup.1 is selected from partially or fully halogenated C.sub.1-C.sub.6 alkyl, partially or fully halogenated C.sub.1-C.sub.6 sulfenyl, partially or fully halogenated C.sub.1-C.sub.6 sulfinyl, and partially or fully halogenated C.sub.1-C.sub.6 sulfonyl; R.sup.2 is selected from H, CH.sub.3, C.sub.2H.sub.5, n-propyl, isopropyl, cyclopropyl, allyl and propargyl; R.sup.3 is selected from H, CH.sub.3, C.sub.2H.sub.5, n-propyl, isopropyl, cyclopropyl, allyl and propargyl; Ar is a phenyl or 5- or 6-membered heteroaryl substituted with R.sup.Ar; R.sup.Ar is selected from halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, S(═O).sub.mR.sup.e, phenyl, phenoxy, phenylcarbonyl, phenylthio and benzyl, wherein the phenyl ring is unsubstituted or substituted by radicals R.sup.f; R.sup.e is selected from C.sub.1-C.sub.3 alkyl, C.sub.3-C.sub.6 cycloalkyl, C.sub.1-C.sub.3 haloalkyl, and C.sub.3-C.sub.6 halocycloalkyl; R.sup.f is selected from Cl, F, Br, OCH.sub.3, OC.sub.2H.sub.5, SCH.sub.3, SC.sub.2H.sub.5, CN, CH.sub.3, C.sub.2H.sub.5, n-propyl, isopropyl, cyclopropyl, allyl, propargyl, CF.sub.3, CHF.sub.2, and CF.sub.2CF.sub.3.

5. The compound of formula (I-B) according to claim 1, wherein R.sup.Y is CH.sub.3 or C.sub.2H.sub.5; R.sup.1 is selected from CF.sub.3, CF.sub.2CF.sub.3, CF(CF.sub.3).sub.2, SCF.sub.3, OCF.sub.3, OCHF.sub.2, S(═O)CF.sub.3, and S(═O).sub.2CF.sub.3; R.sup.2 is selected from H, CH.sub.3, and C.sub.2H.sub.5; R.sup.3 is selected from H, CH.sub.3, and C.sub.2H.sub.5; Ar is a phenyl or 5- or 6-membered heteroaryl substituted with S(═O).sub.mR.sup.e at the ortho position to bond connecting to 9-membered heteroaryl of compound of formula (I), and optionally further substituted with 1 or 2 R.sup.Ar.

6. The compound of formula (I) according to claim 1, wherein R.sup.1 is partially or completely halogenated C.sub.1-C.sub.2-alkyl.

7. The compound of formula (I) according to claim 1, wherein Ar is substituted with S(═O).sub.2R.sup.e at the ortho-position to the bond connecting to the 9-membered heteroaryl of formula (I), and further substituted with one radical R.sup.Ar.

8. The compound of formula (I) according to claim 7, wherein Re is CH.sub.2CH.sub.3.

9. The compound of formula (I) according to claim 1, wherein Ar is pyridyl.

10. The compound of formula (I) according to claim 1, wherein Ar is a group of formula Ar-10h: ##STR00058##

11. The compound of formula (I) according to claim 1, wherein R.sup.x is selected from partially or fully halogenated C.sub.1-C.sub.3-alkyl.

12. The compound of formula (I) according to claim 1, wherein R.sup.2 is H.

13. The compound of formula (I) according to claim 1, wherein: the compound of formula (I) is selected to be the compound of formula (I-A); R.sup.x selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.4-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, which are unsubstituted or substituted by halogen; phenyl and benzyl, wherein the phenyl ring is unsubstituted or substituted by radicals R.sup.f; R.sup.2 is selected from H, CH.sub.3, and C.sub.2H.sub.5; R.sup.4 is selected from H, CH.sub.3, and C.sub.2H.sub.5; and Ar is a phenyl or 5- or 6-membered heteroaryl substituted with S(═O).sub.mR.sup.e at the ortho position to bond connecting to 9-membered heteroaryl of compound of formula (I-A), and optionally further substituted with 1 or 2 R.sup.Ar.

14. A composition comprising the compound of formula I, as defined in claim 1, an N-oxide or an agriculturally acceptable salt thereof.

15. The composition according to claim 14, comprising additionally a further active substance.

16. A seed treated with a compound of the formula (I), as defined in claim 15, or the enantiomers, diastereomers or salts thereof, or the composition, as defined in claim 14, in an amount of from 0.1 g to 10 kg per 100 kg of seed.

17. A method for combating or controlling invertebrate pests, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound of the formula (I) according to claim 16 or the composition according to claim 14.

18. A method for protecting growing plants from attack or infestation by invertebrate pests, which method comprises contacting a plant, or soil or water in which the plant is growing, with a pesticidally effective amount of at least one compound of the formula (I), according to claim 1.

19. A method for protecting growing plants from attack or infestation by invertebrate pests, which method comprises contacting a plant, or soil or water in which the plant is growing, with a pesticidally effective amount of at least one compound of the formula (I), according to the composition according to claim 14.

20. A method for treating or protecting an animal from infestation or infection by invertebrate pests which comprises bringing the animal in contact with a pesticidally effective amount of at least one compound of the formula (I) as defined in claim 1, a stereoisomer thereof and/or at least one veterinarily acceptable salt thereof.

21. The method of claim 18, wherein the compound of formula (I) is the compound of formula (I-A), R.sup.x is selected from C.sub.1-C.sub.3 alkyl, C.sub.2-C.sub.3 alkenyl, C.sub.2-C.sub.3 alkynyl, C.sub.3-C.sub.6 cycloalkyl, and C.sub.1-C.sub.3 haloalkyl; R.sup.1 is selected from partially or fully halogenated C.sub.1-C.sub.6 alkyl, partially or fully halogenated C.sub.1-C.sub.6 sulfenyl, partially or fully halogenated C.sub.1-C.sub.6 sulfinyl, and partially or fully halogenated C.sub.1-C.sub.6 sulfonyl; R.sup.2 is selected from H, CH.sub.3, C.sub.2H.sub.5, n-propyl, isopropyl, cyclopropyl, allyl and propargyl; R.sup.4 is selected from H, CH.sub.3, C.sub.2H.sub.5, n-propyl, isopropyl, cyclopropyl, allyl and propargyl; Ar is a phenyl or 5- or 6-membered heteroaryl substituted with R.sup.Ar; R.sup.Ar is selected from halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, S(═O).sub.mR.sup.e, phenyl, phenoxy, phenylcarbonyl, phenylthio and benzyl, wherein the phenyl ring is unsubstituted or substituted by radicals R.sup.f, R.sup.e is selected from C.sub.1-C.sub.3 alkyl, C.sub.3-C.sub.6 cycloalkyl, C.sub.1-C.sub.3 haloalkyl, and C.sub.3-C.sub.6 halocycloalkyl; R.sup.f is selected from Cl, F, Br, OCH.sub.3, OC.sub.2H.sub.5, SCH.sub.3, SC.sub.2H.sub.5, CN, CH.sub.3, C.sub.2H.sub.5, n-propyl, isopropyl, cyclopropyl, allyl, propargyl, CF.sub.3, CHF.sub.2, and CF.sub.2CF.sub.3.

22. The method of claim 18, wherein the compound of formula (I) is the compound of formula (I-A), R.sup.x is CH.sub.3 or C.sub.2H.sub.5; R.sup.1 is selected from CF.sub.3, CF.sub.2CF.sub.3, CF(CF.sub.3).sub.2, SCF.sub.3, OCF.sub.3, OCHF.sub.2, S(═O)CF.sub.3, and S(═O).sub.2CF.sub.3; R.sup.2 is selected from H, CH.sub.3, and C.sub.2H.sub.5; R.sup.4 is selected from H, CH.sub.3, and C.sub.2H.sub.5; Ar is a phenyl or 5- or 6-membered heteroaryl substituted with S(═O).sub.mR.sup.e at the ortho position to bond connecting to 9-membered heteroaryl of compound of formula (I), and optionally further substituted with 1 or 2 R.sup.Ar.

23. The method of claim 18, wherein the compound of formula (I) is the compound of formula (I-B), R.sup.y is selected from C.sub.1-C.sub.3 alkyl, C.sub.2-C.sub.3 alkenyl, C.sub.2-C.sub.3 alkynyl, C.sub.3-C.sub.6 cycloalkyl, and C.sub.1-C.sub.3 haloalkyl; R.sup.1 is selected from partially or fully halogenated C.sub.1-C.sub.6 alkyl, partially or fully halogenated C.sub.1-C.sub.6 sulfenyl, partially or fully halogenated C.sub.1-C.sub.6 sulfinyl, and partially or fully halogenated C.sub.1-C.sub.6 sulfonyl; R.sup.2 is selected from H, CH.sub.3, C.sub.2H.sub.5, n-propyl, isopropyl, cyclopropyl, allyl and propargyl; R.sup.3 is selected from H, CH.sub.3, C.sub.2H.sub.5, n-propyl, isopropyl, cyclopropyl, allyl and propargyl; Ar is a phenyl or 5- or 6-membered heteroaryl substituted with R.sup.Ar; R.sup.Ar is selected from halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, S(═O).sub.mR.sup.e, phenyl, phenoxy, phenylcarbonyl, phenylthio and benzyl, wherein the phenyl ring is unsubstituted or substituted by radicals R.sup.f, R.sup.e is selected from C.sub.1-C.sub.3 alkyl, C.sub.3-C.sub.6 cycloalkyl, C.sub.1-C.sub.3 haloalkyl, and C.sub.3-C.sub.6 halocycloalkyl; R.sup.f is selected from Cl, F, Br, OCH.sup.3, OC.sub.2H.sub.5, SCH.sub.3, SC.sub.2H.sub.5, CN, CH.sub.3, C.sub.2H.sub.5, n-propyl, isopropyl, cyclopropyl, allyl, propargyl, CF.sub.3, CHF.sub.2, and CF.sub.2CF.sub.3.

24. The method of claim 18, wherein the compound of formula (I) is the compound of formula (I-B), R.sup.Y is CH.sub.3 or C.sub.2H.sub.5; R.sup.1 is selected from CF.sub.3, CF.sub.2CF.sub.3, CF(CF.sub.3).sub.2, SCF.sub.3, OCF.sub.3, OCHF.sub.2, S(═O)CF.sub.3, and S(═O).sub.2CF.sub.3; R.sup.2 is selected from H, CH.sub.3, and C.sub.2H.sub.5; R.sup.3 is selected from H, CH.sub.3, and C.sub.2H.sub.5; Ar is a phenyl or 5- or 6-membered heteroaryl substituted with S(═O).sub.mR.sup.e at the ortho position to bond connecting to 9-membered heteroaryl of compound of formula (I), and optionally further substituted with 1 or 2 R.sup.Ar.

Description

EXAMPLES

(1) The present invention is now illustrated in further details by the following examples, without imposing any limitation thereto.

(2) With appropriate modification of the starting materials, the procedures as described in the examples below were used to obtain further compounds of formula I. The compounds obtained in this manner are listed in the Tables that follows, together with physical data.

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

(4) Analytical HPLC—Method 1: Phenomenex Kinetex 1,7 μm XB-C18 100A; 50×2,1 mm. Elution: acetonitrile+0.1% trifluoroacetic acid (TFA)/water+0.1% trifluoroacetic acid (TFA) in a ratio of from 5:95 to 95:5 in 1.5 minutes at 50° C. Method 2: BEH C18 1.7 μm; 50×2,1 mm. Elution: acetonitrile+0.1% formic acid (FA)/water+0.1% 0.1% formic acid (FA) in a ratio of from 5:95 to 95:5 in 5 minutes at 40° C.

(5) .sup.1H-NMR: The signals are characterized by chemical shift (ppm, δ [delta]) vs. tetramethylsilane, respectively CDCl.sub.3 for .sup.13C-NMR, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: m=multiplet, q=quartet, t=triplet, d=doublet and s=singlet.

(6) Abbreviations used are: d for day(s), h for hour(s), min for minute(s), r.t./room temperature for 20-25° C., Rt for retention time; DMSO for dimethyl sulfoxide, OAc for acetate, EtOAc for ethyl acetate, THF for tetrahydrofuran, m-CPBA for meta-chloroperbenzoic acid, Tf.sub.2O for triflic anhydride, PE for petroleum ether, Mel for methyl iodide, dppfPdCl.sub.2 for [1,1′-bis(diphenylphosphino)ferrocene]-dichloropalladium(II), DIPEA for diisopropylethylamine and t-BuOH for tert-butanol.

Example C-1

2-(2-chlorophenyl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (C-1 of Table 1)

(7) Step 1: To a solution of triphosgene (29.6 g) in CH.sub.2Cl.sub.2 (200 mL) was added a solution of p-methoxybenzylamine (13.7 g) in CH.sub.2Cl.sub.2 (200 mL), followed by the dropwise addition of Et.sub.3N (30 mL) in CH.sub.2Cl.sub.2 (100 mL). The resulting mixture was stirred at 25° C. for 14 h. Water (500 mL) was added and the reaction mixture was extracted with CH.sub.2Cl.sub.2 (3×200 mL). The organic layers were combined, washed with sat. NH.sub.4C.sub.1 (600 mL), brine (600 mL), dried over Na.sub.2SO.sub.4, filtered, and concentrated to afford 1-(isocyanatomethyl)-4-methoxy-benzene (17 g, crude) as yellow oil. .sup.1H NMR (CDCl.sub.3, 400 MHz) δ 7.26 (d, J=8.8 Hz, 2H), 6.95 (d, J=8.4 Hz, 2H), 4.45 (s, 2H), 3.85 (s, 3H).

(8) Step 2: To a solution of ethyl (Z)-3-amino-4,4,4-trifluoro-but-2-enoate (19 g) in DMF (500 mL) was added NaH (6 g) in portions at 0° C. The reaction mixture was then stirred at 0° C. for 1 h. The mixture was then added to 1-(isocyanatomethyl)-4-methoxy-benzene (17 g) at 0° C. The resulting mixture was stirred at 0° C. to 25° C. for 14 h. The solvent was removed under reduced pressure and water (1 L) was added, and the organic layer was separated. The aqueous layer was extracted with EtOAc (3×500 mL). The organic layers were combined, washed with brine (500 mL), dried over Na.sub.2SO.sub.4, filtered, and concentrated to afford crude 3-[(4-methoxyphenyl)methyl]-6-(trifluoromethyl)-1H-pyrimidine-2,4-dione (15 g) as yellow oil. .sup.1H NMR (MeOD, 400 MHz) δ 7.27 (d, J=8.8 Hz, 2H), 6.77 (d, J=8.4 Hz, 2H), 5.80 (s, 1H), 5.02 (s, 2H) 3.70 (s, 3H).

(9) Step 3: To a solution of 3-[(4-methoxyphenyl)methyl]-6-(trifluoromethyl)-1H-pyrimidine-2,4-dione (35 g) and K.sub.2CO.sub.3 (16 g) in DMF (300 mL) was added Mel (16.5 g, 7.24 mL, 116.2 mmol) at 25° C. The resulting mixture was then stirred at 25° C. for 12 h. The solvent was removed under reduced pressure. Water (300 mL) was added and the organic layer was separated. The aqueous layer was extracted with EtOAc (3×300 mL). The organic layers were combined, washed with brine (500 mL), dried over Na.sub.2SO.sub.4, filtered, and concentrated to afford crude 3-[(4-methoxyphenyl)methyl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4-dione (30 g) as yellow solid. .sup.1H NMR (MeOD, 400 MHz) δ 7.35 (d, J=8.8 Hz, 2H), 6.83 (d, J=8.8 Hz, 2H), 6.28 (s, 1H), 5.02 (s, 2H), 3.75 (s, 3H), 3.46 (s, 3H).

(10) Step 4: To a solution of 3-[(4-methoxyphenyl)methyl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4-dione (30 g) in CH.sub.3CN (200 mL) and water (50 mL) was added ceric ammonium nitrate (78.5 g) at 25° C. Then the reaction mixture was stirred at 25° C. for 14 h then an additional portion (50 g) of ceric ammonium nitrate was added. The resulting mixture was stirred at 25° C. for 14 h. Water (200 mL) was added and the organic layer was separated The aqueous layer was extracted with EtOAc (3×100 mL). The organic layers were combined, washed with aq. NaHCO.sub.3 (500 mL), dried over Na.sub.2SO.sub.4, filtered, and concentrated. The residue was purified by silica gel chromatography (PE:EtOAc=10:1 to 1:1 gradient) to afford 1-methyl-6-(trifluoromethyl)pyrimidine-2,4-dione (8 g) as yellow solid. .sup.1H NMR (MeOD, 400 MHz) δ 6.20 (s, 1H), 3.44 (s, 3H).

(11) Step 5: To a solution of 1-methyl-6-(trifluoromethyl)pyrimidine-2,4-dione (8 g) in DCM (150 mL) and pyridine (30 mL) was added dropwise Tf.sub.2O (36.7 g) at 0° C. The mixture was then stirred at 0° C. to 25° C. for 3 h. Gaseous ammonia was passed through MeOH (50 mL) at −700° C. for 20 mins and the resulting methanol ammonia solution was poured into the reaction mixture. The resulting mixture was stirred at 25° C. for 12 h. The solvent was removed under reduced pressure. The residue was purified by preparative HPLC to afford 4-amino-1-methyl-6-(trifluoromethyl)pyrimidin-2-one (3.4 g) as yellow solid. .sup.1H NMR (DMSO-d.sub.6, 400 MHz) δ 7.62 (s, 1H), 7.52 (s, 1H), 6.24 (s, 1H), 3.30 (s, 3H).

(12) Step 6: A solution of 4-amino-1-methyl-6-(trifluoromethyl)pyrimidin-2-one (300 mg), 2-bromo-1-(2-chlorophenyl)ethanone (435 mg) in dimethylcarbonate (6 mL) was stirred at 110° C. for 13 h. The solvent was removed under reduced pressure. The residue was purified by preparative HPLC to afford 2-(2-chlorophenyl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (197 mg) as an off-white solid. .sup.1H NMR (DMSO-d.sub.6, 400 MHz) δ 8.38 (s, 1H), 8.14 (dd, J=2.0, 8.0 Hz, 1H), 7.59 (dd, J=1.2, 8.0 Hz, 1H), 7.53-7.38 (m, 3H), 3.59 (s, 3H).

Example C-4

2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-5-one (C-4 of Table 2)

(13) Step 1: A solution of ethyl 4,4,4-trifluoro-3-oxo-butanoate (46.0 g) and 2-(triphenylphosphoranylidene)acetonitrile (112.8 g) in ether (1 L) was stirred for 12 h at 20° C. The mixture was filtered and the filtrate was concentrated to give a residue, which was purified by chromatography (PE:EtOAc=10:1) to give ethyl 4-cyano-3-(trifluoromethyl)but-3-enoate (43.0 g, 83% yield) as light yellow oil. .sup.1H NMR (CDCl.sub.3, 400 MHz) δ 6.15 (s, 1H), 4.24 (q, J=7.2 Hz, 2H), 3.56 (s, 2H), 1.30 (t, J=7.2 Hz, 3H).

(14) Step 2: To a solution of ethyl 4-cyano-3-(trifluoromethyl)but-3-enoate (43.0 g) in EtOH (500 mL) was added N.sub.2H.sub.4.H.sub.2O (52.0 g), then the mixture was stirred for 12 h at 20° C. The mixture was filtered and the filtrate was concentrated to give a residue, which was purified by preparative HPLC to afford 1,6-diamino-4-(trifluoromethyl)pyridin-2-one (4.5 g) as an off-white solid.

(15) Step 3: To a solution of 1,6-diamino-4-(trifluoromethyl)pyridin-2-one (7.0 g) in DMF (105 mL) was added Mel (5.1 g), then the mixture was sealed and stirred for 12 h at 70° C. The mixture was concentrated to give a residue, which was purified by preparative HPLC to afford 6-amino-1-(methylamino)-4-(trifluoromethyl)pyridin-2-one (2.8 g) as yellow solid. .sup.1H NMR (CDCl.sub.3, 400 MHz) δ 6.21 (d, J=1.8 Hz, 1H), 5.67 (d, J=1.9 Hz, 1H), 5.39 (br s, 2H), 2.76 (s, 3H).

(16) Step 4: A mixture of 6-amino-1-(methylamino)-4-(trifluoromethyl)pyridin-2-one (1.5 g,) and 3-ethylsulfanylpyridine-2-carbaldehyde (1.2 g) in DMF (20 mL) was stirred at 130° C. for 12 h. The solvent was removed to afford 2-(3-ethylsulfanyl-2-pyridyl)-3-methyl-7-(trifluoromethyl)-1,2-dihydro-[1,2,4]triazolo[1,5-a]pyridin-5-one (2.5 g, crude) as light yellow solid.

(17) Step 5: To a mixture of 2-(3-ethylsulfanyl-2-pyridyl)-3-methyl-7-(trifluoromethyl)-1,2-dihydro-[1,2,4]triazolo[1,5-a]pyridin-5-one (550 mg,) in CH.sub.2Cl.sub.2 (10 mL) was added m-CPBA (938 mg, 85% purity) and the mixture was stirred for 1 h at 25° C. The solvent was removed to give a residue, which was purified by preparative HPLC to afford 2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-7-(trifluoromethyl)-1,2-dihydro-[1,2,4]triazolo[1,5-a]pyridin-5-one (45 mg) as off-white solid. .sup.1H NMR (CDCl.sub.3, 400 MHz) δ 8.69 (d, J=4.6 Hz, 1H), 8.38-8.33 (m, 1H), 7.56 (dd, J=4.9, 7.9 Hz, 1H), 6.49 (s, 1H), 6.22 (s, 1H), 6.18 (s, 1H), 5.86 (d, J=1.5 Hz, 1H), 4.09-3.99 (m, 1H), 3.98-3.88 (m, 1H), 1.39 (t, J=7.4 Hz, 3H).

(18) Step 6: A mixture of 2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-7-(trifluoromethyl)-1,2-dihydro-[1,2,4]triazolo[1,5-a]pyridin-5-one (200 mg,) and Pd/C (100 mg) in xylene (10 mL) was stirred for 12 h at 130° C. under O.sub.2 (15 psi). The mixture was filtered and the filtrate was concentrated to give a residue, which was purified by preparative-H PLC to afford 2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-5-one (38 mg, 17.4% yield) as light yellow solid. LC/MS t.sub.R=2.39 min, M+1=389.

(19) By analogous procedures to the procedure described above for example C-1, the following examples of formula I-A were prepared, wherein the substituents Ar, R.sup.1, R.sup.2, R.sup.x, R.sup.4 and X are as depicted in the Table 1.

(20) ##STR00019##

(21) TABLE-US-00002 TABLE 1 Physicochemical data: Example HPLC-Retention [min].sup.1 No Ar R.sup.1 R.sup.2 R.sup.x R.sup.4 X M + 1 t.sub.R (min) C-1  0 CF.sub.3 H CH.sub.3 H O 329.sup.2 3.48.sup.2 C-2  CF.sub.3 H CH.sub.3 H O 387.sup.2 3.82.sup.2 C-5  CF.sub.3 H CH.sub.3 H O 455 1.151 C-6  CF.sub.3 H CH.sub.3 H O 465.9 1.164 C-7  CF.sub.3 H CH.sub.3 H O 324 1.126 C-8  CF.sub.3 H CH.sub.3 H O 301 0.955 C-9  CF.sub.3 H CH.sub.3 H O 300 1.086 C-10 CF.sub.3 H CH.sub.3 H O 362 1.19 C-11 CF.sub.3 H CH.sub.3 H O 324.1 1.142 C-12 CF.sub.3 H CH.sub.3 H O 371.9 1.243 C-13 0 CF.sub.3 H CH.sub.3 H O 294.1 1.114 C-14 CF.sub.3 H CH.sub.3 H O 455 1.151 C-15 CF.sub.3 H CH.sub.3 H O 361.9 1.329 C-16 CF.sub.3 H CH.sub.3 H O 361.9 1.261 C-17 CF.sub.3 H CH.sub.3 H O 378 1.277 C-18 CF.sub.3 H CH.sub.3 H O 430 1.381 C-19 CF.sub.3 H CH.sub.3 H O 278 1.283 C-20 CF.sub.3 H CH.sub.3 H O 333.9 1.228 C-21 CF.sub.3 H CH.sub.3 H O 370 1.317 C-22 CF.sub.3 H CH.sub.3 H O 186 1.213 C-23 0 CF.sub.3 H CH.sub.3 H O 380 1.278 C-24 CF.sub.3 H CH.sub.3 H O 462 1.252 C-25 CF.sub.3 H CH.sub.3 H O 330 1.105 C-26 CF.sub.3 H CH.sub.3 H O 362 1.258 C-27 CF.sub.3 H CH.sub.3 H O 363 1.112 C-28 CF.sub.3 H CH.sub.3 H O 434 1.361 C-29 OCH.sub.2CF.sub.3 H CH.sub.3 H O 417.sup.2 2.15.sup.2 C-30 CF.sub.3 H CH.sub.3 H O 392 1.035 C-31 CF.sub.3 H CH.sub.3 CH.sub.3 O 308 1.143 C-32 CF.sub.3 H CH.sub.3 H O 405 1.259 C-33 0 CF.sub.3 H CH.sub.3 H S 471 1.269 C-34 CF.sub.3 H CH.sub.3 H O 463 1.20 C-35 CF.sub.3 H CH.sub.3 H O 427 1.09 C-36 CF.sub.3 H CH.sub.3 H O 497 1.304 1) Analytical HPLC - Method 1 unless otherwise stated; 2) Analytical HPLC - Method 2

(22) By analogous procedures to the procedure described above for example C-4, the following examples of formula I-B were prepared, wherein the substituents Ar, R.sup.1, R.sup.2, R.sup.3, R.sup.y and X are as depicted in the Table 2.

(23) ##STR00054##

(24) TABLE-US-00003 TABLE 2 Physicochemical data: HPLC-Retention [mm].sup.1 Example No Ar R.sup.1 R.sup.2 R.sup.3 R.sup.y X M + 1 t.sub.R (min) C-3 CF.sub.3 H H CH.sub.3 O 329 2.77 C-4 CF.sub.3 H H CH.sub.3 O 387 2.39 1) Analytical HPLC - Method 2

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

(26) If not otherwise specified, most test solutions are prepared as follow:

(27) The active compound is dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water:acetone. The test solution is prepared at the day of use.

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

(29) Boll Weevil (Anthonomus gandis)

(30) For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 96-well-microtiter plates containing an insect diet and 5-10 A. grandis eggs.

(31) The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 5 μl, using a custom built micro atomizer, at two replications.

(32) After application, microtiter plates were incubated at about 25±1° C. and about 75±5% relative humidity for 5 days. Egg and larval mortality was then visually assessed.

(33) In this test, compound C-1 and C-2 at 800 ppm showed over 75% mortality in comparison with untreated controls.

(34) Tobacco Budworm (Heliothis virescens) (2nd Instar Larvae)

(35) The active compounds were formulated by a Tecan liquid handler in 100% cyclohexanone as a 10,000 ppm solution supplied in tubes. The 10,000 ppm solution was serially diluted in 100% cyclohexanone to make interim solutions. These served as stock solutions for which final dilutions were made by the Tecan in 50% acetone:50% water (v/v) into 10 or 20 ml glass vials. A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01% (v/v). The vials were then inserted into an automated electrostatic sprayer equipped with an atomizing nozzle for application to plants/insects.

(36) Cotton plants were grown 2 plants to a pot and selected for treatment at the cotyledon stage. Test solutions were sprayed onto the foliage by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into perforated plastic bags with a zip closure. About 10 to 11 budworm larvae were placed into the bag and the bags zipped closed. Test plants were maintained in a growth room at about 25° C. and about 20-40% relative humidity for 4 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the bags. Mortality and reduced feeding were assessed 4 days after treatment, compared to untreated control plants.

(37) In this test, compound C-2 at 800 ppm showed over 75% mortality in comparison with untreated controls.

(38) Vetch Aphid (Megoura viciae)

(39) For evaluating control of vetch aphid (Megoura viciae) through contact or systemic means the test unit consisted of 24-well-microtiter plates containing broad bean leaf disks.

(40) The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the leaf disks at 2.5 μl, using a custom built micro atomizer, at two replications.

(41) After application, the leaf disks were air-dried and 5-8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids were then allowed to suck on the treated leaf disks and incubated at about 23±1° C. and about 50±5% relative humidity for 5 days. Aphid mortality and fecundity was then visually assessed.

(42) In this test, compound C-2 and C-4 at 800 ppm showed over 75% mortality in comparison with untreated controls.

(43) Cowpea Aphid (Aphis craccivora)

(44) The active compound is dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water:acetone. Surfactant (Kinetic® HV) is added at a rate of 0.01% (vol/vol). The test solution is prepared at the day of use.

(45) Potted cowpea plants were colonized with approximately 30-50 aphids of various stages by manually transferring a leaf tissue cut from infested plant 24 hours before application. Plants were sprayed with the test solutions using a DeVilbiss® hand atomizer at 20-30 psi (≈1.38 to 2.07 bar) after the pest population has been checked. Treated plants are maintained on light carts at about 25-26° C. Percent mortality was assessed after 72 hours.

(46) In this test, compound C-2 at 300 ppm showed over 75% mortality in comparison with untreated controls.

(47) Rice Green Leafhopper (Nephotettix virescens)

(48) Four to five-week old rice seedlings with cut upper leaf portion were cleaned and washed 24 hours before spraying. The active compounds were formulated in 1:1 acetone:water (vol:vol), and 0.01% vol/vol surfactant (Kinetic® HV) was added. Potted rice seedlings were sprayed with 5-6 ml test solution, air dried, covered with Mylar cages and inoculated with 10 adults. Treated rice plants were kept at about 28-29° C. and relative humidity of about 50-60%. Percent mortality was recorded after 72 hours.

(49) In this test, compound C-2 at 300 ppm showed over 75% mortality in comparison with untreated controls.

(50) Rice Brown Plant Hopper (Nilaparvata lugens)

(51) Four to five-week old rice seedlings were cleaned and washed 24 hours before spraying. The active compounds were formulated in 1:1 acetone:water (vol:vol) and 0.01% vol/vol surfactant (Kinetic® HV) was added. Potted rice seedlings were sprayed with 5-6 ml test solution, air dried, covered with Mylar cages and inoculated with 10 adults. Treated rice plants were kept at about 28-29° C. and relative humidity of about 50-60%. Percent mortality was recorded after 72 hours.

(52) In this test, compound C-2 at 300 ppm showed over 75% mortality in comparison with untreated controls.

(53) Diamond Back Moth (Plutella xylostella)

(54) The active compound is dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water:acetone. Surfactant (Kinetic® HV) is added at a rate of 0.01% (vol/vol). The test solution is prepared at the day of use.

(55) Leaves of cabbage were dipped in test solution and air-dried. Treated leaves were placed in petri dishes lined with moist filter paper and inoculated with ten 3.sup.rd instar larvae. Mortality was recorded 72 hours after treatment. Feeding damages were also recorded using a scale of 0-100%.

(56) In this test, compound C-2 and C-4 at 300 ppm showed over 75% mortality in comparison with untreated controls.

(57) Green Peach Aphid (Myzus persicae) (Mixed Life Stages)

(58) The active compounds were formulated by a Tecan liquid handler in 100% cyclohexanone as a 10,000 ppm solution supplied in tubes. The 10,000 ppm solution was serially diluted in 100% cyclohexanone to make interim solutions. These served as stock solutions for which final dilutions were made by the Tecan in 50% acetone:50% water (v/v) into 10 or 20 ml glass vials. A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01% (v/v). The vials were then inserted into an automated electrostatic sprayer equipped with an atomizing nozzle for application to plants/insects.

(59) Bell pepper plants at the first true-leaf stage were infested prior to treatment by placing heavily infested leaves from the main colony on top of the treatment plants. Aphids were allowed to transfer overnight to accomplish an infestation of 30-50 aphids per plant and the host leaves were removed. The infested plants were then sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood, removed, and then maintained in a growth room under fluorescent lighting in a 24-hr photoperiod at about 25° C. and about 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated control plants, was determined after 5 days.

(60) In this test, compound C-2 at 300 ppm showed over 75% mortality in comparison with untreated controls.

(61) Southern Armyworm (Spodoptera eridania), 2nd Instar Larvae

(62) The active compounds were formulated by a Tecan liquid handler in 100% cyclohexanone as a 10,000 ppm solution supplied in tubes. The 10,000 ppm solution was serially diluted in 100% cyclohexanone to make interim solutions. These served as stock solutions for which final dilutions were made by the Tecan in 50% acetone:50% water (v/v) into 10 or 20 ml glass vials. A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01% (v/v). The vials were then inserted into an automated electrostatic sprayer equipped with an atomizing nozzle for application to plants/insects.

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

(64) In this test, compound C-2 at 300 ppm showed over 75% mortality in comparison with untreated controls.