Bicyclic pesticidal 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 ##STR00048## wherein X is O or S; R.sup.x is 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 with 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.e, phenyl and benzyl, wherein the phenyl ring is unsubstituted or substituted with radicals R.sup.f; R.sup.1 is H, 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.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkoxy, C.sub.1-C.sub.6-alkylsulfenyl, C.sub.1-C.sub.6-alkylsulfinyl, or C.sub.1-C.sub.6-alkylsulfonyl which are substituted or unsubstituted with halogen; R.sup.2, R.sup.3 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 with 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 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, and benzyl wherein the phenyl ring is unsubstituted or substituted by radicals R.sup.f; Ar is phenyl or 5- or 6-membered heteroaryl, 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 with 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, and benzyl wherein the phenyl ring is unsubstituted or substituted by radicals R.sup.f; Het is 5- or 6-membered heteroaryl or 5- or 6-membered heterocyclyl, which is unsubstituted or substituted with R; R is halogen, oxo (═O), 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-haloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.’-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.1-C.sub.6-alkoxycarbonyl, 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, phenyl, 5- or 6-membered heteroaryl, or 5- or 6-membered heterocyclyl, wherein cyclic groups of R are unsubstituted or substituted with radicals R.sup.f; provided that R.sup.Ar and Het both are not present on the same atom of Ar; each R.sup.a is selected from the group consisting of 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 with 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 with radicals R.sup.f; each R.sup.b is selected from the group consisting of 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 with halogen, —(C═O)R, —C(═O)OR, —C(═O)NR, C.sub.1-C.sub.6-alkylen-CN, phenyl and benzyl, wherein the phenyl is unsubstituted or substituted with radicals R.sup.f; each R.sup.c is selected from the group consisting of 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-hd.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 with halogen, C.sub.1-C.sub.6-alkylen-CN, phenyl and benzyl, wherein the phenyl ring is unsubstituted or substituted with radicals R.sup.f; each moiety NR.sup.bR.sup.c may also form an N-bound, saturated 3- to 8-membered heterocycle, which in addition to the nitrogen atom may have 1 or 2 further heteroatoms or heteroatom moieties selected from the group consisting of 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 with radicals selected from the group consisting of 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 the group consisting of 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 with halogen, phenyl and benzyl, wherein the phenyl ring is unsubstituted or substituted with radicals R.sup.f; each R.sup.e is selected from the group consisting of 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 with halogen, phenyl and benzyl, wherein the phenyl ring is unsubstituted or substituted with R.sup.f; each R.sup.f is 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, 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, and C.sub.3-C.sub.6-cycloalkoxy-C.sub.1-C.sub.4-alkyl, which are unsubstituted or substituted with halogen; m is 0, 1 or 2; n is 0, 1 or 2; and the N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof.

2. The compound of formula I of claim 1, wherein X is O.

3. The compound of formula I of claim 1, wherein Het is selected from the group consisting of thiophenyl, oxazolidinyl, imidazolidinyl, pyrrolidinyl, piperidinyl, pyridinyl, oxazolyl, thiazolyl, pyrazolyl, imidazolyl, triazolyl, oxadiazolyl, tetrazolyl, and thiadiazolyl; wherein the Het is unsubstituted or substituted with R selected from the group consisting of halogen, oxo (═O), C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, 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, and C.sub.1-C.sub.6-alkoxycarbonyl.

4. The compound of formula I of claim 1, wherein R.sup.x is selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloalkyl, and C.sub.1-C.sub.6-haloalkyl; R.sup.1 is selected from the group consisting of partially or completely halogenated C.sub.1-C.sub.6-alkyl, partially or completely halogenated C.sub.1-C.sub.6-alkylsulfenyl, partially or completely halogenated C.sub.1-C.sub.6-alkylsulfinyl, and partially or completely halogenated C.sub.1-C.sub.6-alkylsulfonyl; R.sup.2 is selected from the group consisting of H, halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-cycloalkyl, and C.sub.3-C.sub.6-cycloalkoxy; R.sup.3 is selected from the group consisting of H, halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-cycloalkyl, and C.sub.3-C.sub.6-cycloalkoxy; Ar is a phenyl or 5- or 6-membered heteroaryl; n is 1 or 2; R.sup.Ar is selected from the group consisting of halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.6-haloalkoxy, 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, and benzyl wherein the phenyl ring is unsubstituted or substituted by radicals R.sup.f; R.sup.e is selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6-haloalkyl, and C.sub.3-C.sub.6-halocycloalkyl; R.sup.f is selected from the group consisting of halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, and C.sub.2-C.sub.6-alkynyl, which are unsubstituted or substituted with halogen; m is 0, 1, or 2.

5. The compound of formula I of claim 1, wherein Ar is 5- or 6-membered heteroaryl containing one heteroatom selected from the group consisting of 0, N, and S.

6. The compound of formula I of claim 1, wherein R.sup.x is C.sub.1-C.sub.6-alkyl; R.sup.1 is selected from the group consisting of partially or completely halogenated C.sub.1-C.sub.6-alkyl, partially or completely halogenated C.sub.1-C.sub.6-alkylsulfenyl, partially or completely halogenated C.sub.1-C.sub.6-alkylsulfinyl, and partially or completely halogenated C.sub.1-C.sub.6-alkylsulfonyl; R.sup.2 is selected from the group consisting of H, halogen, and C.sub.1-C.sub.6-alkyl; R.sup.3 is selected from the group consisting of H, halogen, and C.sub.1-C.sub.6-alkyl; Ar is pyridinyl or thiophenyl substituted with R.sup.Ar as 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 R.sup.Ar selected from the group consisting of halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, phenyl, and benzyl, wherein the phenyl ring of R.sup.Ar is unsubstituted or substituted with radicals R.sup.f; R.sup.e is selected from the group consisting of C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6-haloalkyl, and C.sub.3-C.sub.6 halocycloalkyl; R.sup.f is selected from the group consisting of halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, and C.sub.2-C.sub.6-alkynyl, which are unsubstituted or substituted with halogen; m is 0, 1, or 2; Het is selected from the group consisting of thiophenyl, oxazolidinyl, imidazolidinyl, pyrrolidinyl, piperidinyl, pyridinyl, oxazolyl, thiazolyl, pyrazolyl, imidazolyl, triazolyl, oxadiazolyl, and thiadiazolyl; wherein the Het is unsubstituted or substituted with R; R is selected from the group consisting of halogen, oxo (═O), C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, and C.sub.1-C.sub.6-alkoxycarbonyl.

7. The compound of formula I of claim 1, which corresponds to the compound of formula I-a, ##STR00049## wherein the circle in the ring containing Q denotes that the ring is aromatic ring; Q is S or N; R.sup.x is C.sub.1-C.sub.6-alkyl; R.sup.1 is selected from the group consisting of partially or completely halogenated C.sub.1-C.sub.6-alkyl, partially or completely halogenated C.sub.1-C.sub.6-alkylsulfenyl, partially or completely halogenated C.sub.1-C.sub.6-alkylsulfinyl, and partially or completely halogenated C.sub.1-C.sub.6-alkylsulfonyl R.sup.Ar is S(═O).sub.mR.sup.e; wherein R.sup.e is C.sub.1-C.sub.6-alkyl; Het is selected from the group consisting of thiophenyl, oxazolidinyl, imidazolidinyl, pyrrolidinyl, piperidinyl, pyridinyl, oxazolyl, thiazolyl, pyrazolyl, imidazolyl, triazolyl, oxadiazolyl, and thiadiazolyl; wherein the Het is unsubstituted or substituted with R; R is selected from the group consisting of halogen, oxo (═O), C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, and C.sub.1-C.sub.6-alkoxycarbonyl; m is 0, 1, or 2; o is 1 or 2.

8. The compound of formula I of claim 1, wherein X is O; R.sup.1 is partially or completely halogenated C.sub.1-C.sub.6-alkyl; R.sup.x is C.sub.1-C.sub.6-alkyl; R.sup.2 is H; R.sup.3 is H or C.sub.1-C.sub.6-alkyl; Het is selected from the group consisting of thiophenyl, pyrrolidinyl, piperidinyl, pyrazolyl, pyridinyl, triazolyl, and tetrazolyl; wherein the Het is unsubstituted or substituted with R; R is selected from the group consisting of halogen, oxo (═O), and C.sub.1-C.sub.6-haloalkyl; Ar is pyridinyl substituted with R.sup.Ar as S(═O).sub.mR.sup.e at the ortho position to bond connecting to 9-membered heteroaryl of compound of formula I; R.sup.e is C.sub.1-C.sub.6-alkyl.

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

10. The composition of claim 9, comprising additionally a further active substance.

11. A seed comprising a compound of the formula I, as defined in claim 1, or the enantiomers, diastereomers or salts thereof, in an amount of from 0.1 g to 10 kg per 100 kg of seed.

12. A seed comprising the composition of claim 9, in an amount of from 0.1 g to 10 kg per 100 kg of seed.

13. 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 of claim 1.

14. 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 of claim 1.

15. 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.

16. 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 the composition of claim 9.

17. 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 the composition of claim 9.

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 exam-ples 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) LC/MS Method:

(4) Machine: Shimadzu Nexera UHPLC+Shimadzu LCMS 20-20, ESI

(5) Column: Phenomenex Kinetex 1.7 μm XB-C18 100A, 50×2.1 mm″

(6) Method:

(7) Mobile Phase: A: water+0.1% TFA; B:ACN

(8) Temperature: 60° C.

(9) Gradient:5% B to 100% B in 1.50 min; 100% B 0.25 min

(10) Flow: 0.8 ml/min to 1.0 ml/min in 1.51 min

(11) MS method: ESI positive

(12) Mass range (m/z): 100-700

Example 1: Synthesis of 2-[3-ethylsulfonyl-6-[3-(trifluoromethyl)-1,2,4-triazol-1-yl]-2-pyridyl]-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (I-1-1)

(13) a) 2-bromo-1-(5-bromo-3-ethylsulfonyl-2-pyridyl)ethenone was synthesized following the pub-lished procedures: WO2016/71214. b) 1-(6-chloro-3-ethylsulfonyl-2-pyridyl)ethenone:

(14) Step 1: To a solution of 3,6-dichloropicolinic acid (120 g, 0.628 mol) in toluene (2 L), at room temperature, was added thionyl chloride (68.38 mL, 0.942 mol) and DMF (9.0 mL). The reaction was then warmed to 110° C. and stirred for 2 h. The reaction mixture was then concentrated in vacuo, to afford a residue. The residue was dissolved in toluene (2 L) and then ethane thiol (40.8 g, 0.659 mol) was added in a dropwise manner over 15 min, the reaction was then stirred for 1h at room temperature. The reaction mixture was then concentrated under reduced pressure to afford a residue. The residue was purified by column chromatography eluting with 10% EtOAc-Petether to afford S-ethyl 3,6-dichloropyridine-2-carbothioate a yellow solid (120 g, 81% yield). .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.77 (d, 1H, J=8.4 Hz), 7.44 (d, 1H, J=8.4 Hz), 3.03 (q, 2H, J=7.2 Hz), 1.36 (t, 3H, J=7.2 Hz).

(15) Step 2: To a solution of sodium hydroxide (37.45 g, 0.936 mol) in water (200 mL) was added ethanethiol (67.64 mL, 0.936 mol) in a dropwise manner over 15 min, the reaction was then stirred at the same temperature for 30 min. Then tetrabutylammonium bromide (45.27 g, 0.14 mol) was added and the reaction stirred for 30 min. A solution of S-ethyl 3,6-dichloropyridine-2-carbothioate (110 g, 0.468 mol) in toluene (300 mL) was then added to the reaction mixture in dropwise manner at room temperature and the reaction stirred for an additional 5 h at room temperature. The reaction mixture was then poured in to water (500 mL) and extracted with ethylacetate (3×600 mL). The combined organic layers were dried over anhydrous Na.sub.2SO.sub.4 and concentrated under reduced pressure to afford a residue. The crude residue was purified by column chromatography eluting with 15% EtOAc-Petether to afford S-ethyl 6-chloro-3-ethylsulfanyl-pyridine-2-carbothioate as an off white solid (98 g, 80% yield). .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.63 (d, 1H, J=8.4 Hz), 7.40 (d, 1H, J=8.8 Hz), 3.02 (q, 2H, J=7.2 Hz), 2.96 (q, 2H, J=7.6 Hz), 1.40 (t, 3H, J=7.2 Hz), 1.36 (t, 3H, J=7.2 Hz)

(16) Step 3: To a solution of S-ethyl 6-chloro-3-ethylsulfanyl-pyridine-2-carbothioate (70 g, 0.268 mol) in ethanol (300 mL) was added a solution lithium hydroxide (17.28 g, 0.402 mol) then the reaction mixture stirred at room temperature for 5 h. The reaction mixture was then concentrated under reduced pressure to afford a residue. The residue was dissolved in cooled water, acidified with 2N HCl upon which 6-chloro-3-ethylsulfanyl-pyridine-2-carboxylic acid precipitated as an off white solid. The 6-chloro-3-ethylsulfanyl-pyridine-2-carboxylic acid was collected, dried and used without further purification (55 g, 94% yield). .sup.1H NMR (400 MHz, DMSO-d.sub.6): δ 13.63 (s, 1H), 7.94 (d, 1H, J=8.4 Hz), 7.63 (d, 1H, J=8.4 Hz), 2.99 (q, 2H, J=7.2 Hz), 1.24 (t, 3H, J=7.2 Hz).

(17) Step 4: To a solution of 6-chloro-3-ethylsulfanyl-pyridine-2-carboxylic acid (55 g, 0.253 mol) in toluene (600 mL) at room temperature, was added thionyl chloride (27 mL, 0.380 mol) and DMF (1.5 mL) and then the reaction mixture was warmed to 110C and stirred for 2 h. The reaction mixture was then cooled to room temperature and concentrated under reduced pressure to obtain a residue. The residue was taken up in DCM (1 L) and added to a solution of N,O-dimethylhydroxylamine hydrochloride (47.32 g, 0.484 mol) & DIPEA (127.11 mL, 0.727 mol) in DCM (1 L) in a dropwise manner at 0° C. over 2 h. The reaction mixture was then allowed to warm to room temperature and stir for 4 h. The reaction mixture was then poured in to water (600 mL) and extracted with DCM (2×600 mL). The combined organic layers were dried over anhydrous Na.sub.2SO.sub.4 and concentrated under reduced pressure to afford a residue. The crude residue was purified by column chromatography eluting with 20% EtOAc-Petether to afford 6-chloro-3-ethylsulfanyl-N-methoxy-N-me-thyl-pyridine-2-carboxamide as a brown gum (54 g, 85% yield). .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.71 (d, 1H, J=8.4 Hz), 7.31 (d, 1H, J=8.4 Hz), 3.60 (s, 3H), 3.37 (s, 3H), 2.92 (t, 2H, J=7.2 Hz), 1.26 (t, 3H, J=7.2 Hz).

(18) Step 5: To a solution of 6-chloro-3-ethylsulfanyl-N-methoxy-N-methyl-pyridine-2-carboxamide (54 g, 0.207 mol) in dry THF (500 mL) at 0° C. was added CH.sub.3MgBr (207.69 mL, 0.623 mol, 3M in diethyl ether) in a dropwise manner, then the reaction mixture was allowed to warm to room temperature and stir for 4 h. The reaction was then quenched through the addition of a saturated aqueous NH.sub.4Cl solution (500 mL) and extracted with EtOAc (2×700 mL). The combined organic layers were dried over anhydrous Na.sub.2SO.sub.4 and concentrated under reduced pressure to afford a residue. The crude residue was purified by column chromatography eluting with 15% EtOAc-Petether to afford 1-(6-chloro-3-ethylsulfanyl-2-pyridyl)ethenone as an off white solid (38 g, 85% yield). .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.64 (d, 1H, J=8.8 Hz), 7.39 (d, 1H, J=8.4 Hz), 2.91 (q, 2H, J=7.6 Hz), 2.69 (s, 3H), 1.39 (t, 3H, J=7.6 Hz).

(19) Step 6: To a solution of 1-(6-chloro-3-ethylsulfanyl-2-pyridyl)ethanone (38 g, 0.176 mol) in CH.sub.2Cl.sub.2 (500 mL) at 0° C. was added m-CPBA (76.25 g, 0.441 mol) in a portionwise manner, the reaction mixture was then allowed to warm to room temperature and stir for 16 h. The reaction mixture was then poured in to water (1.0 L) and extracted with CH.sub.2Cl.sub.2 (2×1 L). The combined organic layers were washed with a 1M NaOH solution (2×500 mL) and water (2×500 mL), dried over anhydrous Na.sub.2SO.sub.4 and concentrated under reduced pressure to afford a residue. The crude residue was purified by column chromatography eluting with 20% EtOAc-Petether to afford 1-(6-chloro-3-ethyl-sulfonyl-2-pyridyl)ethenone as a white solid (33 g, 75% yield). .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.29 (d, 1H, J=8.4 Hz), 7.60 (d, 1H, J=8.0 Hz), 3.54 (q, 2H, J=7.6 Hz), 2.70 (s, 3H), 1.35 (t, 3H, J=7.2 Hz). c) 2-bromo-1-(5-bromo-3-ethylsulfonyl-2-pyridyl)ethanone

(20) To a solution of 1-(6-chloro-3-ethylsulfonyl-2-pyridyl)ethenone (10.00 g, 40.4 mmol) in acetic acid (140 mL) at room temperature, was sequentially added HBr (33% in Acetic acid) (8.60 g, 49.1 mmol), and bromine (6.55 g, 50.0 mmol). The reaction was then stirred at room temperature overnight, and then poured into 500 mL of stirring ice water, upon which a white solid precipitated. The solid was collected dried in a vacuum oven at 50 C for 18 hrs to afford the desired product (2-bromo-1-(5-bromo-3-ethylsulfonyl-2-pyridyl)ethenone)contaminated with 30% of the chloride containing product (2-bromo-1-(6-chloro-3-ethylsulfonyl-2-pyridyl)ethanone). This mixture was used in the next step without further purification.

(21) LC-MS 2-bromo-1-(5-bromo-3-ethylsulfonyl-2-pyridyl)ethenone: mass calculated for C.sub.9H.sub.10NO.sub.3SBr2 [M+H]+ 372.0, found 371.7; t.sub.R=1.027 min (t.sub.R: retention time).

(22) LC-MS 2-bromo-1-(6-chloro-3-ethylsulfonyl-2-pyridyl)ethenone: mass calculated for C.sub.9H.sub.10NO.sub.3SBrCl [M+H]+ 325.9, found 325.8; t.sub.R=1.007 min (t.sub.R: retention time). d) 2-(6-bromo-3-ethylsulfonyl-2-pyridyl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one:

(23) A solution of 3.0 g of the 7:3 mixture of 2-bromo-1-(5-bromo-3-ethylsulfonyl-2-pyridyl)ethenone and 2-bromo-1-(6-chloro-3-ethylsulfonyl-2-pyridyl)ethenone generated above and 4-amino-1-methyl-6-(trifluoromethyl)pyrimidin-2-one (1.55, 8.02 mmol) was dissolved in 70 ml 1,4-Dioxan and heated to 110° C. for 72 hrs. The reaction was then cooled to room temperature and concentrated in vacuo to afford a residue. The residue was purified by silica gel chromatography (25% n-heptane/CH2Cl2) to afford 1.55 g of a 7:3 mixture of 2-(6-bromo-3-ethylsulfonyl-2-pyridyl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one and 2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one as a off white solid.

(24) LC-MS 2-(6-bromo-3-ethylsulfonyl-2-pyridyl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one: mass calculated for C.sub.15H.sub.13N.sub.4O.sub.3F3SBr [M+H].sup.+ 466.2, found 466.9; t.sub.R=1.109 min (t.sub.R: retention time).

(25) LC-MS 2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one: mass calculated for C.sub.15H.sub.13N.sub.4O.sub.3F.sub.3SCl [M+H].sup.+ 421.0, found 420.9; t.sub.R=1.089 min (t.sub.R: retention time). e) 2-[3-ethylsulfonyl-6-[3-(trifluoromethyl)-1,2,4-triazol-1-yl]-2-pyridyl]-6-methyl-7-(trifluoromethyl) imidazo[1,2-c]pyrimidin-5-one (I-1-1):

(26) To a solution 3-(trifluoromethyl)-1H-1,2,4-triazole (0.162 g, 1.18 mmol) in NMP (3 mL) at room temperature, was added NaH (0.072 g, 1.18 mmol, 60% suspension in mineral oil used) in one portion. The reaction was stirred at room temperature for 30 min and then the 7:3 mixture of 2-(6-bromo-3-ethylsulfonyl-2-pyridyl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one and 2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (0.220 g, 0.473 mmol) generated above, was added in one portion. The reaction was then allowed to stir at room temperature overnight. The reaction was then poured into water (50 mL) and extracted to EtOAc (3×50 mL), The combined organic layers were dried over anhydrous Na.sub.2SO.sub.4 and concentrated under reduced pressure to afford a residue. The crude residue was purified by column chromatography eluting with 0-50% EtOAc-cyclohexane to afford 2-[3-ethylsulfonyl-6-[3-(trifluoromethyl)-1,2,4-triazol-1-yl]-2-pyridyl]-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one as a brown solid (0.140 g, 54% yield).

(27) LC-MS: mass calculated for C.sub.18H.sub.14N.sub.7O.sub.3F.sub.6S [M+H].sup.+ 522.4, found 522.0; t.sub.R=1.270 min (t.sub.R: retention time).

Example 2: 2-[3-ethylsulfonyl-5-(2-oxopyrrolidin-1-yl)-2-pyridyl]-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (I-1-3)

(28) a) 4-amino-1-methyl-6-(trifluoromethyl)pyrimidin-2-one

(29) 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.4Cl (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).

(30) 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).

(31) 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 MeI (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).

(32) 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).

(33) 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 −70° 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 H PLC 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). b) 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one:

(34) A solution of 4-amino-1-methyl-6-(trifluoromethyl)pyrimidin-2-one (0.900 g, 4.72 mmol), and 2-bromo-1-(5-bromo-3-ethylsulfonyl-2-pyridyl)ethenone (1.60 g, 2.30 mmol) in 1,4-dioxane (40 mL) was stirred at 140° C. in a microwave for 2.5 hrs. The reaction was then cooled to room temperature, diluted with EtOAc (200 mL), and washed with saturated aq. NaHCO.sub.3 (100 mL), dried over Na.sub.2SO.sub.4, filtered, and concentrated in vacuo to afford a residue. The residue was purified by column chromatography over silica gel (10-80% EtOAc/cyclohexane) to afford 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one as a white solid (0.700 g, 35% yield).

(35) LC-MS: mass calculated for C.sub.15H.sub.12N.sub.4O.sub.3F.sub.3SBr [M+H].sup.+ 364.9, found 364.9; t.sub.R=1.128 min (t.sub.R: retention time). c) 2-[3-ethylsulfonyl-5-(2-oxopyrrolidin-1-yl)-2-pyridyl]-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (I-1-3):

(36) To a solution of compound 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (0.150 g, 0.322 mmol), in DMA (1 mL) was sequentially added pyrrolidin-2-one (0.082 g, 0.967 mmol), tris(dibenzylidene acetone)dipalladium(0) (Pd.sub.2 dba.sub.3) (0.026 g, 0.032 mmol), xantphos (0.056 g, 0.097 mmol), and Cs.sub.2CO.sub.3 (0.210 g, 0.645 mmol). The solution was then stirred at room temperature for 10 minutes, and further reacted at 150° C. for 15 minutes in a microwave reactor (50 W irradiation). The reaction mixture was cooled to room temperature, filtered through a pad of celite and concentrated in vacuo to afford a residue. The residue was purified by column chromatography on silica gel (1.fwdarw.20% MeOH/CH.sub.2Cl.sub.2) to afford 2-[3-ethylsulfonyl-5-(2-oxopyrrolidin-1-yl)-2-pyridyl]-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one as a pale-yellow solid (0.070 g, 46% yield).

(37) LC-MS: mass calculated for C.sub.19H.sub.18N.sub.5O.sub.4F.sub.3S [M+H].sup.+ 470.1, found 470.0; t.sub.R=0.986 min (t.sub.R: retention time).

(38) By analogous procedures to the procedure described above, the following examples of formula I-1 and I-2 were prepared.

(39) ##STR00034##

(40) TABLE-US-00003 TABLE I-1 RT m/z No. R.sup.1 R.sup.2 R.sup.3 (min) (M + H) I-1-1 H H 1.27 522.0 I-1-2 H H 1.038 455.1 I-1-3 H H 0.986 470.0 I-1-4 H H 1.125 482.0 I-1-5 H H 1.033 453.9 I-1-6 H 0 H 1.048 454.0 I-1-7 H H 1.198 468.9 I-1-8 CH.sub.3 H 1.068 467.9 I-1-9 CH.sub.3 H 1.085 468.0 I-1-10 H H 1.14 453.0 I-1-11 H H 1.16 470.1

(41) ##STR00046##

(42) TABLE-US-00004 TABLE I-2 No. R.sup.1 R.sup.2 R.sup.3 RT (min) m/z (M + H) I-2-1 H H 1.032 453.9

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

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

(45) 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.

(46) Boll Weevil (Anthonomus grandis)

(47) 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.

(48) 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.

(49) 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.

(50) In this test, compounds I-1-1, I-2-1, I-1-2, I-1-3, I-1-4, I-1-5, I-1-6, I-1-7, I-1-9, and I-1-10 at 2500 ppm showed over 75% mortality in comparison with untreated controls.

(51) Tobacco Budworm (Heliothis virescens)

(52) For evaluating control of tobacco budworm (Heliothis virescens) the test unit consisted of 96-well-microtiter plates containing an insect diet and 15-25 H. virescens eggs.

(53) The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 10 μl, using a custom built micro atomizer, at two replications.

(54) After application, microtiter plates were incubated at about 28±1° C. and about 80±5% relative humidity for 5 days. Egg and larval mortality was then visually assessed.

(55) In this test, compounds I-1-1, I-2-1, I-1-2, I-1-3, I-1-4, I-1-5, I-1-6, I-1-7, I-1-9, and I-1-10 at 2500 ppm showed over 75% mortality in comparison with untreated controls.

(56) Vetch Aphid (Megoura viciae)

(57) 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.

(58) 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.

(59) 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.

(60) In this test, compounds I-1-2, I-1-3, I-1-4, I-1-6, I-1-9, and I-1-10

(61) at 2500 ppm showed over 75% mortality in comparison with untreated controls.

(62) Cowpea Aphid (Aphis craccivora)

(63) 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.

(64) 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.

(65) In this test, compound I-1-2, I-1-3, I-1-4, I-1-6, I-1-7, I-1-8, and I-1-9

(66) at 300 ppm showed over 75% mortality in comparison with untreated controls.

(67) Rice Green Leafhopper (Nephotettix virescens)

(68) 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.

(69) In this test, compound I-1-3, and I-1-8

(70) at 300 ppm showed over 75% mortality in comparison with untreated controls.

(71) Rice Brown Plant Hopper (Nilaparvata lugens)

(72) 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.

(73) In this test, compound I-1-3 at 300 ppm showed over 75% mortality in comparison with untreated controls.

(74) Diamond Back Moth (Plutella xylostella)

(75) 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.

(76) 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%.

(77) In this test, compound I-1-1, I-1-4, I-1-5, I-1-6, and I-1-8 at 300 ppm showed over 75% mortality in comparison with untreated controls.

(78) For evaluating control of green peach aphid (Myzuspersicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane.

(79) The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were pipetted into the aphid diet, using a custom built pipetter, at two replications.

(80) After application, 5-8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at about 23±1° C. and about 50±5% relative humidity for 3 days. Aphid mortality and fecundity was then visually assessed.

(81) In this test, compounds I-1-1, I-2-1, I-1-2, I-1-3, I-1-4, I-1-5, I-1-6, I-1-7, I-1-9, and I-1-10

(82) at 2500 ppm showed over 75% mortality in comparison with untreated controls.

(83) Southern Armyworm (Spodoptera Eridania)

(84) 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.

(85) Lima bean plants (variety Sieva) were grown 2 plants to a pot and selected for treatment at the 1.sup.st 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 250C 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.

(86) In this test, compound I-1-1, I-2-1, I-1-2, I-1-3, I-1-4, I-1-5, I-1-6, and I-1-9

(87) at 300 ppm showed over 75% mortality in comparison with untreated controls.

(88) Green Soldier Stink Bug (Nezara viridula)

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

(90) Soybean pods were placed in 90×50 mm glass Petri dishes lined with moist filter paper and inoculated with ten late 3rd instar N. viridula. Using a hand atomizer, an approximately 2 ml solution is sprayed into each Petri dish. Treated cups were kept at about 25-26° C. and relative humidity of about 65-70%. Percent mortality was recorded after 5 days.

(91) In this test, compounds I-1-3, and I-1-8 at 300 ppm showed over 75% mortality in comparison with untreated controls.

(92) Silverleaf Whitefly (Bemisia argentifolii)

(93) 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 5 or 10 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.

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

(95) In this test, compounds I-1-1, and I-1-4 at 300 ppm showed over 75% mortality in comparison with untreated controls.

(96) Striped Stem Borer (Chilo suppressalis)

(97) 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.

(98) Ten first-instar larvae are allowed to crawl on sprayed petriplates for 1 minute and then provided with one freshly cut rice straw per plate. After 10 minutes when all of the larvae are inside the straw will then be covered with Petri lid. Percent mortality is recorded after 72 hours after treatment.

(99) In this test, compounds I-1-4 at 300 ppm showed over 75% mortality in comparison with untreated controls.