AZOLINE COMPOUNDS SUBSTITUTED BY A CARBOCYCLIC CONDENSED RING SYSTEM

Abstract

Compounds of formula (I)

##STR00001##

as defined herein are provided. Uses of these compounds for controlling invertebrate pests, protecting plant propagation material and providing an agricultural and a veterinary composition including the compounds are also described. Compounds for use as intermediate compounds in the preparation of compounds I are also described.

Claims

1. Azoline compounds of the formula I ##STR00035## wherein: X.sup.1 is selected from O and CH.sub.2; A is a group selected from A.sup.1, A.sup.2 and A.sup.3; wherein A.sup.1 is a group —C(R.sup.7a)(R.sup.7b)—N(R.sup.51)—C(═O)—R.sup.61; A.sup.2 is a group —CH(═NNH—C(O)—NH—R.sup.62); and A.sup.3 is a heterocyclic ring selected from heterocyclic rings of formulae D-1 to D-66: ##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042## wherein a zigzag line in the heterocyclic rings of formulae D-1 to D-66 denotes an attachment point to a remainder of the azoline compound; k is one of 0, 1, 2 and 3; and each R.sup.11 is independently selected from the group consisting of halogen, cyano, nitro, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy, C.sub.1-C.sub.4-alkylthio, C.sub.1-C.sub.4-haloalkylthio, C.sub.1-C.sub.6-alkylsulfinyl, C.sub.1-C.sub.6-haloalkylsulfinyl, C.sub.1-C.sub.6-alkylsulfonyl, C.sub.1-C.sub.6-haloalkylsulfonyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-haloalkenyl, C.sub.2-C.sub.4-alkynyl and C.sub.2-C.sub.4-haloalkynyl; B.sup.1, B.sup.2, B.sup.3, B.sup.4 and B.sup.5 are independently selected from a group consisting of N and CR.sup.2, wherein no more than one of B.sup.1, B.sup.2, B.sup.3, B.sup.4 and B.sup.5 is N; R.sup.g1 and R.sup.g2 form together a bridging group selected from —CH.sub.2CH.sub.2CH.sub.2— and —CH.sub.2CH.sub.2CH.sub.2CH.sub.2—; R.sup.1 is C.sub.1-haloalkyl; each R.sup.2 is independently selected from a group consisting of hydrogen, halogen, C.sub.1-C.sub.2-haloalkoxy and C.sub.1-C.sub.2-haloalkyl; R.sup.3a and R.sup.3b are independently selected from hydrogen and halogen; R.sup.7a and R.sup.7b are independently selected from hydrogen, cyano, methyl and C.sub.1-haloalkyl; R.sup.51 is selected from a group consisting of hydrogen, C.sub.1-C.sub.3-alkyl, C.sub.2-C.sub.3-alkenyl, C.sub.2-C.sub.3-alkynyl, C.sub.1-C.sub.3-alkoxymethyl and CH.sub.2—CN; R.sup.61 is selected from a group consisting of hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkyl substituted by up to two radicals R.sup.81, C.sub.1-C.sub.6-haloalkyl which carries one radical R.sup.81, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl which carries a CN substituent, C.sub.3-C.sub.6-halocycloalkyl, —N(R.sup.101a)R.sup.101b, —C(═O)N(R.sup.111a)R.sup.111b, —CH═NOR.sup.91, phenyl, phenyl which is substituted with up to 5 substituents R.sup.16 and a heterocyclic ring selected from rings of formulae E-1 to E-63; ##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048## wherein a zigzag line in the rings of formulae E-1 to E-63 denotes an attachment point to a remainder of the azoline compound, k is one of 0, 1, 2 and 3, n is one of 0, 1 and 2, and R.sup.16 is as defined below; R.sup.62 is selected from a group consisting of hydrogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-haloalkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.2-C.sub.4-haloalkynyl, C.sub.3-C.sub.5-cycloalkyl, C.sub.3-C.sub.5-halocycloalkyl, C.sub.3-C.sub.5-cycloalkyl-methyl-, C.sub.3-C.sub.5-cycloalkyl substituted with a CN group, C.sub.1-C.sub.4-alkyl substituted with a CN group, C.sub.1-C.sub.4-alkoxy and C.sub.1-C.sub.4-haloalkoxy; each R.sup.81 is independently selected from OH, CN, C.sub.3-C.sub.6-cycloalkyl C.sub.3-C.sub.6-cycloalkyl which carries a CN substituent, C.sub.3-C.sub.6-cycloalkyl which carries a C.sub.1-haloalkyl substituent, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-haloalkylthio, C.sub.1-C.sub.6-alkylsulfinyl, C.sub.1-C.sub.6-haloalkylsulfinyl, C.sub.1-C.sub.6-alkylsulfonyl, C.sub.1-C.sub.6-haloalkylsulfonyl, —C(═O)N(R.sup.101c)R.sup.101d, phenyl, phenyl substituted with up to 5 substituents R.sup.16, and the heterocyclic ring selected from the rings of formulae E-1 to E-63; R.sup.91 is selected from hydrogen, C.sub.1-C.sub.6-alkyl and C.sub.1-C.sub.6-haloalkyl; R.sup.101a, R.sup.101c and R.sup.111a are independently selected from hydrogen and C.sub.1-C.sub.6-alkyl; R.sup.101b is selected from hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, CH.sub.2—CN, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, C.sub.3-C.sub.6-halocycloalkylmethyl, phenyl, phenyl substituted with up to 5 substituents R.sup.16; and a heterocyclic ring selected from rings of formulae E-1 to E-42 as defined above; R.sup.101d and R.sup.111b are independently selected from hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-haloalkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl C.sub.3-C.sub.6-cycloalkyl which carries a CN substituent, C.sub.3-C.sub.6-halocycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl and C.sub.3-C.sub.6-halocycloalkylmethyl; each R.sup.16 is independently selected from the group consisting of halogen, cyano, nitro, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-haloalkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.2-C.sub.4-haloalkynyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy, C.sub.1-C.sub.4-alkylthio, C.sub.1-C.sub.4-haloalkylthio, C.sub.1-C.sub.4-alkylsulfinyl, C.sub.1-C.sub.4-haloalkylsulfinyl, C.sub.1-C.sub.4-alkylsulfonyl, C.sub.1-C.sub.4-haloalkylsulfonyl, C.sub.1-C.sub.4-alkylcarbonyl, C.sub.1-C.sub.4-haloalkylcarbonyl, aminocarbonyl, C.sub.1-C.sub.4-alkylaminocarbonyl and di-(C.sub.1-C.sub.4-alkyl)aminocarbonyl; and at least one of the N-oxides, stereoisomers and agriculturally or veterinarily acceptable salts thereof.

2. The compounds as claimed in claim 1, where X.sup.1 is O.

3. The compounds as claimed in claim 1, where X.sup.1 is CH.sub.2.

4. The compounds as claimed in claim 1, wherein A is the group A.sup.1, R.sup.7a is hydrogen; R.sup.7b is selected from hydrogen, CH.sub.3, CF.sub.3 and CN; R.sup.51 is selected from hydrogen and C.sub.1-C.sub.3-alkyl; and R.sup.61 is selected from C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.4-alkyl substituted by one radical R.sup.81, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl which carries a CN substituent, C.sub.3-C.sub.6-halocycloalkyl, phenyl, phenyl which is substituted with up to 5 substituents R.sup.16; and the heterocyclic ring selected from the rings of formulae E-1 to E-63; R.sup.81 is selected from CN, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl which carries one of a CN and a CF.sub.3 substituent, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-haloalkylthio, C.sub.1-C.sub.6-alkylsulfinyl, C.sub.1-C.sub.6-haloalkylsulfinyl, C.sub.1-C.sub.6-alkylsulfonyl, C.sub.1-C.sub.6-haloalkylsulfonyl, phenyl, phenyl optionally substituted with up to 3 substituents R.sup.16, and the heterocyclic ring selected from the rings of formulae E-1 to E-63; and the R.sup.16 in phenyl and in the rings of formulae E-1 to E-63 is selected from halogen, cyano, 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.

5. The compounds as claimed in claim 4, wherein R.sup.7a and R.sup.7b are hydrogen; R.sup.51 is hydrogen; and R.sup.61 is selected from C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.4-alkyl substituted by one radical R.sup.81, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl which carries a CN substituent and C.sub.3-C.sub.6-halocycloalkyl; where R.sup.81 is selected from CN, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl which carries one of a CN and a CF.sub.3 substituent, C.sub.3-C.sub.6-halocycloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-haloalkylthio, C.sub.1-C.sub.6-alkylsulfinyl, C.sub.1-C.sub.6-haloalkylsulfinyl, C.sub.1-C.sub.6-alkylsulfonyl and C.sub.1-C.sub.6-haloalkylsulfonyl.

6. The compounds as claimed in claim 1, wherein A is the group A.sup.2, wherein R.sup.62 is selected from hydrogen, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.3-haloalkyl, allyl, propargyl and cyclopropyl.

7. The compounds as claimed in claim 1, wherein A is the group A.sup.3, wherein A.sup.3 is selected from: the ring of formula D-59 wherein k is 0, and the ring of formula D-65 wherein k is 0, and the ring of formula D-65 wherein k is 1, R.sup.11 is CN bound in a 4-position, relative to a 1-position of the attachment point of the ring of formula D-65 to the remainder of the azoline compound and to a 2-position of a second nitrogen ring atom.

8. The compounds as claimed in claim 1, wherein B.sup.1, B.sup.3, B.sup.4 and B.sup.5 are CR.sup.2, and B.sup.2 is CR.sup.2a, wherein R.sup.2a is selected from halogen, C.sub.1-C.sub.2-haloalkoxy and C.sub.1-C.sub.2-haloalkyl.

9. The compounds as claimed in claim 1, wherein R.sup.2 is selected from hydrogen, F, Cl, Br, OCF.sub.3 and CF.sub.3.

10. The compounds as claimed in claim 1, wherein R.sup.g1 and R.sup.g2 form together the bridging group —CH.sub.2—CH.sub.2—CH.sub.2—.

11. The compounds as claimed in claim 1, wherein R.sup.g1 and R.sup.g2 form together the bridging group —CH.sub.2—CH.sub.2—CH.sub.2—CH.sub.2—.

12. The compounds as claimed in claim 1, wherein R.sup.1 is CF.sub.3.

13. The compounds as claimed in claim 1, wherein R.sup.3a and R.sup.3b are independently selected from hydrogen and fluorine.

14. A compound of formula II ##STR00049## wherein: B.sup.1, B.sup.2, B.sup.3, B.sup.4, B.sup.5, X.sup.1, R.sup.1, R.sup.3a, R.sup.3b, R.sup.g1 and R.sup.g2 are as defined in claim 1; and Y is selected from —C(R.sup.7a)(R.sup.7b)—N(H)R.sup.51 and —CN; wherein R.sup.7a, R.sup.7b and R.sup.51 are as defined in claim 1.

15. An agricultural or veterinary composition comprising at least one compound selected from the compounds of the formula I as defined in claim 1, at least one of a stereoisomer thereof, and at least one agriculturally or veterinarily acceptable salt thereof; and at least one of an inert liquid and an inert solid agriculturally or veterinarily acceptable carrier.

16. (canceled)

17. (canceled)

18. A method for protecting at least one of a plant propagation material and plants which grow therefrom from attack or infestation by invertebrate pests, wherein the method comprises treating the at least one of the plant propagation material and plants which grow therefrom with a pesticidally effective amount of at least one compound selected from the compounds of the formula I as defined in claim 1, a stereoisomer thereof and at least one agriculturally acceptable salt thereof.

19. The compounds as claimed in claim 1, wherein any two R.sup.16 present on a shared moeity form a linking group, the linking group selected from: ═O or ═S if the shared moeity is a carbon atom of a saturated ring; and ═N(C.sub.1-C.sub.6-alkyl), ═NO(C.sub.1-C.sub.6-alkyl), and ═NN(H)(C.sub.1-C.sub.6-alkyl) if the shared moeity is one of S in a heterocyclic ring and SO in a heterocyclic ring.

20. The compounds as claimed in claim 5, wherein R.sup.81 is selected from C.sub.1-C.sub.6-alkylsulfonyl and C.sub.1-C.sub.6-haloalkylsulfonyl.

21. The compounds as claimed in claim 6, wherein R.sup.62 is selected from C.sub.1-C.sub.3-alkyl and C.sub.1-C.sub.3-haloalkyl.

22. The compounds as claimed in claim 7, wherein A.sup.3 is the ring of formula D-59 and k is 0.

Description

EXAMPLES

[0419] The present invention is now illustrated in further details by the following examples, without imposing any limitation thereto.

I. PREPARATION EXAMPLES

[0420] Compounds can be characterized e.g. by coupled High Performance Liquid Chromatography/mass spectrometry (HPLC/MS), by .sup.1H-NMR and/or by their melting points.

Analytical HPLC Column:

[0421] Method A: Analytical UPLC column: Phenomenex Kinetex 1.7 μm XB-C18 100A; 50×2.1 mm from Phenomenex, Germany. Elution: acetonitrile/water+0.1% trifluoroacetic acid (TFA) in a ratio from 5:95 to 100:0 in 1.5 min; 100% B 0.24 min; Flow: 0.8 mL/min to 1 mL/min in 1.5 min at 60° C. MS-method: quadrupole electrospray ionization, 80 V (positive mode).

[0422] .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=multiplett, q=quartet, t=triplet, d=doublet and s=singlet.

[0423] Abbreviations used are: d for day(s), h for hour(s), min for minute(s), r.t./room temperature for 20-25° C., THF for tetrahydrofuran, DCE for 1,2-dichloroethane, MTBE for methyl-tert-butylether, DMF for N,N-dimethylformamide, dppf for 1,1′-bis(diphenyl-phosphino)ferrocene, Ph.sub.3P for triphenylphosphine, DIBAL-H for diisopropylaluminum hydride.

C.1 Compound Examples 1

[0424] Compound examples 1-1 to 1-5 correspond to compounds of formula C.1:

##STR00030##

wherein R.sup.2a, R.sup.2b, R.sup.2c and R.sup.61 of each synthesized compound is defined in one row of table C.1 below.

[0425] The compounds were synthesized in analogy to Synthesis Example S.1.

TABLE-US-00002 TABLE C.1 HPLC-MS: Ex. R.sup.2a, R.sup.2b, R.sup.2c —R.sup.61 Method, R.sub.t (min) & [M + H].sup.+ 1-1 Cl, F, Cl —CH.sub.2SO.sub.2CH.sub.3 A 1.367 567.0 1-2 Cl, F, Cl —CH.sub.2CH.sub.3 A 1.421 503.0 1-3 Cl, F, Cl —CH.sub.2CF.sub.3 A 1.455 557.0 1-4 Cl, F, Cl —CH.sub.3 A 1.384 488.9 1-5 Cl, F, Cl -cyclopropyl A 1.423 514.9

Synthesis Example S.1

N-[[7-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]indan-4-yl]methyl]acetamide

[0426] (Compound example 1-4; compound of formula C.1, wherein R.sup.2a and R.sup.2c are Cl, R.sup.2b is F, and —R.sup.61 is —CH.sub.3)

[0427] (7-Acetylindan-4-yl) trifluoromethanesulfonate (CAS 1312609-69-0) was synthesized as described in US 2011/0152246 (p. 118, compound I-IIIf).

Step 1: Methyl 7-acetylindane-4-carboxylate

[0428] To a solution of (7-acetylindan-4-yl) trifluoromethanesulfonate (40 g) in methanol (357 mL) were added Na.sub.2CO.sub.3 (27.5 g) and [1,1′-bis(diphenylphosphino)ferrocene]dichloro-palladium(II) (Pd(dppf)Cl.sub.2, 9.5 g). The solution was pressurized with carbon monoxide (50 Psi) and heated at 50° C. for 5 h. Then, the mixture was filtered and the filtrate was concentrated. The residue was dissolved in CH.sub.2Cl.sub.2 and washed with brine, dried (Na.sub.2SO.sub.4), filtered and concentrated to give a residue, which was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate) to afford the product (18.3 g, 64%).

[0429] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.9 (d, 1H), 7.7 (d, 1H), 4.0 (s, 3H), 3.3-3.2 (m, 4H), 2.6 (s, 3H), 2.1 (m, 2H).

Step 2: Methyl 7-[(3-(3,5-dichloro-4-fluoro-phenyl)-4,4,4-trifluoro-but-2-enoyl]indane-4-carboxylate

[0430] To a solution of the product of step 1 (12 g) and 1-(3,5-dichloro-4-fluoro-phenyl)-2,2,2-trifluoro-ethanone (28.7 g, CAS 1190865-44-1) in DCE (100 mL) was added K.sub.2CO.sub.3 (7.6 g) and triethylamine (7.6 mL). The reaction was stirred at reflux overnight. Then, the mixture was cooled to r.t., filtered and concentrated to give a residue, which was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate) to afford the product (18.75 g, 74%).

[0431] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.8 (m, 1H), 7.5 (m, 1H), 7.3 (m, 1H), 7.2 (m, 2H), 3.9 (s, 3H), 3.2 (m, 2H), 3.1 (m, 2H), 2.0 (m, 2H).

Step 3: Methyl 7-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]indane-4-carboxylate

[0432] To a solution of the product of step 2 (10 g) in THF (167 mL) was added hydroxylamine hydrochloride (3 g), followed by a drop wise addition of a solution of NaOH (3.5 g) in water (83 mL). The reaction was stirred at r.t. overnight, and concentrated. The residue was taken up in ethyl acetate, and the organic layer was washed with water (3×), dried (Na.sub.2SO.sub.4), filtered and concentrated to give a residue, which was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate) to afford the product (6 g, 58%).

[0433] .sup.1H NMR (400 MHz, MeOH-d.sub.4): δ 7.9 (d, 1H), 7.8 (m, 2H), 7.4 (d, 1H), 4.3 (d, 1H), 4.1 (d, 1H), 3.9 (s, 3H), 3.3 (m, 2H), 3.2 (m, 2H), 2.1 (m, 2H).

Step 4: [7-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]indan-4-yl]methanol

[0434] At r.t., to a solution of the product of step 3 (2 g) in THF (167 mL) was added LiBH.sub.4 (0.44 g). The reaction was stirred at 70° C. for 15 h. Then, saturated aqueous NH.sub.4Cl solution (100 mL) was added and the aqueous layer was extracted with ethyl acetate (3×100 mL). The combined organic layers were dried (Na.sub.2SO.sub.4), filtered and concentrated to give a residue, which was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate) to afford the product (1.3 g, 69%).

[0435] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.61 (m, 2H), 7.32 (d, 1H), 7.20 (d, 1H), 4.72 (s, 2H), 4.20-4.13 (m, 1H), 3.75 (m, 1H), 3.21 (m, 2H), 2.95 (m, 2H), 2.21-2.12 (m, 2H).

Step 5: [7-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]indan-4-yl]methyl methanesulfonate

[0436] At 0° C., a solution of the product of step 4 (2 g) in CH.sub.2Cl.sub.2 (60 mL) was treated with Et.sub.3N (3 mL) and methanesulfonyl chloride (“MsCl”, 1 g). The mixture was stirred at 25° C. for 10 h. Then, saturated aqueous NH.sub.4Cl solution (100 mL) was added and the aqueous layer was extracted with ethyl acetate (3×100 mL). The combined organic layers were dried (Na.sub.2SO.sub.4), filtered and concentrated to give a residue, which was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate) to afford the product (2.2 g).

Step 6: [7-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]indan-4-yl]methanamine

[0437] A solution of the product of step 5 (3.8 g) and NaN.sub.3 (0.95 g) in DMF (50 mL) was stirred at r.t. for 13 h. Then, water (100 mL) was added and the aqueous layer was extracted with MTBE (3×100 mL). The combined organic layers were dried (Na.sub.2SO.sub.4), filtered and concentrated. The obtained residue was dissolved in THF (80 mL) and water (80 mL), and Ph.sub.3P (2 g) was added. The mixture was stirred at 85° C. for 2 h. Then, the mixture was extracted with ethyl acetate (3×100 mL) and the combined organic layers were dried (Na.sub.2SO.sub.4), filtered and concentrated to give a residue, which was purified by flash chromatography on silica gel (CH.sub.2Cl.sub.2/CH.sub.3OH) to afford the product (2.2 g, 74%).

[0438] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.21 (br. s, 2H), 7.58 (m, 2H), 7.15 (m, 2H), 4.09 (d, 1H), 3.97 (m, 2H), 3.72 (d, 1H), 3.17 (m, 2H), 2.89 (m, 2H), 2.17-2.00 (m, 2H).

Step 7: N-[[7-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]indan-4-yl]methyl]acetamide

[0439] To a solution of the product of step 6 (0.3 g), acetic acid (0.04 g) and bromotripyrrolidinophosphonium hexafluorophosphate (“PyBroP”, 0.3 g) in CH.sub.2Cl.sub.2 (10 mL) at r.t. was added N,N-diisopropylethylamine (0.22 g). The reaction was stirred at r.t. overnight. Then, the reaction was concentrated to give a residue, which was purified by flash chromatography on silica gel to afford the product (0.2 g, 71%).

[0440] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.6-7.5 (m, 2H), 7.15-7.05 (m, 2H), 6.2 (m, 1H), 4.4-4.3 (m, 2H), 4.1 (d, 1H), 3.75 (d, 1H), 3.2-3.1 (m, 2H), 2.9-2.8 (m, 2H), 2.2-2.1 (m, 2H), 2.1 (s, 3H).

C.2 Compound Examples 2

[0441] Compound examples 2-1 to 2-4 correspond to compounds of formula C.2:

##STR00031##

wherein R.sup.2a, R.sup.2b, R.sup.2c and R.sup.62 of each synthesized compound is defined in one row of table C.2 below.

[0442] The compounds were synthesized in analogy to Synthesis Example S.2.

TABLE-US-00003 TABLE C.2 HPLC-MS: Method, R.sub.t (min) & [M + H].sup.+ Ex. R.sup.2a, R.sup.2b, R.sup.2c —R.sup.62 or .sup.1H-NMR 2-1 Cl, F, Cl —CH.sub.3 A 1.423 517.0 2-2 Cl, F, Cl —CH.sub.2CH.sub.3 A 1.463 531.0 2-3 Cl, F, Cl —CH.sub.2CF.sub.3 A 1.481 584.9 2-4 Cl, F, Cl —CH.sub.2CHF.sub.2 A 1.453 567.0

Synthesis Example S.2

1-[(E)-[7-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]indan-4-yl]methyleneamino]-3-(2,2,2-trifluoroethyl)urea

[0443] (Compound example 2-3; compound of formula C.2, wherein R.sup.2a and R.sup.2c are Cl, R.sup.2b is F and —R.sup.62 is —CH.sub.2CF.sub.3)

Step 1: 7-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]indane-4-carbaldehyde

[0444] A solution of [7-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]indan-4-yl]methanol (i.e. the product of synthesis examples S.1, step 4; 20 g) in CH.sub.2Cl.sub.2 (300 ml) was treated with pyridinium chlorochromate (“PCC”, 14 g) and stirred at r.t. for 15 h. The reaction was filtered and the filtrate was concentrated to afford a residue which was purified by flash chromatography on silica gel (ethyl acetate/petroleum ether) to afford the product (11 g, 55%).

[0445] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 10.20 (s, 1H), 7.73 (d, 1H), 7.60 (m, 2H), 7.35 (d, 1H), 4.17 (d, 1H), 3.78 (d, 1H), 3.35 (m, 2H), 3.23 (m, 2H), 2.21 (m, 2H).

Step 2: 1-[(E)-[7-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]indan-4-yl]methyleneamino]-3-(2,2,2-trifluoroethyl)urea

[0446] To a solution of the product of step 1 (0.3 g) and 1-ammonium-3-(2,2,2-trifluoroethyl) urea hydrochloride (160 mg) in ethanol (8 mL) was added acetic acid (2 drops) and the solution was stirred at reflux for 5 h and at r.t. overnight. The reaction was concentrated to afford a residue which was purified by flash chromatography on silica gel to afford the product (0.31 g, 78%).

[0447] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 9.6 (s, 1H), 7.9 (s, 1H), 7.6 (m, 2H), 7.5 (d, 1H), 7.2 (d, 1H), 6.5 (m, 1H), 4.2 (d, 1H), 4.1-4.0 (m, 2H), 3.75 (d, 1H), 3.3-3.1 (m, 2H), 3.1 (m, 2H), 2.2 (m, 2H).

C.3 Compound Examples 3

[0448] Compound examples 3-1 to 3-3 correspond to compounds of formula C.3:

##STR00032##

wherein R.sup.2a, R.sup.2b, R.sup.2c and R.sup.62 of each synthesized compound is defined in one row of table C.3 below.

[0449] The compounds were synthesized in analogy to Synthesis Example S.3.

TABLE-US-00004 TABLE C.3 HPLC-MS: Ex. R.sup.2a, R.sup.2b, R.sup.2c —R.sup.62 Method, R.sub.t (min) & [M + H].sup.+ 3-1 Cl, H, Cl —CH.sub.2CF.sub.3 A 1.417 565.3 3-2 Cl, H, Cl —CH.sub.2CH.sub.3 A 1.374 513.0 3-3 Cl, H, Cl —CH.sub.3 A 1.326 499.0

Synthesis Example S.3

1-[(E)-[7-[3-(3,5-Dichlorophenyl)-3-(trifluoromethyl)-2,4-dihydropyrrol-5-yl]indan-4-yl]methyleneamino]-3-(2,2,2-trifluoroethyl)urea

[0450] (Compound example 3-1; compound of formula C.3, wherein R.sup.2a and R.sup.2c are Cl, R.sup.2b is H and —R.sup.62 is —CH.sub.2CF.sub.3)

Step 1: [7-[3-(3,5-Dichlorophenyl)-4,4,4-trifluoro-but-2-enoyl]indan-4-yl]trifluoromethanesulfonate

[0451] To a solution of (7-acetylindan-4-yl) trifluoromethanesulfonate (60 g) in DCE (800 mL) was added 1-(3,5-dichlorophenyl)-2,2,2-trifluoro-ethanone (118 g, CAS 130336-16-2), triethylamine (26 g) and K.sub.2CO.sub.3 (35 g). The mixture was heated at reflux for 16 h, filtered, and concentrated. The residue was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate) to afford the product (65 g, 63%).

[0452] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.51 (d, 1H), 7.31-7.24 (m, 2H), 7.1 (m, 3H), 3.19 (m, 2H), 3.0 (m, 2H), 2.16-2.10 (m, 2H).

Step 2: [7-[3-(3,5-Dichlorophenyl)-4,4,4-trifluoro-3-(nitromethyl)butanoyl]indan-4-yl]trifluoromethanesulfonate

[0453] To a solution of the product of the product of step 1 (15 g) in CH.sub.3CN (200 mL) was added 1,8-diazabicyclo[5.4.0]undec-7-ene (“DBU”, 17 g) and CH.sub.3NO.sub.2 (8.6 g). The mixture was stirred at r.t. for 40 min. Then, the pH was adjusted to pH 5 with a 2 M aqueous HCl solution and the aqueous layer was extracted with ethyl acetate (3×500 mL). The combined organic phases were concentrated and the residue was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate) to afford the product (13 g, 79%).

[0454] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.83 (d, 1H), 7.45 (s, 1H), 7.31-7.24 (m, 1H), 7.21 (s, 2H), 5.67-5.58 (m, 1H), 5.49 (d, 1H), 4.12-3.94 (m, 2H), 3.32-3.03 (m, 4H), 2.18 (m, 2H).

Step 3: [7-[3-(3,5-Dichlorophenyl)-3-(trifluoromethyl)-2,4-dihydropyrrol-5-yl]indan-4-yl]trifluoromethanesulfonate

[0455] To a solution of the product of step 2 (26 g) in methanol (200 mL) was added acetic acid (200 mL) and iron powder (7.4 g) at r.t. The mixture was stirred at 80° C. for 12 h, concentrated and poured into a saturated aqueous NaHCO.sub.3 solution (100 mL). The aqueous layer was extracted with ethyl acetate (3×500 mL). The combined organic layers were concentrated to afford a residue, which was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate) to afford the product (23 g, 70%).

[0456] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.50 (d, 1H), 7.43-7.36 (m, 1H), 7.27 (m, 2H), 7.17 (d, 1H), 4.94 (d, 1H), 4.47 (d, 1H), 3.78 (d, 1H), 3.48 (d, 1H), 3.32 (m, 2H), 3.07 (m, 2H), 2.18 (m, 2H).

Step 4: 7-[3-(3,5-Dichlorophenyl)-3-(trifluoromethyl)-2,4-dihydropyrrol-5-yl]indane-4-carbaldehyde

[0457] To a solution of the product of step 3 (8 g) in DMF (100 mL) was added triethylsilane (3.4 g), Na.sub.2CO.sub.3 (1.9 g), and Pd(dppf)Cl.sub.2 (1.08 g). Under a CO-atmosphere, the mixture was stirred at 65° C. overnight, and then added to water (1 L). The aqueous layer was extracted with ethyl acetate (3×). The combined organic layers were washed with water (2×), dried (Na.sub.2SO.sub.4), filtered and concentrated to give a residue, which was purified by flash chromatography on silica gel (ethyl acetate/cyclohexane) to afford the product (1.7 g, 27%).

[0458] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 10.25 (s, 1H), 7.75 (d, 1H), 7.6 (d, 1H), 7.4 (s, 1H), 7.3 (m, 2H), 4.95 (d, 1H), 4.5 (d, 1H), 3.8 (d, 1H), 3.5 (d, 1H), 3.4-3.3 (m, 2H), 3.3-3.2 (m, 2H), 2.2 (m, 2H).

Step 5: 1-[(E)-[7-[3-(3,5-Dichlorophenyl)-3-(trifluoromethyl)-2,4-dihydropyrrol-5-yl]indan-4-yl]methyleneamino]-3-(2,2,2-trifluoroethyl)urea

[0459] To a solution of the product of step 4 (0.3 g) and 1-ammonium-3-(2,2,2-trifluoroethyl) urea hydrochloride (190 mg) in ethanol (5 mL) was added acetic acid (0.5 mL) and the solution was stirred at reflux overnight. The reaction was concentrated and re-dissolved in ethyl acetate. The organic layer was washed with water (3×), dried (Na.sub.2SO.sub.4), filtered and concentrated to give a residue, which was purified by flash chromatography on silica gel (ethyl acetate/cyclohexane) to afford the product (0.32 g, 80%).

C.4 Compound Examples 4

[0460] Compound examples 4-1 to 4-4 correspond to compounds of formula C.4:

##STR00033##

wherein R.sup.2a, R.sup.2b, R.sup.2c, X.sup.1 and A.sup.3 of each synthesized compound is defined in one row of table C.4 below.

[0461] The compounds were synthesized in analogy to Synthesis Example S.4.

TABLE-US-00005 TABLE C.4 R.sup.2a, R.sup.2b, HPLC-MS: Ex. R.sup.2c X.sup.1 -A.sup.3 Method, R.sub.t (min) & [M + H].sup.+ 4-1 Cl, F, Cl O 1,2,4-triazol-1-yl A 1.381 485.3 4-2 Cl, H, Cl CH.sub.2 1,2,4-triazol-1-yl A 1.371 465.0 4-3 Cl, F, Cl CH.sub.2 1,2,4-triazol-1-yl A 1.398 483.2 4-4 Cl, H, Cl O 1,2,4-triazol-1-yl A 1.451 467.2

Synthesis Example S.4

5-(3,5-Dichloro-4-fluoro-phenyl)-3-[7-(1,2,4-triazol-1-yl)indan-4-yl]-5-(trifluoromethyl)-4H-isoxazole

[0462] (Compound example 4-1; compound of formula C.4, wherein R.sup.2a and R.sup.2c are Cl, R.sup.2b is F, X.sup.1 is O and -A is 1,2,4-triazol-1-yl)

Step 1: 1-[7-(1,2,4-Triazol-1-yl)indan-4-yl]ethanone

[0463] To a solution of (7-acetylindan-4-yl) trifluoromethanesulfonate (10 g) in DMF (30 mL) were added 1H-[1,2,4]-triazole (3.1 g), CuI (1.2 g), K.sub.3PO.sub.4 (13.8 g) and (1S,2S)—N1,N2-dimethylcyclohexane-1,2-diamine (0.23 g). The mixture was stirred at 120° C. overnight.

[0464] Water was added and the aqueous layer was extracted with MTBE (3×). The combined organic layers were dried (Na.sub.2SO.sub.4), filtered and concentrated to give a residue, which was purified by flash chromatography on silica gel (ethyl acetate/cyclohexane) to afford the product (0.86 g, 12%).

[0465] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.5 (s, 1H), 8.15 (s, 1H), 7.8 (d, 1H), 7.5 (d, 1H), 3.35 (t, 2H), 3.1 (t, 3H), 2.6 (s, 3H), 2.2-2.1 (m, 2H).

Step 2: 3-(3,5-Dichloro-4-fluoro-phenyl)-4,4,4-trifluoro-1-[7-(1,2,4-triazol-1-yl)indan-4-yl]but-2-en-1-one

[0466] To a solution of the product of step 1 (1.5 g) in DCE (10 mL) was added 1-(3,5-dichloro-4-fluoro-phenyl)-2,2,2-trifluoro-ethanone (1.52 g, CAS 1190865-44-1), triethylamine (0.29 g) and K.sub.2CO.sub.3 (0.4 g). The mixture was heated at reflux overnight, filtered, and concentrated. The residue was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate) to afford the product (1.07 g, 78%).

[0467] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.5 (s, 1H), 8.15 (s, 1H), 7.7 (d, 1H), 7.6 (d, 1H), 7.3 (s, 1H), 7.2 (m, 2H), 3.2 (t, 2H), 3.05 (t, 3H), 2.2-2.1 (m, 2H).

Step 3: 5-(3,5-Dichloro-4-fluoro-phenyl)-3-[7-(1,2,4-triazol-1-yl)indan-4-yl]-5-(trifluoromethyl)-4H-isoxazole

[0468] To a solution of the product of step 2 (0.5 g) in ethanol (10 mL) was added hydroxylamine hydrochloride (0.1 g) and triethlyamine (0.16 g). The reaction was stirred at reflux for 20 h, and concentrated. The residue was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate) to afford the product (30 mg, 7%).

C.5 Compound Examples 5

[0469] Compound examples 5-1 to 5-2 correspond to compounds of formula C.5:

##STR00034##

wherein R.sup.2a, R.sup.2b, R.sup.2c and R.sup.61 of each synthesized compound is defined in one row of table C.5 below.

[0470] The compounds were synthesized in analogy to Synthesis Example S.5.

TABLE-US-00006 TABLE C.5 HPLC-MS: Ex. R.sup.2a, R.sup.2b, R.sup.2c —R.sup.61 Method, R.sub.t (min) & [M + H].sup.+ 5-1 Cl, H, Cl —CH.sub.2CH.sub.3 A 1.256 483.1 5-2 Cl, H, Cl —CH.sub.2SO.sub.2CH.sub.3 A 1.203 547.1

Synthesis Example S.5

Step 1: [7-[3-(3,5-Dichlorophenyl)-3-(trifluoromethyl)-2,4-dihydropyrrol-5-yl]indan-4-yl]methanol

[0471] At −78° C., a solution of 7-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-2,4-dihydropyrrol-5-yl]indane-4-carbaldehyde (i.e. the product of Synthesis Example S.3, Step 4, 1 g) in toluene (30 mL) was treated with DIBAL-H (1 M in toluene, 0.5 mL) and stirred at −78° C. for 1 h. Then, methanol was added dropwise (1 mL) at −78° C., and the solution was warmed to r.t. Then, a solution of Rochelle's salt (potassium sodium tartrate, CAS 304-59-6) was added, followed by vigorous stirring at r.t. overnight. The aqueous layer was extracted with ethyl acetate (2×). The organic layers were combined and washed with water (2×), dried (Na.sub.2SO.sub.4), filtered, and concentrated to obtain the crude product (0.59 g, 59%).

[0472] The crude product of step 1 was then transformed into compounds of formula C.5 following the same chemical sequence as described in Synthesis Example S.1 (steps 5, 6, 7)

II. EVALUATION OF PESTICIDAL ACTIVITY

[0473] The activity of the compounds of formula I of the present invention can be demonstrated and evaluated by the following biological test.

B.1 Diamond Back Moth (Plutella Xylostella)

[0474] The active compound was dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water: aceteone. Surfactant (Kinetic HV) was added at a rate of 0.01% (vol/vol).The test solution was prepared at the day of use.

[0475] 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%.

[0476] In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 2-1, 2-2, 2-3, 2-4, 3-1, 3-2, 3-3, 4-1 and 4-2 at 300 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.2 Green Peach Aphid (Myzus persicae)

[0477] For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane.

[0478] 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.

[0479] 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.

[0480] In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 2-1, 2-2, 2-3, 2-4, 3-1, 3-2 and 3-3 at 2500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.3 Vetch Aphid (Megoura viciae)

[0481] 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.

[0482] 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.

[0483] 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.

[0484] In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 2-1, 2-2, 2-3, 2-4, 3-1, 3-2 and 3-3 at 2500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.4 Tobacco Budworm (Heliothis virescens)

[0485] 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.

[0486] 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.

[0487] 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.

[0488] In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 2-1, 2-2, 2-3, 2-4, 3-1, 3-2 and 3-3 at 2500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.5 Boll Weevil (Anthonomus grandis)

[0489] 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.

[0490] 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.

[0491] 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.

[0492] In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 2-1, 2-2, 2-3, 2-4, 3-1, 3-2 and 3-3 at 2500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.6 Mediterranean Fruitfly (Ceratitis capitata)

[0493] For evaluating control of Mediterranean fruitfly (Ceratitis capitata) the test unit consisted of microtiter plates containing an insect diet and 50-80 C. capitata eggs. 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.

[0494] 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.

[0495] In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 2-1, 2-2, 2-3, 2-4, 3-1, 3-2 and 3-3 at 2500 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.7 Orchid Thrips (Dichromothrips Corbetti)

[0496] Dichromothrips corbetti adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions. For testing purposes, the test compound is diluted in a 1:1 mixture of acetone:water (vol:vol), plus Kinetic HV at a rate of 0.01% v/v.

[0497] Thrips potency of each compound was evaluated by using a floral-immersion technique. All petals of individual, intact orchid flowers were dipped into treatment solution and allowed to dry in Petri dishes. Treated petals were placed into individual re-sealable plastic along with about 20 adult thrips. All test arenas were held under continuous light and a temperature of about 28° C. for duration of the assay. After 3 days, the numbers of live thrips were counted on each petal. The percent mortality was recorded 72 hours after treatment.

[0498] In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 2-1, 2-2, 2-3, 2-4, 4-1 and 4-2 at 300 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.8 Rice Green Leafhopper (Nephotettix virescens)

[0499] 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.

[0500] In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 2-1, 3-3 and 4-1 at 300 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.9 Red Spider Mite (Tetranychus kanzawai)

[0501] The active compound was dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water: acetone. Add surfactant (Kinetic HV) was added at a rate of 0.01% (vol/vol).The test solution was prepared at the day of use.

[0502] Potted cowpea beans of 4-5 days of age were cleaned with tap water and sprayed with 1-2 ml of the test solution using air driven hand atomizer. The treated plants were allowed to air dry and afterwards inoculated with 30 or more mites by clipping a cassava leaf section from rearing population. Treated plants were placed inside a holding room at about 25-27° C. and about 50-60% relative humidity. Percent mortality was assessed 72 hours after treatment.

[0503] In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 2-2, 2-3 and 2-4 at 300 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.10 Southern Armyworm (Spodoptera eridania)

[0504] The active compounds were formulated in cyclohexanone as a 10,000 ppm solution supplied in tubes. The tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01% (v/v).

[0505] 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 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.

[0506] In this test, the compounds 1-3, 1-4, 1-5, 3-1, 3-3, at 10 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.11 Green Soldier Stink Bug (Nezara viridula)

[0507] The active compound was dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water: acetone. Surfactant (Kinetic HV) was added at a rate of 0.01% (vol/vol).The test solution was prepared at the day of use.

[0508] Soybean pods were placed in glass Petri dishes lined with moist filter paper and inoculated with ten late 3rd instar N. viridula. Using a hand atomizer, approximately 2 ml solution is sprayed into each Petri dish. Assay arenas were kept at about 25° C. Percent mortality was recorded after 5 days.

[0509] In this test, the compounds 1-1, 1-2, 1-3, 1-4, 1-5, 2-1, at 300 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.12 Neotropical Brown Stink Bug (Euschistus heros)

[0510] The active compound was dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water: acetone. Surfactant (Kinetic HV) was added at a rate of 0.01% (vol/vol).The test solution was prepared at the day of use.

[0511] Soybean pods were placed in microwavable plastic cups and inoculated with ten adult stage E. heros. Using a hand atomizer, approximately 1 ml solution is sprayed into each cup, insects and food present. A water source was provided (cotton wick with water). Each treatment was replicated 2-fold. Assay arenas were kept at about 25° C. Percent mortality was recorded after 5 days.

[0512] In this test, the compounds 1-3, 1-4, 1-5 at 100 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.

B.13 Brown Marmorated Stink Bug (Halyomorpha halys)

[0513] The active compound was dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water: acetone. Surfactant (Kinetic HV) was added at a rate of 0.01% (vol/vol).The test solution was prepared at the day of use.

[0514] Row peanuts and soybean seeds were placed into microwavable plastic cups and inoculated with five adult stage H. halys. Using a hand atomizer, approximately 1 ml solution is sprayed into each cup, insects and food present. A water source was provided (cotton wick with water). Each treatment is replicated 4-fold. Assay arenas are kept at about 25° C. Percent mortality was recorded after 5 days.

[0515] In this test, the compounds 1-3, 1-5 at 100 ppm, respectively, showed a mortality of at least 75% in comparison with untreated controls.