SUBSTITUTED GLUTARIMIDE DERIVATIVES

Abstract

The invention relates to glutarimide compounds of formula I, (I) wherein the variables have the meanings as defined in the specification, to compositions comprising them, to active compound combinations comprising them, and to their use for protecting growing plants and animals from attack or infestation by invertebrate pests, furthermore, to seed comprising such compounds.

##STR00001##

Claims

1. A glutarimide compound of formula I ##STR00016## wherein W—Z is —O—N═, —CH.sub.2—N═, or —CH.sub.2—CH═; R.sup.1 halomethyl; R.sup.2a halogen, halomethyl, or halomethoxy; R.sup.2b, R.sup.2c are independently H, or as defined for Rea; R.sup.3 is halogen, CN, NO2, C, C.sub.2 alkyl, halomethyl, C.sub.1-C.sub.2-alkoxy, alkyl, C.sub.1-C.sub.2-haloalkoxy, or S(O).sub.m—C.sub.1-C.sub.2-haloalkyl; R.sup.4 is H, or as defined for R.sup.3; or R.sup.3 and R.sup.4 form together with the C-atoms they are bound to a 5-, or 6-membered saturated, partially, or fully unsaturated carbocyclic ring; R.sup.5, R.sup.6 are independently H, CN, C, C.sub.1-C.sub.10 alkyl, C.sub.3-C.sub.8-cycloalkyl, C.sub.2-C.sub.10-alkenyl, C.sub.3-C.sub.8-cycloalkenyl, C.sub.2-C.sub.10-alkynyl, OR.sup.10, S(O).sub.mR.sup.10, S(O).sub.mN(R.sup.10).sub.2, N(R.sup.10).sub.2, which aliphatic groups are unsubstituted, partially or fully halogenated and/or substituted with one or more R.sup.a; phenyl which is unsubstituted or substituted with one or more R.sup.A; and 3- to 7-membered saturated, partially or fully unsaturated heterocycle comprising 1, 2 or 3 heteroatoms 0, N(O).sub.n or S(O).sub.m as ring members, which heterocycle is unsubstituted or substituted with one or more R.sup.A, R.sup.10 is independently H, C.sub.3-C.sub.8-cycloalkyl, C.sub.3-C.sub.8-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.8-halocycloalkyl, 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, which groups are unsubstituted or substituted with one or more R.sup.a, R.sup.a is CN, N.sub.3, NO.sub.2, SCN, SF.sub.5, Si(C.sub.1-C.sub.4-alkyl).sub.3, OR.sup.a1, OSO.sub.2R.sup.a1, S(O).sub.mR.sup.a1, N(R.sup.a2)R.sup.a3, C(═O)N(R.sup.a2)R.sup.a3, C(═S)N(R.sup.a2)R.sup.a3, C(═O)R.sup.a1, C(═O)OR.sup.a1, CH═NOR.sup.a1, C.sub.3-C.sub.8-cycloalkyl, C.sub.3-C.sub.8-halocycloalkyl, which cyclic moieties may be substituted with R.sup.a4; phenyl which is unsubstituted or substituted with one or more R.sup.A; and 3- to 7-membered saturated, partially or fully unsaturated heterocycle comprising 1, 2 or 3 heteroatoms O, N(O).sub.n or S(O).sub.m as ring members, which heterocycle is unsubstituted or substituted with one or more R.sup.A, m is 0, 1, or 2; n is 0, or 1; R.sup.a1 H, 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 and hetaryl which aromatic rings are unsubstituted or partially or fully substituted with R.sup.A; R.sup.a2 is H, or C.sub.1-C.sub.6-alkyl, R.sup.a3 is H, 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, or C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-halocycloalkyl, C.sub.3-C.sub.6-cycloalkylmethyl, or C.sub.3-C.sub.6-halocycloalkylmethyl which rings are unsubstituted or substituted with a cyano; R.sup.a4 is independently OH, CN, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, S(O).sub.m—C.sub.1-C.sub.6-alkyl, S(O).sub.m—C.sub.1-C.sub.6-haloalkyl, C(═O)N(R.sup.a2)R.sup.a3, C.sub.3-C.sub.6-cycloalkyl, or C.sub.3-C.sub.6-halocycloalkyl which cycles are unsubstituted or substituted with one or more R.sup.a11; or phenyl, partially or fully unsaturated heterocycle which rings are unsubstituted or substituted with one or more R.sup.A; R.sup.a11 is independently OH, cyano, C.sub.1-C.sub.2-alkyl, or C.sub.1-C.sub.2-haloalkyl; R.sup.A is independently selected from halogen, CN, NO.sub.2, 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, S(O).sub.m—C.sub.1-C.sub.4-alkyl, S(O).sub.m—C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkylcarbonyl, C.sub.1-C.sub.4-haloalkylcarbonyl, C(═O)N(R.sup.a2)R.sup.a3; or two R.sup.A present on the same carbon atom of a saturated or partially saturated ring may form together ═O or ═S; or two R.sup.A present on the same S or SO ring member of a heterocyclic ring may together form a group ═N(C.sub.1-C.sub.6-alkyl), ═NO(C.sub.1-C.sub.6-alkyl), ═NN(H)(C.sub.1-C.sub.6-alkyl) or ═NN(C.sub.1-C.sub.6-alkyl).sub.2; and the N-oxides, stereoisomers and agriculturally or veterinarily acceptable salts thereof.

2. The compound of formula I according to claim 1, which corresponds to formula I.a ##STR00017##

3. The compound of formula I according to claim 1, which corresponds to formula I.Aa ##STR00018##

4. The compound of formula I according to claim 1, which corresponds to formula I.1 ##STR00019##

5. The compound of formula I according to claim 1, which corresponds to formula I.2 ##STR00020##

6. The compound of formula I according to claim 1, which corresponds to formula I.3 ##STR00021##

7. The compound of formula I according to claim 1, wherein R.sup.1 is halomethyl.

8. The compound of formula I according to claim 1, wherein R.sup.3 is halogen, NO.sub.2, CN, CH.sub.3, fluoromethyl, CF.sub.3, SCH.sub.3, or OCH.sub.3, and R.sup.4 is H.

9. The compound of formula I according to claim 1, wherein R.sup.5 is H, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl, or C.sub.2-C.sub.6-alkynyl.

10. The compound of formula I according to claim 1, wherein R.sup.6 is C.sub.1-C.sub.6-alkyl which is unsubstituted or substituted with phenyl or C(═O)—C.sub.1-C.sub.6-alkoxy; or R.sup.6 is C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.3-haloalkyl, C.sub.3-C.sub.4-cycloalkyl, C.sub.1-C.sub.3-alkoxy, C.sub.1-C.sub.3-haloalkoxy, C.sub.1-C.sub.4-alkylamino, and di-C.sub.1-C.sub.4-alkylamino.

11. The compound of formula I according to claim 1, wherein R.sup.1 is halomethyl; R.sup.2a, R.sup.2b, R.sup.2c are each selected from H, Cl, and F; R.sup.3 is Cl or CH.sub.3; R.sup.4 is H, or R.sup.3 and R.sup.4 together form a C.sub.3-carbon chain; R.sup.5 is H; and R.sup.6 is H, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.2-haloalkyl, c-C.sub.3H.sub.5, C.sub.1-C.sub.2-alkoxy, or di-C.sub.1-C.sub.4-alkylamino.

12. A composition comprising at least one compound according to claim 1 and/or at least one agriculturally acceptable salt thereof, and at least one inert liquid and/or solid agriculturally acceptable carrier.

13. An agricultural composition for combating animal pests comprising at least one compound as defined in claim 1 and at least one inert liquid and/or solid acceptable carrier and, if desired optionally, at least one surfactant.

14. A method for combating or controlling invertebrate pests, comprising contacting said pest or its food supply, habitat, or breeding grounds with a pesticidally effective amount of at least one compound as defined in claim 1.

15. A method for protecting growing plants from attack or infestation by invertebrate pests, comprising contacting a plant, or soil or water in which the plant is growing, with a pesticidally effective amount of at least one compound as defined in claim 1.

Description

EXAMPLES

A. Preparation Examples

[0189] With appropriate modification of the starting materials, the procedures given in the synthesis description were used to obtain further compounds I. The compounds obtained in this manner are listed in the table that follows, together with physical data.

[0190] The products shown below were characterized by melting point determination, by NMR spectroscopy or by the masses ([m/z]) or retention time (RT; [min.]) determined by HPLC-MS or HPLC spectrometry.

[0191] HPLC-MS=high performance liquid chromatography-coupled mass spectrometry;

[0192] HPLC method A: HPLC Phenomenex Kinetex 1.7 μm XB—C18 100A, 50×2.1 mm″, Mobile Phase: A: water+0.1% TFA; B:CAN; Temperature: 60° C.; Gradient: 5% B to 100% B in 1.50 min; 100% B 0.25 min; Flow: 0.8 ml/min to 1.0 ml/min in 1.51 min; MS method: ESI positive; Mass range (m/z): 100-700″.

[0193] HPLC method B: HPLC method: Phenomenex Kinetex 1.7 μm XB—C18 100A; 50×2.1 mm; mobile phase: A: water+0.1% trifluoroacetic acid (TFA); B: acetonitrile; gradient: 5-100% B in 1.50 minutes; 100% B 0.25 min; flow: 0.8-1.0 ml/min in 1.51 minutes at 60° C. MS: ESI positive, m/z 100-1400.

[0194] The synthesis of 2-chloro-4-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]benzoic acid and related carboxylic acids was performed in analogy to WO 2017/050922, WO 2013/026695, and WO 2016/102482.

Example 1: 2-chloro-4[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(3R)-1-methyl-2,6-dioxo-3-piperidyl]benzamide [Compound 1-1 of table C]

[0195] Step 1: 2-chloro-4[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(3R)-1-methyl-2,6-dioxo-3-piperidyl]benzamide: To a solution of 479 mg 2-chloro-4[5-(3,5-di-chloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]benzoic acid, 281 mg (3R)-3-amino-1-methyl-piperidine-2,6-dionehydrobromide (commercial), 587 mg PyBroP in 5 mL dichloromethane was added 0.75 mL diisopropyl ehtylamine at 20-25° C. and stirred for about 14 h. The mixture was concentrated at reduced pressure and purified via flash chromatography on silica gel to obtain the title compound (413 mg, 68%). HPLC-MS: 1.342 min; m/z=581.8

Example 2: 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(3R)-1-(2,2-difluoroethyl)-2,6-dioxo-3-piperidyl]-2-methyl-benzamide [Compound 1-18 of table C]

[0196] Step 1: Benzyl N-[(3R)-1-(2,2-difluoroethyl)-2,6-dioxo-3-piperidyl]carbamate: To a solution of N-carbobenzoxy-D-glutamic acid (25.2 g, 89.4 mmol; commercial) and iPr.sub.2NEt (19.0 mL, 112 mmol, 1.25 equiv) dissolved in CH.sub.2Cl.sub.2 (250 mL) at ambient temperature was added 1,1′-carbonyldiimidazole (18.0 g, 112 mmol, 1.25 equiv) portionwise and the resulting mixture was stirred at that temperature for 4 h. To this mixture, 2,2-difluoroethylamine hydrochloride (11.6 g, 1.1 equiv) was added and stirring was continued for another 18 h. After that time, another portion of 1,1′-carbonyldiimidazole (18.0 g, 112 mmol, 1.25 equiv) was added before heating the mixture at reflux for 3 h. The resulting reaction mixture was allowed to cool to ambient temperature, and the organic phase washed with HCl solution (10% in H.sub.2O, 1×200 mL) and NaCl solution (sat. aqueous, 1×100 mL), dried over Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure. Purification by column chromatography (EtOAc/cyclohexane 0:100 to 100:0, gradient) afforded the title compound (25.0 g, 86%) in an enantiomeric ratio of 77:23. If desired, the enantiomeric ratio could be further enhanced via recrystallization from MTBE. HPLC-MS: 0.963 min; m/z=326.8.

[0197] Step 2: (3R)-3-amino-1-(2,2-difluoroethyl)piperidine-2,6-dione hydrobromide: Benzyl N-[(3R)-1-(2,2-difluoroethyl)-2,6-dioxo-3-piperidyl]carbamate (10.7 g, 32.7 mmol) was added to HBr, 33% in AcOH (100 mL) at ambient temperature and the resulting reaction mixture was stirred at that temperature for 3 h. After that time, the mixture was poured on cold H.sub.2O (300 mL), the aqueous phase was washed with CH.sub.2Cl.sub.2 (1×300 mL) and concentrated under reduced pressure. Residual water was removed by co-distillation with EtOAc to afford the title compound (8.96 g, quantitative). HPLC-MS: 0.232 min; m/z=192.8.

[0198] Step 3: 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(3R)-1-(2,2-difluoro-ethyl)-2,6-dioxo-3-piperidyl]-2-methyl-benzamide [Compound 1-18 of table C]: From the above (3R)-3-amino-1-(2,2-difluoroethyl)piperidine-2,6-dione hydrobromide the title compound was synthesized in analogy as described for example 1 (step 1).

[0199] HPLC-MS: 1.353 min; m/z=592.1.

Example 3: 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(3R)-1-(2,2-di-fluoroethyl)-2,6-dioxo-3-piperidyl]-2-methyl-benzamide [Compound 3-1 of table C]

[0200] Step 1: (3R)-3-amino-1-(methylamino)piperidine-2,6-dione hydrochloride: To a solution of benzyl N-[(3R)-3-(benzyloxycarbonylamino)-2,6-dioxo-1-piperidyl]-N-methyl-carbamate (1.40 g, 3.29 mmol; obtained analogously as described in example 2, step 1) dissolved in THF (10 mL) at ambient temperature under an atmosphere of N.sub.2 was added HCl solution, 1.0 M in H.sub.2O (4.6 mL, 4.6 mmol), followed by Pd(OH).sub.2, 20 wt % on carbon (139 mg, 0.197 mmol). The flask was purged with H.sub.2 using a gas burette and the resulting suspension was vigorously stirred under an atmosphere of H.sub.2 for 3 h. After that time, the flask was purged with N.sub.2 and the resulting reaction mixture filtered through a short plug of Celite, eluting with MeOH. The filtrate was concentrated under reduced pressure, the residue dried via azeotropical distillation with EtOAc, to afford the title compound (0.492 g, 77%) in crude form which was used in the next step without further purification. HPLC-MS: 0.160 min; m/z=158.1.

[0201] Step 3: 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(3R)-1-(2,2-difluoro-ethyl)-2,6-dioxo-3-piperidyl]-2-methyl-benzamide [Compound 3-1 of table C]: From the above (3R)-3-amino-1-(methylamino)piperidine-2,6-dione hydrochloride the title compound was synthesized in analogy as described for Example 1 (step 1). HPLC-MS: 1.244 min; m/z=557.8.

TABLE-US-00004 TABLE C Compounds of formula I.1 (R.sup.1 = CF.sub.3, R.sup.5 = H) SR-I [00013] racR-I [00014] RR-I [00015] No. R.sup.2a R.sup.2b R.sup.2c R.sup.3 R.sup.4 W—Z Formula R.sup.6 HPLC Method HPLC Rt [min] M + H [m/z] 1-1 Cl F Cl Cl H O—N racR-I CH.sub.3 B 1.337 581.8 1-2 Cl F Cl Cl H O—N racR-I C.sub.2H.sub.5 B 1.381 595.8 1-3 Cl F Cl Cl H O—N racR-I c-C.sub.3H.sub.5 B 1.355 607.7 1-4 Cl F Cl Cl H O—N racR-I H B 1.277 567.7 1-5 Cl F Cl Cl H O—N racR-I N(CH.sub.3).sub.2 B 1.313 609.9 1-6 Cl F Cl Cl H O—N racR-I CH.sub.2CHF.sub.2 B 1.381 631.9 1-7 Cl F Cl Cl H O—N racR-I OCH.sub.3 A 1.319 597.8 1-8 Cl H Cl Cl H O—N racR-I CH.sub.3 A 1.325 563.8 1-9 Cl H Cl CH.sub.3 H O—N racR-I CH.sub.3 A 1.312 542.0 1-10 Cl F Cl CH.sub.3 H O—N racR-I CH.sub.3 A 1.323 559.9 1-11 Cl H Cl Cl H O—N racR-I C.sub.2H.sub.5 A 1.355 577.8 1-12 Cl H Cl CH.sub.3 H O—N racR-I C.sub.2H.sub.5 A 1.344 556.1 1-13 Cl F Cl CH.sub.3 H O—N racR-I C.sub.2H.sub.5 A 1.352 574.1 1-14 Cl H Cl CH.sub.3 H O—N SR-I CH.sub.3 A 1.344 541.9 1-15 Cl H Cl CH.sub.3 H O—N SR-I C.sub.2H.sub.5 A 1.356 555.9 1-16 Cl F Cl CH.sub.3 H O—N racR-I CH.sub.2CHF.sub.2 A 1.361 610.0 1-17 Cl H Cl Cl H O—N racR-I CH.sub.2CHF.sub.2 A 1.363 612.0 1-18 Cl H Cl CH.sub.3 H O—N racR-I CH.sub.2CHF.sub.2 A 1.353 592.1 1-19 Cl F Cl Cl H O—N racR-I CH.sub.2CH.sub.2F B 1.349 612.0 1-20 Cl F Cl CH.sub.3 H O—N racR-I CH.sub.2CH.sub.2F A 1.337 592.1 1-21 Cl H Cl Cl H O—N racR-I CH.sub.2CH.sub.2F A 1.339 596.0 1-22 Cl H Cl CH.sub.3 H O—N racR-I CH.sub.2CH.sub.2F A 1.330 574.0 1-23 Cl F Cl CH.sub.3 H O—N SR-I C.sub.2H.sub.5 A 1.350 573.9 1-24 Cl H Cl CH.sub.3 H O—N racR-I CH.sub.2-c-C.sub.3H.sub.5 A 1.384 582.1 1-25 Cl H Cl Cl H O—N racR-I CH.sub.2-c-C.sub.3H.sub.5 A 1.394 602.0 1-26 Cl F Cl CH.sub.3 H O—N racR-I CH.sub.2-c-C.sub.3H.sub.5 A 1.390 600.1 1-27 Cl F Cl Cl H O—N racR-I CH.sub.2-c-C.sub.3H.sub.5 A 1.400 620.0 1-28 Cl F Cl Cl H O—N racR-I CH.sub.2CH(CH.sub.3).sub.2 A 1.425 623.7 1-29 Cl F Cl CH.sub.3 H O—N racR-I CH.sub.2CH(CH.sub.3).sub.2 A 1.415 601.9 1-30 Cl H Cl Cl H O—N racR-I CH.sub.2CH(CH.sub.3).sub.2 A 1.418 605.8 1-31 Cl H Cl CH.sub.3 H O—N racR-I CH.sub.2CH(CH.sub.3).sub.2 A 1.408 584.4 1-32 Cl F Cl Cl H O—N racR-I NHCH.sub.3 A 1.279 596.6 1-33 Cl F Cl CH.sub.3 H O—N racR-I NHCH.sub.3 A 1.284 575.0 1-34 Cl H Cl Cl H O—N racR-I NHCH.sub.3 A 1.283 579.0 1-35 Cl H Cl CH.sub.3 H O—N racR-I NHCH.sub.3 A 1.270 557.1 2-1 Cl H Cl —CH.sub.2—CH.sub.2—CH.sub.2— CH.sub.2—N racR-I NHCH.sub.3 A 1.245 580.9 3-1 Cl F H Cl H CH.sub.2—CH racR-I NHCH.sub.3 A 1.244 557.8

[0202] II. Evaluation of Pesticidal Activity:

[0203] The activity of the compounds of formula I of the present invention can be demonstrated and evaluated by the following biological test.

[0204] B.1 Diamond Back Moth (Plutella xylostella)

[0205] 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.

[0206] 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%.

[0207] In this test, compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 1-11, 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, 1-20, 1-21, 1-22, 1-23, 1-24, 1-25, 1-26, 1-27, 1-28, 1-29, 1-30, 1-31, 1-32, 1-33, 1-34, 1-35, 2-1, and 3-1, resp., at 300 ppm showed over 75% mortality in comparison with untreated controls.

[0208] B.2 Green Peach Aphid (Myzus persicae)

[0209] 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 mem brane.

[0210] 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.

[0211] 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.

[0212] In this test, compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 1-11, 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, 1-20, 1-21, 1-22, 1-23, 1-24, 1-25, 1-26, 1-27, 1-28, 1-29, 1-30, 1-31, 1-33, 1-34, 1-35, 2-1, and 3-1, resp., at 2500 ppm showed over 75% mortality in comparison with untreated controls.

[0213] B.3 Vetch aphid (Megoura viciae)

[0214] 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.

[0215] 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.

[0216] 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.

[0217] In this test, compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 1-11, 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, 1-20, 1-21, 1-22, 1-23, 1-24, 1-25, 1-26, 1-27, 1-28, 1-29, 1-30, 1-31, 1-33, 1-34, 1-35, 2-1, and 3-1, resp., at 2500 ppm showed over 75% mortality in comparison with untreated controls.

[0218] B.4 Tobacco Budworm (Heliothis Virescens)

[0219] 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.

[0220] 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.

[0221] 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.

[0222] In this test, compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 1-11, 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, 1-20, 1-21, 1-22, 1-23, 1-24, 1-25, 1-26, 1-27, 1-28, 1-29, 1-30, 1-31, 1-33, 1-34, 1-35, 2-1, and 3-1, resp., at 2500 ppm showed over 75% mortality in comparison with untreated controls.

[0223] B.5 Boll Weevil (Anthonomus grandis)

[0224] 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.

[0225] 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.

[0226] 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.

[0227] In this test, compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 1-11, 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, 1-20, 1-21, 1-22, 1-23, 1-24, 1-25, 1-26, 1-27, 1-28, 1-29, 1-30, 1-31, 1-33, 1-34, 1-35, 2-1, and 3-1, resp., at 2500 ppm showed over 75% mortality in comparison with untreated controls.

[0228] B.7 Orchid thrips (Dichromothrips Corbetti)

[0229] 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.

[0230] 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.

[0231] In this test, compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 1-11, 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, 1-20, 1-21, 1-22, 1-23, 1-24, 1-25, 1-26, 1-27, 1-28, 1-29, 1-30, 1-31, 1-32, 1-33, 1-34, 1-35, 2-1, and 3-1, resp., at 300 ppm showed over 75% mortality in comparison with untreated controls.

[0232] B.8 Rice Green Leafhopper (Nephotettix Virescens)

[0233] 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.

[0234] In this test, compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-8, 1-9, 1-10, 1-11, 1-12, 1-13, 1-14, 1-15, I-1-16, 1-17, 1-18, 1-19, 1-20, 1-21, 1-22, 1-23, 1-24, 1-25, 1-26, 1-27, 1-28, 1-29, 1-30, 1-31, 1-32, 1-33, 1-34, 1-35, and 2-1, resp., at 300 ppm showed over 75% mortality in comparison with untreated controls.

[0235] B.9 Red Spider Mite (Tetranychus kanzawai)

[0236] 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.

[0237] 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.

[0238] In this test, compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-8, 1-9, 1-10, 1-11, 1-12, 1-13, 1-14, 1-15, 1-16, 1-18, 1-19, 1-20, 1-21, 1-22, 1-23, 1-24, 1-25, 1-26, 1-27, 1-28, 1-29, 1-31, 1-32, 1-33, 1-34, 1-35, 2-1, and 3-1, resp., at 300 ppm showed over 75% mortality in comparison with untreated controls.

[0239] B.10 Southern Armyworm (Spodoptera Eridania)

[0240] 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).

[0241] 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.

[0242] In this test, compounds 1-1, 1-2, 1-5, 1-6, and 1-9, resp., at 10 ppm showed over 75% mortality in comparison with untreated controls.

[0243] B.11 Green Soldier Stink Bug (Nezara viridula)

[0244] 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. 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.

[0245] In this test, compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-8, 1-9, 1-10, 1-11, 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, 1-20, 1-21, 1-22, 1-23, 1-24, 1-25, 1-26, 1-27, 1-28, 1-29, 1-30, 1-31, 1-32, 1-33, 1-34, 1-35, 2-1, and 3-1, resp., at 300 ppm showed over 75% mortality in comparison with untreated controls.

[0246] B.12 Neotropical Brown Stink Bug (Euschistus heros)

[0247] 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.

[0248] 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.

[0249] In this test, compounds 1-1, 1-2, 1-5, 1-6, 1-8, 1-9, 1-10, 1-12, 1-15, 1-16, 1-17, 1-18, 1-19, 1-21, 1-22, 1-23, 1-24, and 1-25, resp., at 500 ppm showed over 75% mortality in comparison with untreated controls.

[0250] B.13 Brown Marmorated Stink Bug (Halyomorpha halys)

[0251] 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.

[0252] 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).

[0253] Each treatment is replicated 4-fold. Assay arenas are kept at about 25° C. Percent mortality was recorded after 5 days.

[0254] In this test, compounds 1-1, 1-2, 1-5, 1-6, 1-8, 1-9, 1-10, 1-11, 1-12, 1-13, 1-15, 1-16, 1-17, 1-18, 1-19, 1-20, 1-21, 1-22, 1-23, 1-24, and 1-25, resp., at 100 ppm showed over 75% mortality in comparison with untreated controls.