Pyrimidinium compounds and their mixtures for combating animal pests

Abstract

The present invention relates to pyrimidinium compounds of formula (I), to the stereoisomers, salts, tautomers and N-oxides thereof, their mixtures and to compositions comprising such compounds or mixtures. The invention also relates to methods and uses of these pyrimidinium compounds and of compositions thereof, for combating and controlling animal pests. Furthermore, the invention relates also to pesticidal methods of applying such substituted pyrimidinium compounds. The pyrimidinium compounds of the present invention are defined by the following general formula (I): ##STR00001##
wherein R1, R2 and Het are defined as in the description.

Claims

1. A mixture comprising: (1) a compound of formula I-R-1 or a salt thereof: ##STR00027## and (2) at least one compound II selected from the group consisting of spinetoram, spinosad, flufenoxuron, triflumezopyrim, indoxacarb, flonicamid, alpha-cypermethrin, fluxametamide, pymetrozine, oxazosulfyl, furametpyr, metalaxyl, probenazole, dicyclomet, penflufen, pyroquilon, simeconazol, buprofezin, tricyclazol, and combinations thereof; wherein: the ratio of the compound of formula I-R-1 and the compound II is between 1000:1 to 1:1000; and an enantiomeric excess between the compound of formula I-R-1 and any corresponding S-enantiomer in the mixture is at least 90%.

2. The mixture of claim 1, wherein the ratio of the compound of formula I-R-1 and the compound II is between 100:1 and 1:100.

3. The mixture of claim 1, wherein the enantiomeric excess between the compound of formula I-R-1 and any corresponding S-enantiomer in the mixture is at least 95%.

4. The mixture of claim 1, wherein the enantiomeric excess between the compound of formula I-R-1 and any corresponding S-enantiomer in the mixture is at least 98%.

5. A pesticidal composition comprising a liquid or solid carrier and the mixture of claim 1.

6. A seed comprising the mixture of claim 1 in an amount of from 0.1 g to 10 kg per 100 kg of seeds.

7. A method for controlling insects, acarids or nematodes comprising contacting an insect, acarid or nematode or their food supply, habitat, breeding grounds or their locus with the mixture of claim 1.

8. A method of protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting the plant, or soil or water in which the plant is growing, with a pesticidally effective amount of the mixture of claim 1.

9. A method for protection of plant propagation material comprising contacting the plant propagation material with the mixture of claim 1 in pesticidally effective amounts.

10. The method of claim 8, wherein the plant is a rice plant and the insects are selected from the group consisting of Hemiptera, Lepidoptera, Coleoptera, Diptera, Thysanoptera, Orthoptera, Isoptera, Hymenoptera, Acari, and Crustacea.

Description

EXAMPLES

Synthesis Example: 3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-8-ium-5-olate (Corresponding to Compound I-1)

Step 1: 2-chloro-N-methoxy-N-methyl-acetamide

(1) N-Methoxymethanamine hydrochloride (345 g) and water (1.5 L) were cooled to 0° C. To this reaction mixture, K.sub.2CO.sub.3 (1466 g) was added in lots, then methyl tert-butyl ether (1000 mL) was added at 0° C. The reaction mixture was cooled to −5° C. Chloroacetylchloride (400 g) in methyl tert-butyl ether (500 ml) was added drop wise at −5° C. to 0° C. and stirred for 2 hours at 0° C. The reaction mixture was allowed to come to 20-25° C. From the organic layer, the desired product was obtained as white solid (438 g, 90% yield; 98.45% HPLC purity).

Step 2: 2-chloro-1-(2-chlorothiazol-5-yl) ethanone

(2) 2-chlorothiazole (187 ml) in 750 ml tetrahydrofurane under nitrogen atmosphere were cooled to −20° C. Isopropylmagnesium chloride×LiCl (1684 ml, 1.3 molar in tetrahydrofurane) was added drop wise and stirred at −20° C. for 60 minutes. A solution of 2-chloro-N-methoxy-N-methyl-acetamide (250 g) in tetrahydrofurane was added drop wise at −20° C. to −25° C. The reaction mixture was stirred at −20° C. for 90 minutes. Saturated aqueous ammonium chloride solution was added at −20° C., then the reaction mixture was brought to 20-25° C. The two phases were separated and the aqueous phase was extracted with ethyl acetate. From the combined organic layers, the desired crude product was obtained as dark brown colored oil, which was treated with activated charcoal and silica in methyl tert-butyl ether to get the crude product as pale brown colored oil (335 g) for direct use in the next step.

Step 3: N-[2-chloro-1-(2-chlorothiazol-5-yl) ethylidene]-2-methyl-propane-2-sulfinamide

(3) To crude 2-chloro-1-(2-chlorothiazol-5-yl) ethanone (335 g) in tetrahydrofurane at 20-25° C. under nitrogen atmosphere, tert-butyl sulfinamide (206 g) and Ti(OEt).sub.4 (396 ml) are added. The mixture was heated to 50° C. and stirred for 2 hours, then cooled to 20-25° C. and diluted with ethyl acetate. After adding water, the mixture was stirred for 30 minutes, then filtered. The organic phase was evaporated to obtain the desired crude product as brown colored oil. After treatment with activated charcoal and silica in methyl tert-butyl ether, the crude product was obtained as pale brown colored oil (365 g) for direct use in the next step.

Step 4: N-[2-chloro-1-(2-chlorothiazol-5-yl) ethyl]-2-methyl-propane-2-sulfinamide

(4) To N-[2-chloro-1-(2-chlorothiazol-5-yl) ethylidene]-2-methyl-propane-2-sulfinamide (365 g) in tetrahydrofurane and methanole at −5° C., NaBH.sub.4 (23 g) was added lot wise and stirred for 30 minutes. Saturated aqueous ammonium chloride solution was added at 0° C. After extracting with ethyl acetate, the organic layer yielded the desired crude product as brown colored oil (310 g).

Step 5: 2-chloro-1-(2-chlorothiazol-5-yl) ethanamine hydrochloride

(5) N-[2-chloro-1-(2-chlorothiazol-5-yl) ethyl]-2-methyl-propane-2-sulfinamide was stirred with HCl in methanole (1 molar, 620 mL) at 20-25° C. for 12 hours. Removal of methanole under vacuum yielded a pale yellow sticky solid (244 g), which was washed with methyl tert-butyl ether and subsequently with ethyl acetate to get a pale yellow color solid (78 g, 26% yield over steps 2 to 5, >98% purity).

Step 6: 4-(2-chlorothiazol-5-yl)-N-methyl-thiazolidin-2-imine

(6) 2-chloro-1-(2-chlorothiazol-5-yl) ethanamine hydrochloride (285 g) in methyl tert-butyl ether and 2 molar aqueous NaOH solution (1060 mL) were stirred for 20 minutes at 23° C. The organic layer yielded the free amine as pale brown colored oil (230 g).

(7) The amine (230 g) in ethanole was reacted with triethylamine NEt3 (351 ml) and Me-NCS (143.2 g) at 22 to 25° C. for 18 hours. The reaction mass was concentrated to obtain a brown colored residue, to which aqueous NaOH solution (114 g in 920 mL of water) was added. The resulting mixture was heated to 100° C. for 2 hours, then cooled to 20-25° C. and diluted with water. After extraction with ethyl acetate, the organic layer yielded crude 4-(2-chlorothiazol-5-yl)-N-methyl-thiazolidin-2-imine as brown colored solid (256 g), which was stirred with 20% ethyl acetate in heptane (300 mL) for 30 minutes. After filtering, the product was obtained as a brown colored solid (245 g, 85% yield).

Step 7: 3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a] pyrimidin-8-ium-5-olate (I-1)

(8) 4-(2-chlorothiazol-5-yl)-N-methyl-thiazolidin-2-imine (110 g) in toluene was stirred at 110 to 115° C. After adding bis(4-chlorophenyl) 2-phenylpropanedioate (226 g), the reaction mixture was stirred at this temperature for 2 hours, then cooled to 40 to 45° C. After removal of toluene under vacuum, a brown solid was obtained, which was triturated with methyl tert-butyl ether to obtain a yellow color solid.

(9) Stirring in methyl tert-butyl ether (1 L) at 22 to 25° C. for 14 hours yielded a pale yellow solid (160 g). Further purification by dissolving in dichloromethane and precipitating with methyl tertbutyl ether yielded the desired product as fine pale yellow colored powder (129 g, 80% yield).

(10) *: HPLC Method: Retention time in minutes; mass charge ratio m/z

(11) HPLC Method A:

(12) MSD4/5: Shimadzu Nexera UHPLC+Shimadzu LCMS 20-20, ESI

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

(14) Mobile Phase: A: water+0.1% trifluoroacetic acid; B: acetonitrile, Temperature: 60° C.

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

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

(17) MS method: ESI positive, Mass range (m/z): 100-700

(18) HPLC Method B:

(19) MSD4/5: Shimadzu Nexera UHPLC+Shimadzu LCMS 20-20, ESI

(20) Column: Agilent Eclipse Plus C18, 50 mm×4.6 mm×3

(21) Mobile phase: A=10 mM ammonium formate (0.1% Formic Acid) B=acetonitrile (0.1% Formic Acid), Flow=1.2 ml/min. Column oven: 30 C

(22) Gradient:=10% B to 100% B—1.5 min, hold for 1 min, 2.51 min—10% B; Run Time=3.50 min

(23) HPLC Method C:

(24) same as Method A, but MS method: ESI positive, Mass range (m/z): 100-1400

Example—Separation of the Enantiomers

R-3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a] pyrimidin-8-ium-5-olate and

S-3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a] pyrimidin-8-ium-5-olate

(25) The enantiomers of 3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-8-ium-5-olate from example 1 can be separated by preparative chiral supercritical fluid chromatography. 126 g of rac-3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a] pyrimidin-8-ium-5-olate were separated. This yielded 53.4 g of R-3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a] pyrimidin-8-ium-5-olate at a retention time of 1.94 min and 57.7 g of S-3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a] pyrimidin-8-ium-5-olate at a retention time of 1.41 min. These retention times refer to the analytical method cited below. The configuration of the chiral centre was determined by X-ray analysis.

(26) Analytical Separation Method:

(27) Instrument: Thar analytical SFC

(28) Column: Chiralpak AS-H, 150×4.6 mm i.d., 5 u

(29) Mobile phase: A for CO.sub.2 and B for MeOH, Gradient: B %=40%

(30) Flow rate: 4.0 mL/min, Back pressure: 100 bar, Column temperature: 35° C.

(31) Wavelength: 220 nm

(32) Preparative Separation Method:

(33) Instrument: Thar 80 preparative SFC

(34) Column: Chiralcel OJ-H, 250×30 mm I.D. 5 u

(35) Mobile phase: A for CO.sub.2 and B for CH.sub.3CN, Gradient: B %=50%

(36) Flow rate: 80 g/min, Back pressure: 100 bar, Column temperature: 40° C.

(37) Wavelength: 220 nm

(38) Cycletime: 6.5 min

(39) Sample preparation: Racemic material was dissolved in mixed solution of MeOH—CH.sub.3CN-DCM (1:1:0.5) to 20 mg/mL and filtrated through membrane with pore sized 0.45 um.

(40) Injection: 4 mL per injection.

(41) After separation, the fractions were dried off via rotary evaporator at bath temperature 35° C. to get the two enantiomers.

(42) Preparation of Compound of Formula I with Enantiomeric Excess:

(43) The characterization can be done by coupled High Performance Liquid Chromatography/mass spectrometry (HPLC/MS), Gas chromatography (GC), by NMR or by their melting points.

(44) HPLC method: Agilent Eclipse Plus C18, 150 mm×4.6 mm ID×5 um

(45) Gradient A=0.1% TFA in Water, B=0.1% TFA in Acetonitrile.

(46) Flow=1.4 ml/min., column oven temperature=30 C

(47) Gradient program=10% B-100% B—5 min, hold for 2 min, 3 min—10% B.

(48) Run Time=10 min

(49) LCMS method 1: C18 Column (50 mm×3.0 mm×3μ)

(50) Gradient A=10 Mm Ammonium formate in water, B=0.1% Formic acid in acetonitrile

(51) Flow=1.2 ml/min., column oven temperature=40° C.

(52) Gradient program=10% B to 100% B in 1.5 min., hold for 1 min 100% B, 1 min—10% B

(53) Run time: 3.75 min

(54) Chiral HPLC method 1: ChiralPak IA column, 150 mm×4.6 mm×5μ

(55) Mobile phase A=heptane, B=isopropanol,

(56) Flow=1.0 ml/min, column oven temperature=40° C.

(57) Gradient program=10% B Isocratic; run time: 20 min

(58) Chiral HPLC method 3: ChiralPak IA column, 150 mm×4.6 mm×5μ

(59) Mobile phase A=heptane, B=isopropanol,

(60) Flow=1.0 ml/min, column oven temperature=40° C.

(61) Gradient program=40% B Isocratic; run time: 20 min

(62) .sup.1H-NMR: The signals are characterized by chemical shift (ppm) vs. tetramethylsilane, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: m=multiplet, q=quartet, t=triplet, d=doublet and s=singlet.

(63) Abbreviations used are: h for hour(s), min for minute(s), rt for retention time and ambient temperature for 20-25° C.

Example 1: Preparation of Compound of Formula I-1 with Enantiomeric Excess of Compound I-R-1((3R)-3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium-5-olate)

Step-1: Preparation of 2-chloro-N-methoxy-N-methyl-acetamide

(64) A 3 L four necked flask equipped with Teflon-blade stirrer, reflux condenser and thermo-pocket was charged with N-methoxymethanamine hydrochloride (345 g), water (1.6 litre) and the resulting reaction mixture was cooled to 0 to −5° C. Then potassium carbonate (1466 g) was added in lots to the above reaction mixture followed by the addition of methyl tert-butyl ether (1.4 litre). The chloroacetyl chloride (400 g) was dissolved in tert-butyl methyl ether (0.2 litre) and added dropwise in to the above kept reaction mixture at −5° C. to 0° C. and the reaction mixture was stirred for 2 h at 0° C. The reaction mixture was allowed to come to ambient temperature and two phases were separated. The organic layer was dried over sodium sulfate, filtered and evaporated to provide 2-chloro-N-methoxy-N-methyl-acetamide as white solid (440 g, 90% yield and 98.0% area purity by HPLC).

Step-2: Preparation of 2-chloro-1-(2-chlorothiazol-5-yl)ethenone

(65) A 5 L, four necked flask equipped with Teflon-blade stirrer, reflux condenser and thermo-pocket was charged with 2-chlorothiazole (250 g), TH F (0.75 L) and the resulting reaction mixture was cooled to 0 to −5° C. Then isopropylmagnesium chloride lithium chloride (1.929 L, 1.3 M solution in THF) was added over 0.5 h into the above kept reaction mixture at 0 to −5° C. The reaction mixture was then heated to 40° C. and the reaction was continued at 40° C. for 2 h. The formation of chloro-(2-chlorothiazol-5-yl)magnesium species was confirmed by quenching the small aliquot of the reaction mixture with iodine and monitoring the formation of 2-chloro-5-iodo-thiazole by GC analysis (96% conversion was observed by GC analysis). The reaction mixture was cooled to 0 to −5° C. and the solution of 2-chloro-N-methoxy-N-methyl-acetamide (343 g) in THE (0.25 L) was added dropwise. The reaction was continued at −5 to 0° C. for 1 h and the reaction progress was monitored by HPLC. The reaction mixture was quenched with 1.5 N aq. HCl solution (1 L) at −5 to 0° C. and then warmed to ambient temperature. The two phases were separated and the aqueous phase extracted with methyl tert-butyl ether (2×300 mL). The combined organic layers were dried over sodium sulfate, filtered and evaporated to obtain crude residue. The crude product was dissolved in methyl tert-butyl ether (0.7 L) at ambient temperature and activated charcoal (4 g) and silica (80 g, 60-120 mesh) were added. The slurry was stirred for 0.5 h, filtered through Buchner funnel and washed with methyl tert-butyl ether (0.3 L). The filtrate was evaporated to obtain 2-chloro-1-(2-chlorothiazol-5-yl)ethanone as pale brown colored oil (409 g, 46% area purity by HPLC)

Step-3: Preparation of [2-(2-chlorothiazol-5-yl)-2-oxo-ethyl] acetate

(66) A 0.25 L, three necked flask equipped with teflon-blade stirrer, reflux condenser and thermo-pocket was charged with 2-chloro-1-(2-chlorothiazol-5-yl)ethanone (15 g, 46 area % HPLC purity) and dimethylformamide (45 mL) at ambient temperature. Then sodium acetate (12.55 g) was added in portions and reaction was continued at ambient temperature for 4 h. The reaction progress was monitored by HPLC (>95% conversion by HPLC). The reaction was quenched with water (50 mL) and extracted with methyl tert-butyl ether (3×100 mL). The two phases were separated and the combined organic phases were dried over sodium sulfate, filtered and evaporated to obtain crude residue (17 g). The crude product was purified by silica gel column chromatography to obtain [2-(2-chlorothiazol-5-yl)-2-oxo-ethyl]acetate as yellow colored solid (7.5 g).

Step-4: Preparation of 1-(2-chlorothiazol-5-yl)-2-hydroxy-ethanone

(67) A 250 mL, three necked flask equipped with magnetic stirrer, reflux condenser and thermo-pocket was charged with [2-(2-chlorothiazol-5-yl)-2-oxo-ethyl]acetate (7.5 g) and 1 N HCl in MeOH (50 mL). The resulting solution was stirred for 5 h and reaction progress was monitored by TLC. The methanol from reaction mixture was distilled under vacuum and crude residue obtained was purified by column chromatography to obtain 1-(2-chlorothiazol-5-yl)-2-hydroxy-ethanone as pale yellow solid (2.8 g, 84% area purity by HPLC).

Step-5: Preparation of 4-(2-chlorothiazol-5-yl)-5H-oxathiazole 2,2-dioxide

(68) A 100 mL, three neck flasks equipped with magnetic stirrer, reflux condenser and thermo-pocket was charged with 1-(2-chlorothiazol-5-yl)-2-hydroxy-ethanone (1 g), toluene (20 mL), chlorosulfonamide (0.975 g) and p-toluenesulfonic acid (0.214 g). The resulting solution was heated to 100° C. and stirred for 1 h. The reaction progress was monitored by HPLC (>95% conversion). The reaction mixture was quenched with water and extracted with MTBE (15 mL×2). The two phases were separated, organic phase was evaporated and purified by column chromatography 4-(2-chlorothiazol-5-yl)-5H-oxathiazole 2,2-dioxide (0.42 g).

Step-6: Preparation of (4R)-4-(2-chlorothiazol-5-yl)oxathiazolidine 2,2-dioxide

(69) a) Preparation of Rhodium Catalyst—RhCl[(R,R)-TsDPEN]Cp*:

(70) A 250 mL, three necked flask equipped with teflon-blade stirrer, nitrogen inlet and thermo-pocket was charged with [RhCl.sub.2Cp*].sub.2 (2.0 g), (1R,2R)—N-p-toluenesulfonyl-1,2-diphenylethylenediamine (2.38 g), dichloromethane (68 mL) and triethylamine (1.72 ml) under nitrogen atmosphere. The resulting slurry was stirred for 0.5 h at 22-27° C. and distilled water was added (40 mL). The two phases were separated and the organic phase was washed with water (40 mL). The organic phase was dried over sodium sulfate, filtered and evaporated to get brown coloured solid residue. The brown residue was triturated with n-heptane (20 mL), filtered and dried under nitrogen atmosphere to get obtain RhCl [(R,R)-TsDPEN]Cp* as red coloured solid (3.4 g).

(71) b) Preparation of HCOOH-NEt.sub.3 Mixture:

(72) In a 2 liter, 3 neck round bottom flask Formic acid (275 mL, >=99% w/w) was added and cooled to 0° C. To this, triethylamine 250 mL, >=99% w/w) was added slowly at 0° C. and used immediately in reaction.

(73) c) Preparation of (4R)-4-(2-chlorothiazol-5-yl)oxathiazolidine 2,2-dioxide:

(74) A 100 ml, two necked flask equipped with magnetic stirrer, condenser and thermo-pocket was charged with 4-(2-chlorothiazol-5-yl)-5H-oxathiazole 2,2-dioxide (0.5 g) and dimethylformamide (15 mL, 30V) was degassed with nitrogen for 10 min. Then RhCl[(R,R)-TsDPEN]Cp* (27 mg) was added followed by dropwise addition of HCOOH-NEt.sub.3 (2.5 mL, in a ratio of 5:2). The resulting mixture was stirred for 2 h. The HPLC showed >97% conversion. The reaction mixture was quenched with water (15 ml) and extracted with methyl tert-butyl ether (3×50 mL). The combined organic phase was evaporated to obtain (4R)-4-(2-chlorothiazol-5-yl)oxathiazolidine 2,2-dioxide (500 mg; 90 area % HPLC purity (rt=3.645 min.), >99% ee by chiral HPLC method 1).

Step-7: Preparation of (4R)-4-(2-chlorothiazol-5-yl)-N-methyl-thiazolidin-2-imine

(75) A 100 mL, three necked flask equipped with magnetic stirrer, reflux condenser and thermo-pocket was charged with (4R)-4-(2-chlorothiazol-5-yl)oxathiazolidine 2,2-dioxide (0.5 g, with 99% ee), ethanol (2 ml), methyl isothiocyanate (0.228 g) and triethylamine (0.56 ml) at ambient temperature. The resulting mixture was stirred for 14 h at 22-27° C. Then organic volatiles were re-moved under vacuum and sodium hydroxide (0.2 g) and water (2 mL) were added into the reaction flask. The reaction mixture was heated to 100° C. and stirred for 2 h. The reaction was diluted with water (2 mL) and extracted with methyl tert-butyl ether (2×50 mL). The organic phases were dried over sodium sulfate and evaporated under vacuum to provide (4R)-4-(2-chlorothiazol-5-yl)-N-methyl-thiazolidin-2-imine as brown oil [0.34 g, m/z=234 amu (M+H.sup.+)].

Step-8: Preparation of (3R)-3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium-5-olate

(76) A 50 mL, three necked flask equipped with magnetic stirrer, reflux condenser and thermo-pocket was charged with (E,4R)-4-(2-chlorothiazol-5-yl)-N-methyl-thiazolidin-2-imine (0.34 g), toluene (2 mL) and heated to 110° C. under nitrogen atmosphere. Then bis(2,4,6-trichlorophenyl) 2-phenylpropanedioate (0.857 g) was added in lots into the reaction mass kept at 110° C. After stirring at 110° C. for 2 h, HPLC showed >99% conversion. The reaction was cooled below 50° C. and the precipitated pale yellow colored solid was filtered through sintered funnel and then solid residue was washed with methyl tert-butyl ether (4 mL) and dried under vacuum to provide (3R)-3-(2-chlorothiazol-5-yl)-8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium-5-olate (110 mg, m/z=378 amu (M+H.sup.+) & 95.2% enantiomeric excess by chiral HPLC method 3). .sup.1H NMR (300 MHz, DMSO-d6): 3.42 (s, 3H), 3.94 (d, J=12 Hz, 1H), 4.25-4.32 (m, 1H), 6.48 (d, J=8.1 Hz, 1H), 7.06-7.11 (m, 1H), 7.21-7.26 (m, 2H), 7.6 (d, J=7.5 Hz, 1H), 7.96 (s, 1H).

Biological Examples

(77) If not otherwise specified, the test solutions are prepared as follows:

(78) 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.

(79) Test compound I-R-1 used in below biological examples is in 95% enantiomeric excess unless otherwise specified.

(80) Test compound I-S-1 used in below biological examples is in 95% enantiomeric excess unless otherwise specified.

(81) B.1 Rice Green Leafhopper (Nephotettix virescens):

(82) Rice seedlings are cleaned and washed 24 hours before spraying. The active compounds are formulated in 50:50 acetone:water (vol:vol), and 0.1% vol/vol surfactant (EL 620) is added. Potted rice seedlings are sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants are kept at about 28-29° C. and relative humidity of about 50-60%. Percent mortality is recorded after 72 hours.

(83) B.2 Rice Brown Plant Hopper (Nilaparvata lugens):

(84) Rice seedlings are cleaned and washed 24 hours before spraying. The active compounds are formulated in 50:50 acetone:water (vol:vol) and 0.1% vol/vol surfactant (EL 620) is added. Potted rice seedlings are sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants are kept at about 28-29° C. and relative humidity of about 50-60%. Percent mortality is recorded after 72 hours.

(85) B.3 Cowpea aphid (Aphis craccivora):

(86) For evaluating control of Cowpea aphid through contact or systemic means the test unit consists of 24-well-microtiter plates containing broad bean leaf disks.

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

(88) After application, the leaf disks are air-dried and 5-8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids are 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 is then visually assessed.

(89) B.4 Thrips (Dichromothrips Corbetti):

(90) Dichromothrips corbetti adults used for bioassay are 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 0.01% vol/vol Alkamuls® EL 620 surfactant.

(91) Thrips potency of each compound is evaluated by using a floral-immersion technique. Plastic petri dishes are used as test arenas. All petals of individual, intact orchid flowers are dipped into treatment solution and allowed to dry. Treated flowers are placed into individual petri dishes along with about 20 adult thrips. The petri dishes v then covered with lids. All test arenas are held under continuous light and a temperature of about 28° C. for duration of the assay. After 3 days, the numbers of live thrips are counted on each flower, and along inner walls of each petri dish. The percent mortality is recorded 72 hours after treatment.

(92) Tables A below shows activity data:

(93) TABLE-US-00003 TABLE A Test species Dose Cowpea Rice green Rice brown Compound (ppm) aphid leafhopper plant hopper Thrips Mortality % I-1 1 80 50 54 — (racemic mixture) I-R-1 1 90 100 90 — I-S-1 1 0 0 0 — I-1 10 — — — 73 (racemic mixture) Test species I-R-1 10 — — — 100 I-S-1 10 — — — 0

(94) B.3. Rice Stem Borer

(95) B.3a Vial Bioassays

(96) Field-collected rice straws were washed with tap water and cut for a certain of length. Straws were air dried before placing individually in vials (=replicate, 3×). About 125 μl test solution was sprayed per vial. Treated rice straws in vials were air dried under the laboratory hood. After air-drying, each straw was inoculated with 10 newly-emerged (0-day old) stem borer larvae. Vials were then covered. Set-up was kept in a holding room maintained at 27° C. and 65% RH for three days. At 3 days after inoculation, rice straws were manually dissected for larval mortality assessment. The data (Table C) show activity against two species of rice stem borers.

(97) TABLE-US-00004 TABLE C Efficacy of mesoionic compounds against rice stem borers Test species Chilo suppressalis Life stage 1.sup.st instar Evaluation 3 DAT/3 DAI compound Dose (ppm) Mortality (%) I-1 300 80 (racemic mixture) I-R-1 300 83

(98) B.3b Foliar Spraying

(99) All three pots (=replicates) of four to five-week old potted rice per treatment were simultaneously sprayed with 12 mL test solution. After spray application, plants were air dried in the laboratory before inoculation. After air-drying, 5 to 6-day old egg masses of CHILSU were used for inoculation. All stem borer-infested potted rice plants were transferred inside the screenhouse 1 day after inoculation until the final assessment. Assessment was done 10 days after treatment and inoculation. Whole plant damage was assessed before cutting each hill at the basal portion for tiller dissection. Each dissected tiller was inspected looking for dead (if possible) and alive stemborer larvae.

(100) The results showed that the tested compound have excellent activity against striped rice stem borer in terms of larvae mortality and feed suppression

(101) TABLE-US-00005 TABLE D Efficacy of mesoionic compounds against rice striped stem borer by foliar spraying Test species Chilo suppressalis Life stage Neonates Evaluation 14 DAT compound Dose (ppm) Mortality (%) Feeding damage (%) I-1 200 96 15 (racemic mixture) I-R-1 200 99 7

(102) B.3c Drench Application

(103) The test solution was poured onto the soil of each potted rice plant (=replicate) with five tillers each pot. After drench application, treated plants were transferred inside the screenhouse for three days prior to stemborer inoculation inside the laboratory. Three days after drench application, 5 to 6-day old egg masses of CHILSU were used for inoculation. All stemborer-infested potted rice plants were transferred inside the screenhouse 1 day after inoculation until the final assessment. Assessment was done 12 days after treatment (9 days after inoculation). Whole plant damage was assessed before cutting each hill at the basal portion for tiller dissection. Each dissected tiller was inspected looking for dead (if possible) and alive stemborer larvae.

(104) The data (Table 3) showed that similar results were obtained through drench application when compared with foliar application for all tested compound against striped rice stem borer in terms of larvae mortality and feed suppression

(105) TABLE-US-00006 TABLE E Efficacy of mesoionic compounds against rice striped stem borer by drench application Test species Chilo suppressalis Life stage Neonates Evaluation 14 DAT compound Dose (mg) Mortality (%) Feeding damage (%) I-1 10 96 15 (racemic mixture) I-R-1 10 99 7

(106) Examples of Mixtures:

(107) Synergism can be described as an interaction where the combined effect of two or more compounds is greater than the sum of the individual effects of each of the compounds. The presence of a synergistic effect in terms of percent control, between two mixing partners (X and Y) can be calculated using the Colby equation (Colby, S. R., 1967, Calculating Synergistic and Antagonistic Responses in Herbicide Combinations, Weeds, 15, 20-22):

(108) $E=X+Y-\frac{XY}{100}$

(109) When the observed combined control effect is greater than the expected combined control effect (E), then the combined effect is synergistic.

(110) The following tests demonstrate the control efficacy of compounds, mixtures or compositions of this invention on specific pests, wherein the compound I-R-1 is in 95% enantiomeric excess unless otherwise specified. However, the pest control protection afforded by the compounds, mixtures or compositions is not limited to these species. In certain instances, combinations of a compound of this invention with other invertebrate pest control compounds or agents are found to exhibit synergistic effects against certain important invertebrate pests.

(111) The analysis of synergism or antagonism between the mixtures or compositions was determined using Colby's equation.

(112) Test 1

(113) 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.

(114) The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Concentrations of formulated compounds or mixtures were sprayed onto the leaf disks at 2.5 μl, using a custom built micro atomizer, at two replications.

(115) For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

(116) 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 23±1° C., 50±5% RH for 5 days. Aphid mortality and fecundity was then visually assessed. For the mixture tested the results are listed in table 1.

(117) TABLE-US-00007 TABLE 1 I-R-1 and Spinetoram. solo application combination Spinetoram I-R-1 Spinetoram + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Vetch Aphid 2 50 20 0 20 + 2 100

(118) Test 2

(119) 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.

(120) The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Concentrations of formulated compounds or mixtures were pipetted into the aphid diet, using a custom built pipetter, at two replications.

(121) For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

(122) 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 23±1° C., 50±5% RH for 3 days. Aphid mortality and fecundity was then visually assessed.

(123) For the mixture tested the results are listed in tables 2.1 to 2.6.

(124) TABLE-US-00008 TABLE 2.1 I-R-1 and Spinosad. solo application combination Spinosad I-R-1 Spinosad + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Green Peach Aphid 4 0 2 25 4 + 2 100

(125) TABLE-US-00009 TABLE 2.2 I-R-1 and Flufenoxuron. solo a pplication combination Flufenoxuron I-R-1 Flufenoxuron + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Green Peach Aphid 0.8 0 2 0 0.8 + 2 100

(126) TABLE-US-00010 TABLE 2.3 I-R-1 and Triflumezopyrim. solo application combination Triflumezopyrim I-R-1 Triflumezopyrim + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Green Peach Aphid 0.4 0 0.4 50 0.4 + 0.4 100

(127) TABLE-US-00011 TABLE 2.4 I-R-1 and Indoxacarb. solo application combination Indoxacarb I-R-1 Indoxacarb + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control% (ppm) control % Green Peach Aphid 2 0 50 0 2 + 2 100

(128) TABLE-US-00012 TABLE 2.5 I-R-1 and Flonicamid. solo application combination Flonicamid I-R-1 Flonicamid + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Green Peach Aphid 2 0 2 50 2 + 2 100

(129) TABLE-US-00013 TABLE 2.6 I-R-1 and Alpha-Cypermethrin. solo application combination Alpha-Cypermethrin I-R-1 Alpha-Cypermethrin + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Green Peach Aphid 10 0 2 25 10 + 2 100

(130) Test 3

(131) For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 24-well-microtiter plates containing an insect diet and 20-30 A. grandis eggs.

(132) The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 20 μl, using a custom built micro atomizer, at two replications.

(133) For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

(134) After application, microtiter plates were incubated at 23±1° C., 50±5% RH for 5 days. Egg and larval mortality was then visually assessed. For the mixture tested the results are listed in table 3.1 to table 3.3.

(135) TABLE-US-00014 TABLE 3.1 I-R-1 and Flufenoxuron. solo application combination Flufenoxuron I-R-1 Flufenoxuron + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Boll Weevil 0.8 0 50 0 0.8 + 50 75

(136) TABLE-US-00015 TABLE 3.2 I-R-1 and Spinetoram. solo application combination Spinetoram I-R-1 Spinetoram + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Boll Weevil 4 0 2 0 4 + 2 100

(137) TABLE-US-00016 TABLE 3.3 I-R-1 and Fluxametamide. solo application combination Fluxametamide I-R-1 Fluxametamide + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Boll Weevil 0.4 25 2 0 0.4 + 2 100

(138) Test 4

(139) 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.

(140) The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 10 μl, using a custom built micro atomizer, at two replications.

(141) For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

(142) After application, microtiter plates were incubated at 28±1° C., 80±5% RH for 5 days. Egg and larval mortality was then visually assessed. For the mixture tested the results are listed in tables 4.1 and 4.2.

(143) TABLE-US-00017 TABLE 4.1 I-R-1 and Pymetrozine. solo application combination Pymetrozine I-R-1 Pymetrozine + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Tobacco budworm 10 0 10 0 10 + 10 50

(144) TABLE-US-00018 TABLE 4.2 I-R-1and Alpha-Cypermethrin. solo application combination Alpha-Cypermethrin I-R-1 Alpha-Cypermethrin + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Tobacco budworm 2 50 0.4 0 2 + 0.4 100

(145) For evaluating control of Greenhouse Whitefly (Trialeurodes vaporariorum) the test unit consisted of 96-well-microtiter plates containing a leaf disk of egg plant leaf disk with white fly eggs. The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 2.5 μl, using a custom built micro atomizer, at two replications.

(146) For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

(147) After application, microtiter plates were incubated at 23±1° C., 65±5% RH for 6 days. Mortality of hatched crawlers was then visually assessed. For the mixture tested the results are listed in table 5.

(148) TABLE-US-00019 TABLE 5 I-R-1 and Oxazosulfyl. solo application combination Oxazosulfyl I-R-1 Oxazosulfyl + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Greenhouse Whitefly 50 50 2 0 50 + 2 100

(149) Test 6:

(150) For evaluating control of brown planthopper (Nilaparvata lugens) by foliar spray method. Clean potted rice seedlings with upper leaf portion cut are properly labeled. Placed three potted rice plants per treatment concentration/combination on top of the rotating disc (270 mm) and sprayed with the 12 mL spray solution. Treated plants are allowed to air-dry in the laboratory for about an hour. After air-drying, covered each treated rice plant. Each treated plant was infested with brown planthoppers using a suction vacuum. Plants are maintained at 27° C.±1° C., 50±5% RH and 24 hours light conditions in a holding room. Percent mortality is recorded 7 days after infestation by counting both the dead and alive brown planthoppers on the plants and on the water. The average control after 7 days of compounds and mixtures tested are given in table 6.1 to 6.2.

(151) TABLE-US-00020 TABLE 6.1 I-R-1and Pymetrozine. solo application combination Pymetrozine I-R-1 Pymetrozine + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % brown planthopper 300 26 5 62 300 + 5 85

(152) TABLE-US-00021 TABLE 6.2 I-R-1 and Spinetoram. solo application combination Spinetoram I-R-1 Spinetoram + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % brown planthopper 70 62 5 62 70 + 5 100

(153) Test 7:

(154) 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.

(155) The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Concentrations of formulated compounds or mixtures were sprayed onto the leaf disks at 2.5 μl, using a custom built micro atomizer, at two replications.

(156) For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

(157) 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 23±1° C., 50±5% RH for 5 days. Aphid mortality and fecundity was then visually assessed. For the mixture tested the results are listed in tables 7.1 and 7.2.

(158) TABLE-US-00022 TABLE 7.1 solo application combination Furametpyr I-R-1 Furametpyr + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Vetch Aphid 2500 0 2 25 2500 + 2 75

(159) TABLE-US-00023 TABLE 7.2 solo application combination Metalaxyl I-R-1 Metalaxyl + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Vetch Aphid 2500 0 2 25 2500 + 2 50

(160) Test 8:

(161) 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.

(162) The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Concentrations of formulated compounds or mixtures were pipetted into the aphid diet, using a custom built pipetter, at two replications.

(163) For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

(164) 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 23±1° C., 50±5% RH for 3 days. Aphid mortality and fecundity was then visually assessed. For the mixture tested the results are listed in tables 8.1 and 8.2.

(165) TABLE-US-00024 TABLE 8.1 solo application combination Probenazole I-R-1 Probenazole + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Green Peach Aphid 500 0 0.4 0 500 + 0.4 75

(166) TABLE-US-00025 TABLE 8.2 solo application combination Dicyclomet I-R-1 Dicyclomet + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Green Peach Aphid 2500 0 0.4 0 2500 + 0.4 75

(167) Test 9:

(168) For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 24-well-microtiter plates containing an insect diet and 20-30 A. grandis eggs.

(169) The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 20 μl, using a custom built micro atomizer, at two replications.

(170) For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

(171) After application, microtiter plates were incubated at 23±1° C., 50±5% RH for 5 days. Egg and larval mortality was then visually assessed. For the mixture tested the results are listed in tables 9.1 and 9.2.

(172) TABLE-US-00026 TABLE 9.1 solo application combination Penflufen I-R-1 Penflufen + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Boll Weevil 2500 0 50 25 2500 + 50 50

(173) TABLE-US-00027 TABLE 9.2 solo application combination Metalaxyl I-R-1 Metalaxyl + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Boll Weevil 500 0 10 25 500 + 10 50

(174) Test 10:

(175) 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.

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

(177) For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

(178) After application, microtiter plates were incubated at 28±1° C., 80±5% RH for 5 days. Egg and larval mortality was then visually assessed. For the mixture tested the results are listed in tables 10.1 and 10.2.

(179) TABLE-US-00028 TABLE 10.1 solo application combination Probenazole I-R-1 Probenazole + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Tobacco budworm 2500 0 10 0 2500 + 10 50

(180) TABLE-US-00029 TABLE 10.2 solo application combination Pyroquilon I-R-1 Pyroquilon + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Tobacco budworm 2500 0 10 25 2500 + 10 50

(181) Test 11:

(182) For evaluating control of Greenhouse Whitefly (Trialeurodes vaporariorum) the test unit consisted of 96-well-microtiter plates containing a leaf disk of egg plant leaf disk with white fly eggs.

(183) The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 2.5 μl, using a custom built micro atomizer, at two replications.

(184) For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

(185) After application, microtiter plates were incubated at 23±1° C., 65±5% RH for 6 days. Mortality of hatched crawlers was then visually assessed. For the mixture tested the results are listed in tables 11.1 and 11.2.

(186) TABLE-US-00030 TABLE 11.1 solo application combination Simeconazol I-R-1 Simeconazol + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Greenhouse Whitefly 2500 0 50 25 2500 + 50 100

(187) TABLE-US-00031 TABLE 11.2 solo application combination Buprofezin I-R-1 Buprofezin + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Greenhouse Whitefly 2500 50 10 0 2500 + 10 100

(188) Test 12:

(189) For evaluating control of yellow fever mosquito (Aedes aegypti) the test unit consisted of 96-well-microtiter plates containing 200 μl of tap water per well and 5-15 freshly hatched A. aegypti larvae.

(190) The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 2.5 μl, using a custom built micro atomizer, at two replications.

(191) For experimental mixtures in these tests identical volumes of both mixing partners at the desired concentrations respectively, were mixed together.

(192) After application, microtiter plates were incubated at 28±1° C., 80±5% RH for 2 days. Larval mortality was then visually assessed. For the mixture tested the results are listed in tables 12.

(193) TABLE-US-00032 TABLE 12 solo application combination Tricyclazol I-R-1 Tricyclazol + I-R-1 use rate Average use rate Average use rate Average insect (ppm) control % (ppm) control % (ppm) control % Yellow Fever Mosquito 2500 50 10 0 2500 + 10 100