WO2007081845A2

WO2007081845A2 - Mixture of indoxacarb and dimehypo

Info

Publication number: WO2007081845A2
Application number: PCT/US2007/000357
Authority: WO
Inventors: S. H. Chang; Kok-Eng Ooi
Original assignee: E. I. Du Pont De Nemours And Company
Priority date: 2006-01-10
Filing date: 2007-01-09
Publication date: 2007-07-19
Also published as: TW200735778A; KR20080106177A; CN101494983A; WO2007081845A3; MY144106A

Abstract

Disclosed is a mixture for protecting a plant from an insect pest comprising indoxacarb and dimehypo, and a method of its use for controlling the insect pest in an agronomic environment.

Description

TITLE MIXTURE OF INDOXACARB AND DIMEHYPO

FIELD OF THE INVENTION

This invention pertains to a mixture for protecting a plant from an insect pest comprising indoxacarb and dimehypo, and a method of its use for controlling the insect pest in agronomic environments.

BACKGROUND OF THE INVENTION

Insecticide applications that can be applied at as low a dose as possible and be effective in controlling pest species of insects while causing as little harm as possible to beneficial insects and minimal disturbance in the environment are in demand by the farming community. Insect pests are very destructive to crop plants and can result in significant loss of crop yield and quality, which results in economic loss to the grower and increased costs to the consumer. Combinations of insecticides are typically used to broaden the spectrum of insect control or enhance the level of control of any given species through additive effect. Certain rare combinations surprisingly give an agronomically useful greater-than-additive or synergistic effect.

Indoxacarb is sold by DuPont as the active ingredient in Avaunt^®, Animate^® and Steward® insecticides for foliar application to control numerous insect pests of agricultural crops (e.g., cotton, vegetables and fruits) including, but not limited to, insects from the order Lepidoptera (e.g., cotton bollworm, beet armyworm, fall armyworm, cabbage and soybean loopers, codling moth and diamondback moth), Coleoptera (e.g., Colorado potato beetles and weevils), and Hemiptera (e.g., leafhoppers, plant bugs, lygus bugs). Indoxacarb is particularly effective and acts rapidly against Lepidopteran insects, which are foliar feeders, but has little effect on beneficials (predators and parasites), which are not phytophagous and only have contact with indoxacarb as a dry residual.

Dimehypo is sold as the active ingredient in Pilarhope®, Helper^® and Spontan® insecticides and used for control of chewing and sucking insects (particularly Lepidoptera and Coleoptera) on many agricultural crops including, but not limited to, rice, vegetables and fruit trees. Dimehypo is an analog of nereistoxin and is generally considered to be a stomach poison having both contact and systemic activity.

Being able to reduce the quantity of chemical agents released in the environment while ensuring effective pest control is always desirable. Although many combinations of pest control agents have been studied, synergism increasing agronomically useful efficacy is generally not found. Synergism has been described as "the cooperative action of two components of a mixture, such that the total effect is greater or more prolonged than the sum of the effects of the two (or more) taken independently" (see P. M. L. Yames, Neth. J. Plant Pathology 1964, 70, 73-80). Therefore, obtaining an insecticidal composition that demonstrates high pest controlling efficacy greater than expected from additive effects, with concomitant reduced crop production cost and reduced environmental load, is highly desirable.

Mixtures of indoxacarb and dimehypo providing surprisingly good control of insect pests have now been discovered. SUMMARY OF THE INVENTION

This invention pertains to a mixture comprising indoxacarb (methyl (4aS)-7-chloro-

2,5-dihydro-2-[[(methoxycarbonyl)[4-(trifluoromethoxy)phenyl]amino]carbonyl]indeno[l₅2- e][l,3,4]oxadiazine-4a(3i-T)-carboxylate) and dimehypo (also known as thiosultap-sodium, and disodium iS,S^J-[2-(dimethylarnino)-l,3-propanediyl] ester thio sulfate), which is useful for controlling an insect pest.

This invention also pertains to an insecticidal composition comprising an insecticidally effective amount of a mixture of indoxacarb and dimehypo, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, and optionally an additional biologically effective compound or agent. This invention also pertains to a method for protecting a plant from an insect pest comprising contacting the insect pest or its environment with an insecticidally effective amount of a mixture comprising indoxacarb and dimehypo.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

Also, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore "a" or "an" should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.

In the context of this disclosure "insect pest control" means inhibition of insect pest development (including mortality, feeding reduction, and/or mating disruption), and related expressions are defined analogously.

The term "agronomic" refers to the production of field crops such as for food and fiber and includes the growth of corn, soybeans and other legumes, rice, cereal (e.g., wheat, oats, barley, rye, rice, maize), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers and cucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruit (berries, cherries) and other specialty crops (e.g., canola, sunflower, olives).

Embodiments of the present invention as described in the Summary of the Invention include:

Embodiment 1. The mixture as described in the Summary of the Invention wherein indoxacarb and dimehypo are in a weight ratio between about 1:1 and about 1:50.

Embodiment IA. The mixture of Embodiment 1 wherein indoxacarb and dimehypo are in a weight ratio between about 1:2.5 and about 1 :40.

Embodiment IB. The mixture of Embodiment 1 wherein indoxacarb and dimehypo are in a weight ratio between about 1 :5 and about 1 :30. Embodiment 1C. The mixture of Embodiment 1 wherein indoxacarb and dimehypo are in a weight ratio between about 1:15 and about 1 :25. Embodiment 2. The method as described in the Summary of the Invention wherein indoxacarb and dimehypo are applied consecutively. Embodiment 2A. The method of Embodiment 2 wherein indoxacarb is applied first and then dimehypo is applied.

Embodiment 2B. The method of Embodiment 2 wherein dimehypo is applied first and then indoxacarb is applied.

Embodiment 2C. The method as described in the Summary of the Invention wherein indoxacarb and dimehypo are applied simultaneously. Embodiment 3. The method as described in the Summary of the Invention wherein the insect pest is a species of the order Lepidoptera. Embodiment 3 A. The method of Embodiment 3 wherein the insect pest is selected from a species of one of the families Crambidae, Gelechiidae, Noctuidae, Plutellidae, Pyralidae and Tortricidae. Embodiment 3B. The method of Embodiment 3 wherein the insect pest is selected from the species Crambus caliginosellus, Crambus teterrellus, Diatraea saccharalis, Keiferia lycopersicella, Pectinophora gossypiella, Earias insulana, Earias vittella, Helicoverpa armigera, Helicoverpa zea, Heliothis virescens, Spodoptera exigua, Spodoptera frugiperda, Spodoptera litura, Plutella xylostella, Chilo suppressalis, Chilo poly chrysus, Cnaphalocrocis medinalis, Marasmia patnalis, Sdropophaga incertulas, Sciropophaga innotata, Sesamia inferens, Archips argyrospila, Archips rosana, Cydia pomonella, Grapholita molesta, Leucinodes spp., Maruca spp., Ostrinia spp., Trichoplusia spp. and Earias spp.. Embodiment 3C. The method of Embodiment 3 wherein the insect pest is selected from the species Sciropophaga incertulas, Sciropophaga innotata, Sesamia inferens,

Chilo suppressalis, Chilo polychrysus, Cnaphalocrocis medinalis and Marasmia patnalis.

Embodiment 3D. The method of Embodiment 3 wherein the insect pest is Sciropophaga incertulas.

Embodiment 3E. The method of Embodiment 3 wherein the insect pest is Sciropophaga innotata. Embodiment 3F. The method of Embodiment 3 wherein the insect pest is Sesamia inferens. Embodiment 3 G. The method of Embodiment 3 wherein the insect pest is Chilo suppressalis. Embodiment 3H. The method of Embodiment 3 wherein the insect pest is Chilo polychrysus.

Embodiment 31. The method of Embodiment 3 wherein the insect pest is Cnaphalocrocis medinalis.

Embodiment 3K. The method of Embodiment 3 wherein the insect pest is Marasmia patnalis. Embodiment 4. The method as described in the Summary of the Invention wherein the insect pest is a species of the order Hemiptera. Embodiment 4A. The method of Embodiment 4 wherein the insect pest is selected from a species of one of the families Cercopidae, Flatidae, Fulgoridae, Miridae,

Adelgidae, Aleyrodidae, Aphididae, Cicadellidae and Delphacidae. Embodiment 4B. The method of Embodiment 4 wherein the insect pest is selected from the species Euryaulax carnifex, Colgar peracutum, Phromnia rosea, Fulgora lanternaria, Lygus lineolaris, Adelges abietis, Bemisia argentifolii, Bemisia tabaci, Aphis spp., Myzus persicae, Nephotettix nigropictus, Laodelphax striatellus, Nilaparvata lugens, Sogatellafurcifera, Sogatodes oryzicola and

Recilia dorsalis.

Embodiment 5. The method as described in the Summary of the Invention wherein the insect pest is a species of the order Thysanoptera.

Embodiment 5 A. The method of Embodiment 5 wherein the insect pest is a species of the family Thripidae. Embodiment 5B. The method of Embodiment 5 wherein the insect pest is a

Frankliniella species. Embodiment 6. The method as described in the Summary of the Invention wherein the plant is in one of the families Brassicaceae, Fabaceae, Lilaceae and Poaceae. Embodiment 7. The method of Embodiment 6 wherein the plant is in the family

Brassicaceae. Embodiment 7A. The method of Embodiment 7 wherein the plant is a Brassica species. Embodiment 7B. The method of Embodiment 7 wherein the plant is Brassica carinata, Brassica oleracea, Brassica juncea, Brassica nigra, Brassica napus or Brassica rapa.

Embodiment 8. The method of Embodiment 6 wherein the plant is in the family Fabaceae.

Embodiment 8 A. The method of Embodiment 8 wherein the plant is selected from species of the genera Phaseolus and Vigna. Embodiment 8B. The method of Embodiment 8 wherein the plant is Phaseolus vulgaris, Phaseolus coccineus, Phaseolus acutifolius, Phaseolus lunatus, Vigna angular is, Vigna radiata or Vigna unguiculata.

Embodiment 9. The method of Embodiment 6 wherein the plant is in the family

Lilaceae. Embodiment 9 A. The method of Embodiment 9 wherein the plant is an Allium species. Embodiment 9B. The method of Embodiment 9 wherein the plant is Allium ascalonicum, Allium cepa, Allium fistulosum, Allium ampeloprasum var. porrum, Allium sativum or Allium schoenoprasum. Embodiment 10. The method of Embodiment 6 wherein the plant is in the family

Poaceae. Embodiment 1OA. The method of Embodiment 10 wherein the plant is an Oryza species. Embodiment 1OB. The method of Embodiment 10 wherein the plant is Oryza sativa or

Oryza glaberrima.

Of note as embodiments are insecticidal compositions of the present invention comprising an insecticidally effective amount of a mixture of Embodiments 1, IA, IB and

1C and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, and optionally an additional biologically effective compound or agent.

Embodiments of this invention, including Embodiments 1-1 OB above, as well as any other embodiments described herein, pertain to the compositions, mixtures and methods of the present invention which can be combined in any manner.

Examples of combinations of Embodiments 1-1 OB include:

Embodiment A. The method as described in the Summary of the Invention wherein the plant is a Brassica carinata, Brassica oleracea, Brassica juncea, Brassica nigra, Brassica napus, Brassica rapa, Phaseolus vulgaris, Phaseolus coccineus,

Phaseolus acutifolius, Phaseolus lunatus, Vigna angularis, Vigna radiata, Vigna unguiculata, Allium ascalonicum, Allium cepa, Allium fistulosum, Allium ampeloprasum var. porrum, Allium sativum, Allium schoenoprasum, Oryza sativa or Oryza glaberrima species. Embodiment B. The method of Embodiment A wherein the plant is Oryza sativa or Oryza glaberήma species.

Application of indoxacarb and dimehypo have now been found to not only protect the plant from certain foliar insects but provide control which is substantially and surprisingly enhanced over the expected simply additive effect of indoxacarb and dimehypo.

Indoxacarb (Chemical Abstracts name: methyl (5)-7-chloro-2,5-dihydro-2- [[(methoxycarbonyl)[4-(trifluoromethoxy)phenyl]amino]carbonyl]indeno[l,2-e][l,3,4]oxa- diazine-4a(3H)-carboxylate) has the molecular formula depicted as Formula I.

Although indoxacarb is most conveniently obtained as a commercial product, it can be prepared as described in U.S. Patent 5,462,938 and U.S. Patent 5,869,657.

Dimehypo (Chemical Abstracts name: disodium 2-dimethylaminopropane-l,3-bisthio- sulfonate, and also known as thiosultap-sodium) has the molecular formula depicted as Formula II and is most conveniently obtained as a commercial product.

H₃C CH₂SSO₃Na

N-CH H₃C CH₂SSO₃Na

π

Formulation/Utility

Mixtures of indoxacarb and dimehypo according to the present invention can generally be used in a formulation or a composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. Mixtures of indoxacarb and dimehypo can be formulated in two ways:

1. Indoxacarb and dimehypo can be formulated separately and applied separately or applied simultaneously in an appropriate weight ratio, e.g., as a tank mix; or

2. Indoxacarb and dimehypo can be formulated together in the weight ratios as defined herein. Therefore useful for the formulations of the present invention are compositions comprising an insecticidally effective amount of indoxacarb and an agriculturally suitable carrier comprising at least one of a surfactant, a solid or a liquid diluent; an insecticidally effective amount of dimehypo and an agriculturally suitable carrier comprising at least one of a surfactant, a solid or a liquid diluent; or an insecticidally effective amount of a mixture of indoxacarb and dimehypo and an agriculturally suitable carrier comprising at least one of a surfactant, a solid or a liquid diluent. The optional additional biologically active compound or agent in compositions of the present invention can also be combined with an agriculturally suitable carrier comprising at least one of a surfactant, a solid or a liquid diluent before or after mixing with indoxacarb and/or dimehypo.

The agriculturally suitable carriers are selected consistent with the physical properties of the active ingredients, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations of indoxacarb and dimehypo, either separately or together or with an optional additional biological compound or agent, can be prepared in conventional ways. Useful formulations include liquids such as solutions (including emulsifϊable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible ("wettable") or water-soluble. Active ingredient(s) can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient(s). Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.

The formulations will typically contain effective amounts of active ingredient(s), diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.

Weight Percent

Active Ingredient Diluent Surfactant

Water-Dispersible and Water- 0.001-90 0-99.999 0-15 soluble Granules, Tablets and Powders.

Suspensions, Emulsions, 1-50 40-99 0-50 Solutions (including Emulsifϊable Concentrates)

Dusts 1-25 70-99 0-5

Granules and Pellets 0.001-99 5-99.999 0-15

High Strength Compositions 90-99 0-10 0-2 Typical solid diluents are described in Watkins, et al.. Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon 's Detergents anώ Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.

Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, JV,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, glycerol esters, poly- oxyethylene/polyoxypropylene block copolymers, and alkylpolyglycosides where the number of glucose units, referred to as degree of polymerization (D.P.), can range from 1 to 3 and the alkyl units can range from Cg to C₁₄ (see Pure and Applied Chemistry 72, 1255- 1264). Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, iV_^/V-dimethylformamide, dimethyl sulfoxide, iV-alkylpyrrolidone, ethylene glycol, polypropylene glycol, propylene carbonate, dibasic esters, paraffins, alkylbenzenes, alkylnaphthalenes, glycerine, triacetine, oils of olive, castor, linseed, rung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as hexyl acetate, heptyl acetate and octyl acetate, and alcohols such as methanol, cyclohexanol, decanol, benzyl and tetrahydrofurfuryl alcohol.

Useful formulations of this invention can also contain materials well known to those skilled in the art as formulation aids such as antifoams, film formers and dyes. Antifoams can include water dispersible liquids comprising polyorganosiloxanes like Rhodorsil 416. The film formers can include polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Dyes can include water dispersible liquid colorant compositions like Pro-lzed^® Colorant Red. One skilled in the art will appreciate that this is a non-exhaustive list of formulation aids. Suitable examples of formulation aids include those listed herein and those listed in McCutcheon 's 2005, Volume 2: Functional Materials published by MC Publishing Company and PCT Publication WO 03/024222.

Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active ^■ material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.

For further information regarding the art of formulation, see T. S. Woods, "The Formulator's Toolbox — Product Forms for Modern Agriculture" in Pesticide Chemistry and Bioscience, The Food— Environment Challenge, T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000. In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. For example, the formulation ingredients of Example E are mixed together as a syrup, the active ingredients are added and the mixture is homogenized in a blender. The resulting slurry is then wet-milled to form a suspension concentrate.

Example A

Wettable Powder indoxacarb 3.0% dimehypo 60.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 25.0%.

Example B

Granule indoxacarb 1% dimehvoo 9% attapulgite granules (low volatile matter,

0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%. Example C

Extruded Pellet indoxacarb 5.0% dimehypo 20.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%

Example D

Emulsifiable Concentrate indoxacarb 1.0% dimehypo 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 69.0%

Example E

Suspension Concentrate indoxacarb 1.0% dimehypo 20.0% polyethoxylated fatty alcohol 15.0% ester derivative of montan wax 3.0% calcium lignosulfonate 2.0% polyethoxylated/polypropoxylated poly glycol block copolymer 1.0% propylene glycol 6.4% poly(dimethylsiloxane) 0.6% antimicrobial agent 0.1% water 50.9%

Mixtures and compositions of the present invention comprising indoxacarb and dimehypo can also be further mixed with at least one additional biologically effective compound or agent such as insecticides, fungicides, nematocides, bactericides, acaricides, semiochemicals, repellents, attractants, pheromones, feeding stimulants to form a multi- component pesticide giving an even broader spectrum of agricultural protection. Examples of such agricultural protectants with which compounds of this invention can be formulated are: insecticides such as abamectin, acephate, carbaryl, carbofuran, cartap, chlorantraniliprole (DPX-E2Y45), chlorpyrifos, chlorpyrifos-methyl, cyfluthrin, cypermethrin, diazinon, fipronil. flubendiamide, monocrotophos, phorate, rotenone, and neonicotinoids such as acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam; fungicides such as azoxystrobin, benomyl, captan, carbendazim, cymoxanil, cyprodinil, difenoconazole, diniconazole, diniconazole-M, edifenphos, epoxiconazole, fenarimol, fenbuconazole, fenpropimorph, fluazinam, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fosetyl-aluminum, furalaxyl, hexaconazole, ipconazole, iprobenfos, iprodione, kresoxim-methyl, mancozeb, maneb, mepronil, metalaxyl, metconazole, myclobutanil, oxadixyl, penconazole, probenazole, prochloraz, propiconazole, pyrifenox, tebuconazole, tetraconazole, thiabendazole, thiophanate-methyl, thiram, tricyclazole and triticonazole, uniconazole; nematocides such as aldoxycarb and fenamiphos; bactericides such as streptomycin; and biological agents including entomopathogenic bacteria, such as Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, and the encapsulated delta-endotoxins of Bacillus thuringiensis (e.g., Cellcap, MPV, MPVII); entomopathogenic fungi, such as green muscardine fungus; and entomopathogenic virus including baculovirus, nucleopolyhedrovirus (NPV) such as Helicoverpa ∑ea nucleopolyhedrovirus (HzNPV), Anagrapha falcifera nucleopolyhedrovirus (AfNPV); and granulosis virus (GV) such as Cydia pomonella granulosis virus (CpGV). The weight ratios of additional biologically effective compounds or agents to the mixtures of this invention typically are between 200:1 and 1:200, preferably between 50:1 to 1:50, more preferably between 10:1 to 1 :10.

Of particular note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with an additional biologically effective compound selected from the group consisting of abamectin, acephate, acetamiprid, carbofuran, cartap, chlorantraniliprole, chlorpyrifos, clothianidin, cyfluthrin, cypermethrin, diazinon, fipronil, flubendiamide, imidacloprid, monocrotophos, phorate, thiacloprid and thiamethoxam.

Of note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with monocrotophos. Of note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with chlorpyrifos. Of note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with imidacloprid. Of note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with fipronil. Of note is a mixture of the present invention comprising indoxacarb and dimehypo further mixed with carbofuran. Of note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with diazinon. Of note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with cartap. Of note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with phorate. Of note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with cypermethrin. Of note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with thiamethoxam. Of note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with abamectin. Of note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with cyfluthrin. Of note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with acephate. Of note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with thiacloprid. Of note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with acetamiprid. Of note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with clothianidin. Of note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with chlorantraniliprole. Of note is a mixture of the invention comprising indoxacarb and dimehypo further mixed with flubendiamide.

General references for these agricultural protectants (i.e. insecticides, fungicides, nematocides, acaricides, herbicides and biological agents) include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2003 and The BioPesticide Manual, 2^nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2001.

In certain instances, combinations with other insecticides having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management. An insect pest is controlled by applying a biologically effective amount of a mixture of this invention to the environment of the insect pest including the locus of infestation, to the area to be protected, or directly on the pest to be controlled. Thus, the present invention comprises a method for the control of an insect pest comprising contacting the insect pest or its environment with a biologically effective amount of a mixture of this invention, or with a composition of the present invention comprising said mixture which can include an effective amount of at least one additional biologically active compound or agent. Examples of suitable compositions comprising a mixture of the invention and/or a mixture of the invention and an effective amount of at least one additional biologically effective compound or agent include granular compositions wherein the additional biologically effective compound is present on the same granule as the mixture of the invention or on granules separate from those of the mixture of this invention. In addition, indoxacarb and dimehypo can be present on separate granules, and any additional biologically effective compound could reside on either of the indoxacarb or dimehypo granules or on a third set of granules. Further, variations of the above types of granules can be combined to provide mixtures and/or compositions of the present invention. Thus in one embodiment, the composition of the present invention comprises a mixture of at least two groups of granules containing different amounts of indoxacarb, dimehypo and any other agricultural protectants (i.e. biologically effective compounds or agents) as active ingredients. For example, one set of granules may comprise indoxacarb, and a second set of granules may comprise dimehypo as active ingredient. These granule mixtures can be in accordance with the general granule mixture disclosure of PCT Patent Publication WO 94/24861 or more preferably the homogenous granule mixture teaching of U.S. Patent 6,022,552.

A preferred method of contact is by spraying. One embodiment of the method of this invention for controlling phytophagous insect pests is by applying to a plant an effective amount of a mixture comprising indoxacarb and dimehypo. Furthermore, a separate composition comprising indoxacarb and a composition comprising dimehypo can be combined as a physical mixture prior to application, e.g., a tank mix, and applied simultaneously. Alternatively, insecticidal compositions containing a composition of only one of indoxacarb and dimehypo can be applied followed by application of a composition of the other of indoxacarb and dimehypo.

The rate of application required for effective control (i.e. "biologically effective amount") will depend on such factors as the species of insect pest to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 100 g/hectare to 2000 g/hectare of aggregate active ingredient are sufficient to control pests in agronomic ecosystems, but as little as 10 g/hectare may be sufficient or as much as 4000 g/hectare may be required. Aggregate active ingredient is defined as the total combined weight of active ingredients. Typically the weight ratio of indoxacarb and dimehypo is between about 1:1 to 1:50, preferably between about 1:2.5 and 1:40, more preferably between about 1 :5 and 1 :30, and most preferably between about 1 :15 and 1:25. Rates of application for a mixture of the present invention according to the method of this invention can be influenced by many factors in the environment and should be determined under actual use conditions. One skilled in the art can easily determine the biologically effective amount necessary for the desired level of insect pest control.

For reasons of insect pest control spectrum and economic importance, protection of agronomic crops from damage or injury caused by insect pests by controlling the insect pests are embodiments of the invention.

The method of the present invention is useful for protecting plants from a wide range of insect pests including eggs, larvae and adults of the order Lepidoptera, such as armyworms, cutworms, loopers, and heliothines in the family Noctuidae (e.g., fall armyworm (Spodoptem frugiperda J. E. Smith), beet armyworm (Spodoptera exigua Hϋbner), black cutworm (Agrotis ipsilon Hufhagel), cabbage looper (Trichoplusia ni Hϋbner), tobacco budworm (Heliothis virescens Fabricius)); borers, casebearers, webworms, coneworms, cabbageworms and skeletonizers from the family Pyralidae (e.g., European corn borer (Ostrinia nubilalis Hϋbner), navel orangeworm (Amyelois transitella Walker)); webworms from the family Crambidae (e.g., sod worm (Herpetogramma licarsisalis Walker), corn root webworm (Cr ambus caligmosellus Clemens)); leafrollers, budworms, seed worms, and fruit worms in the family Tortricidae (e.g., codling moth (Cydia pomonella Linnaeus), grape berry moth (Endopiza viteana Clemens), oriental fruit moth (Grapholita molesta Busck)); and many other economically important lepidoptera such as diamondback moth {Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth (Lymantria dispar Linnaeus)); eggs, foliar feeding, fruit feeding, root feeding, seed feeding and vesicular tissue feeding larvae and adults of the order Coleoptera including weevils from the families Anthribidae, Bruchidae, and Curculionidae (e.g., boll weevil (Anthonomus grandis Boheman), rice water weevil (Lissorhoptrus oryzophilus Kuschel), granary weevil (Sitophilus granarius Linnaeus), rice weevil (Sitophilus oryzae Linnaeus)), annual bluegrass weevil (Listronotus maculicoUis Dietz), bluegrass billbug (Sphenophorus parvulus Gyllenhal), hunting billbug (Sphenophorus venatus vestitus), Denver billbug (Sphenophorus cicatristriatus Fahraeus)); flea beetles, cucumber beetles, rootworms, leaf beetles, potato beetles and leafminers in the family Chrysomelidae (e.g., Colorado potato beetle (Leptinotarsa decemlineata Say), western corn rootworm (Diabrotica virgifera virgifera LeConte)); chafers and other beetles from the family Scarabaeidae (e.g., Japanese beetle (Popillia japonica Newman), oriental beetle (Anomala orientalis Waterhouse), northern masked chafer (Cyclocephala borealis Arrow), southern masked chafer (Cyclocephala immaculata Olivier), black turfgrass ataenius (Ataenius spretulus Haldeman), green June beetle (Cotinis nitida Linnaeus), Asiatic garden beetle (Maladera castanea Arrow), May/June beetles (Phyllophaga spp.) and European chafer (Rhi∑otrogus majalis Razoumowsky)); carpet beetles from the family Dermestidae; wireworms from the family Elateridae; bark beetles from the family Scolytidae and flour beetles from the family Tenebrionidae. In addition, agronomic pests include: eggs, adults and larvae of the order Dermaptera including earwigs from the family Forficulidae (e.g., European earwig (Forficula auricularia Linnaeus), black earwig (Chelisoches morio Fabricius)); eggs, immatures, adults and nymphs of the orders Hemiptera and Homoptera such as, plant bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g., Empoasca spp.) from the family Cicadellidae, planthoppers from the families Flatidae (e.g., citrus planthopper (Colgar peracutum Walker), mango planthopper (Colgarorides acuminate Walker), flatid leaf bug (Phromnia rosea Isalo), and green planthopper (Siphanta acuta Walker)), Fulgoroidae (e.g., lantern fly (Fulgora lanternaria ), peanut bug (Lanternaria lanternaria)) and Delphacidae, treehoppers from the family Membracidae, psyllids from the family Psyllidae, whiteflies from the family Aleyrodidae, aphids from the family Aphididae, phylloxera from the family Phylloxeridae, mealybugs from the family Pseudococcidae, scales from the families Coccidae, Diaspididae and Margarodidae, lace bugs from the family Tingidae, stink bugs from the family Pentatomidae, chinch bugs (e.g., hairy chinch bug (Blissus leucopterus hirtus Montandon) and southern chinch bug (Blissus insularϊs Barber)) and other seed bugs from the family Lygaeidae, spittlebugs from the family Cercopidae (e.g., froghopper (Cercopis sanguinea Geoffroy, Cercopis vulnerata Rossi) and sugarcane froghopper (Euryaulax carnifex Fabricius)), squash bugs from the family Coreidae, and red bugs and cotton stainers from the family Pyrrhocoridae. Also included are eggs, adults and immatures of the order Orthoptera including grasshoppers, locusts and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius and M. differentialis Thomas), American grasshoppers (e.g., Schistocerca americana Drury), desert locust (Schistocerca gregaria Forskal), migratory locust (Locusta migratoria Linnaeus), bush locust (Zonocerus spp.), house cricket (Acheta domesticus Linnaeus), mole crickets (e.g., tawny mole cricket (Scapteriscus vicinus Scudder) and southern mole cricket (Scapteriscus borellii Giglio-Tos)); eggs, adults and immatures of the order Diptera including leafminers, midges, fruit flies (Tephritidae), frit flies (e.g., Oscinella frit Linnaeus), soil maggots, house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g., Fannia canicularis Linnaeus, F. femoralis Stein), stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g., Chrysomya spp., Phormia spp.), and other muscoid fly pests, horse flies (e.g., Tabanus spp.), bot flies (e.g., Gastrophilus spp., Oestrus spp.), cattle grubs (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.), keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g., Aedes spp., Anopheles spp., Culex spp.), black flies

(e.g., Prosimulium spp., Simulium spp.), biting midges, sand flies, sciarids, and other

Nematocera; eggs, immatures and adults of the order Thysanoptera including onion thrips

(Thrips tabaci Lindeman), flower thrips (Frankliniella spp.), and other foliar feeding thrips.

Mixtures of the invention show particularly high activity against pests in the order Lepidoptera (e.g., Chilo polychrysus Meyrick (darkheaded rice borer), Chilo suppressalis Walker (striped rice borer), Cnaphalocrocis medinalis Guenee (rice leaffolder), Crambus caliginosellus Clemens (corn root webworm), Diatraea saccharalis Fabricius (sugarcane borer), Diatraea crambidoides Grote (southern corn borer), Earias insulana Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoverpa armigera Hϋbner (American bollworm), Marasmia patnalis (rice leaffolder), Ostrinia nubilalis Hϋbner (European corn borer), Pseudaletia unipuncta Haworth (armyworm), Pectinophora gossypiella Saunders (pink bollworm), Pieris brassicae Linnaeus (large white butterfly), Pieris rapae Linnaeus (small white butterfly), Plutella xylostella Linnaeus (diamondback moth), Scirpophaga innotata (white stem borer), Scirpophaga incertulas (yellow stem borer), Sesamia inferens (pink stem borer), Spodoptera exigua Hϋbner (beet armyworm), Spodoptera litwra Fabricius (tobacco cutworm, cluster caterpillar), Spodoptera littoralis (leaf worm), Spodoptera frugiperda J. E. Smith (fall armyworm), Trichoplusia ni Hubner (cabbage looper), Leucinodes spp. (e.g., eggplant borer), Maruca spp. (bean pod borers), Ostrinia spp. (e.g., European corn borer) and Trichoplusia spp. (loopers). Mixtures of the invention also have significant activity on members from the order

Hemiptera and Homoptera including: Acyrthosiphon pisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aulacorthum solani Kaltenbach (foxglove aphid), My∑us persicae Sulzer (green peach aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Rhopalosiphum maidis Fitch (corn leaf aphid), Rhopalosiphum padi Linnaeus (bird cherry- oat aphid), Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius (English grain aphid); Bemisia tabaci Gennadius (tobacco whitefly, sweet potato whitefly), Bemisia argentifolii Bellows & Perring (silverleaf whitefly) and Trialeurodes vaporariorum Westwood (greenhouse whitefly); Empoasca fabae Harris (potato leafhopper), Laodelphax striatellus Fallen (smaller brown planthopper). Macrosteles quadrilineatus Forbes (aster leafhopper), Nephotettix cinticeps Uhler (green leafhopper), Nephotettix nigropictus Stal (rice leafhopper), Nilaparvata lugens Stal (brown planthopper), Peregrinus maidis Ashmead (corn planthopper), Recilia dorsalis Motschulsky (zigzag leafhopper), Sogatella furcifera Horvath (white-backed planthopper), Sogatodes oryzicola Muir (rice delphacid), Icerya purchasi Maskell (cottony cushion scale), Acrosternum hilare Say (green stink bug), Anasa tristis DeGeer (squash bug), Blissus leucopterus leucopterus Say (chinch bug), Dysdercus suturellus Herrich-Schaeffer (cotton stainer), Euschistus servus Say (brown stink bug), Eiischistus variolarius Palisot de Beauvois (one-spotted stink bug), Nezara viridula Linnaeus (southern green stink bug), Oebalus pugnax Fabricius (rice stink bug), Euryaulax carnifex Fabricius (sugarcane froghopper) and Phromnia rosea Isalo (flatid leaf bug).

Mixtures of the invention also have significant activity on members from the order Thysanoptera (e.g., Fraήkliniella occidentalis Pergande (western flower thrips), Scirtothrips citri Moulton (citrus thrips), Sericothrips variabilis Beach (soybean thrips), and Thrips tabaci Lindeman (onion thrips)); and the order Coleoptera (e.g., Sitophilus oryzae Linnaeus (rice water weevil)).

Of note are mixtures of this invention which show particularly high activity against pests in the order Lepidoptera such as rice stem borers and folders/rollers in the genera Chilo, Sesamia, Scirpophaga, Cnaphalocrocis and Marasmia. Of note is use of mixtures of this invention for controlling American bollworm

{Helicoverpa armigera Hubner). Of note is use of mixtures of this invention for controlling beet armyworm (Spodoptera exigua Hubner). Of note is use of mixtures of this invention for controlling tobacco cutworm (Spodoptera litura Fabricius). Of note is use of mixtures of this invention for controlling diamondback moth (Plutella xylostella Linnaeus). Of note is use of mixtures of this invention for controlling darkheaded rice borer (Chilo polychrysus Meyrick). Of note is use of mixtures of this invention for controlling striped rice borer (Chilo suppressalis Walker). Of note is use of mixtures of this invention for controlling the rice leaffolder Cnaphalocrocis medinalis Guenee. Of note is use of mixtures of this invention for controlling the rice leaffolder (Marasmia patnalis). Of note is use of mixtures of this invention for controlling the white stem borer (Scirpophaga innotatd). Of note is use of mixtures of this invention for controlling yellow stem borer (Scirpophaga incertulas). Of note is use of mixtures of this invention for controlling pink stem borer (Sesamia inferens). Of note is use of mixtures of this invention for controlling borers of Leucinodes spp., Maruca sp. and Ostrinia sp.. Of note is use of mixtures of this invention for controlling loopers of Trichoplusia spp..

Of note are mixtures of this invention which show particularly high activity against pests in the order Hemiptera and Homoptera such as hoppers and leaf bugs in the genera Euryaulax, Colgar, Phromnia and Fulgora; and whiteflies, aphids and leafhoppers in the genera Adelges Bemisia, Aphis, Myzus, Nephotettix, Laodelphax, Nilaparvata, Sogatella, Sogatodes and Recilia.

Of note is use of mixtures of this invention for controlling of sugarcane froghopper (Euryaulax carnifex Fabricius). Of note is use of mixtures of this invention for controlling bollworm larvae of flatid leaf bug (Phromnia rosea Isalo). Of note is use of mixtures of this invention for controlling of silverleaf whitefly (Bemisia argentifolii Bellows & Perring). Of note is use of mixtures of this invention for controlling aphids (Aphis spp.). Of note is use of mixtures of this invention for controlling green peach aphid (Myzus persicae Sulzer). Of note is use of mixtures of this invention for controlling rice leafhopper (Nephotettix nigropictus Stal). Of note is use of mixtures of this invention for controlling smaller brown planthopper (Laodelphax striatellus Fallen). Of note is use of mixtures of this invention for controlling brown planthopper (Nilaparvata lugens Stal). Of note is use of mixtures of this invention for controlling white-backed planthopper (Sogatella fur cifer a Horvath). Of note is use of mixtures of this invention for controlling rice delphacid (Sogatodes oryzicola Muir). Of note is use of mixtures of this invention for controlling zigzag leafhopper (Recilia dorsalis Motschulsky).

The method of the present invention is useful for protecting a broad range of plants vulnerable to foliar insect pests in agronomic environments. Illustrative of the wide variety of plants that can be protected from insect pests by the method of the present invention are fruit trees such as plant species in the family Rosaceae including pome fruits (e.g., apple (Malus pumila P. Mill.), pear (Pyrus communis L.)) and stone fruits (e.g., cherry (Prunus species such as P. avium (L.) L. and P. cerasus L.), apricot (Prunus armeniaca L.), almond (Prunus dulcis (P. Mill) D. A. Webber), peach (Prunus persica (L.), nectarine (Prunus persica (L.) Batsch var. nucipersica (Suckow) C. Schneider), plum (Prunus domestica L.)), in the family Rutaceae (i.e. citrus, including orange (Citrus sinensis (L.) Osbeck, tangerine (Citrus reticulata Blanco), lemon (Citrus limon (L.) Burm. f.), lime (Citrus aurantifolia (Christmas) Swingle), pummelo (Citrus maxima (Burm. f.) Merr.) and grapefruit (Citrus maxima x sinensis)), in the family Sapindaceae (e.g., loήgan (Dimocarpns longan Lour.), rambutan (Nephelium lappaceum L.), pulasan (Nephelium mutabile Blume), lychee (Litchi chinensis Sonn.)), in the family Anacardiaceae (e.g., mango (Mangifera indica L.)), in the family Bombacaceae (e.g., durian (Durio zibethinus L.)), in the family Moraceae (e.g., jackfruit (e.g., Artocarpus heterophyllus Lam.)), and in the family Myrtaceae (e.g., rose apple (Syzygium jambos (L.) Alston)). Also illustrative are shrubs in the family Rubiaceae such as coffee (e.g., Cqffea arabica L., Coffea canephora Pierre ex Froehner)) and the family Malvaceae such as cotton (e.g., Gossypium hirsulum L., Gossypium barbadense L.); vines in the family Vitaceae such as grape (e.g., Vitis labrusca L., Vitis vinifera L.); plants in the family Asteraceae such as lettuce (Lactuca sativa L.); plants in the family Chenopodiaceae such as garden beets and sugarbeets (both Beta vulgaris L.); plants in the family Cucurbitaceae including Cucumis, Cucurbita and Citrullus species such as cucumbers (e.g., garden cucumber {Cucumis sativus L.)), squash (e.g., winter squash {Cucurbita maxima Duchesne), crookneck squash {Cucurbita moschata (Duchesne ex Lam.) Duchesne ex Poir.), pumpkin {Cucurbita pepo L.)) and melons (e.g., cantaloupe and honeydew {Cucumis melo L.), watermelon {Citrullus lanatus (Thunb.) Matsumura & Nakai)); plants in the family Solanaceae including Solanum and Capsicum species such as tomato {Solarium lycopersicum L.), Cayenne and other garden peppers {Capsicum annuum L.), eggplant {Solanum melongena L.) and Irish potato {Solanum tuberosum L.); cabbages and Brussels sprouts in the family Brassicaceae (alternatively named Cruciferaceae); beans in the family Fabaceae (alternatively named Leguminosae) (e.g., Vigna spp.); onions in the family Lilaceae (e.g., Allium spp); and crop plants in the family Poaceae (e.g., rice (Oryza sativa), maize {Zea mays L.), sugarcane {Saccharum officinarum L.).

Of particular note are the methods of this invention which are useful for protecting plants in the families Brassicaceae, Fabaceae, Lilaceae and Poaceae. Brassicaceae includes crop plants such as Brassica species including Chinese kale {Brassica alboglabrd), cabbage {Brassica carinatd), kale, cauliflower, broccoli and Brussels sprouts (all Brassica oleracea L.), Chinese cabbage {Brassica rapa ssp. chinensis), Chinese mustard or Indian mustard {Brassica juncea or Brassica chinensis), black mustard {Brassica nigra), mustard, oilseed rape, canola and Swede turnip {Brassica napus) and turnip {Brassica rapa). Fabaceae includes crop plants including Phaseolus and Vigna species such as common bean {Phaseolus vulgaris), runner bean {Phaseolus coccineus), tepary bean {Phaseolus acutifolius), lima bean {Phaseolus lunatus), Adzuki bean {Vigna angularis), mung bean {Vigna radiata) and black-eyed pea/bean {Vigna unguiculata). Lilaceae includes crop plants such as Allium species including shallot {Allium ascalonicum), onion {Allium cepa), scallion {Allium fistulosum), leek {Allium ampeloprasum var. porrum), garlic {Allium sativum), and chive {Allium schoenoprasum). Poaceae includes crop plants such as Oryza species such as rice {Oryza sativa Linnaeus and Oryza glaberrima Steud).

Of note is use of mixtures of this invention for protecting Brassica carinata, Brassica oleracea, Brassica juncea, Brassica nigra, Brassica napus or Brassica rapa. Of note is use of mixtures of this invention for protecting Phaseolus vulgaris, Phaseolus coccineus, Phaseolus acutifolius, Phaseolus lunatus, Vigna angularis, Vigna radiata or Vigna unguiculata. Of note is use of mixtures of this invention for protecting Allium ascalonicum, Allium cepa, Allium fistulosum, Allium ampeloprasum var. porrum, Allium sativum or Allium schoenoprasum. Of note is use of mixtures of this invention for protecting Oryza sativa or Oryza glaberrima. The pronounced synergism manifested by mixtures of indoxacarb and dimehypo allows a substantial reduction in the application rates of one or both of these active ingredients, while maintaining good insecticidal efficacy. The greater than expected effect persists for days after application, facilitating rapid knockdown and mortality. Decreasing application rates reduces treatment cost to the farmer and also eases the burden on the environment both from manufacturing waste and crop protection chemical residues.

The presence of a synergistic effect between two active ingredients can be established with the aid of the Colby equation (see Colby, S. R., "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds 1967, 15, 20-22):

Using the method of Colby, the presence of a synergistic interaction between two active ingredients is established by first calculating the predicted activity, p, of the mixture based on activities of the two components applied alone. In the equation above, A is the insecticidal activity as percentage control by one component applied alone at rate x. The B term is the insecticidal activity as percentage control by the second component applied at rate y. The equation calculates p, the predicted insecticidal activity of the mixture of A at rate x with B at rate y if their effects are strictly additive and no interaction has occurred. If the experimentally established effect of the mixture is greater than the predicted activity, p, synergism is present. To use the Colby equation the active ingredients of the mixture are applied in a test separately as well as in combination.

BIOLOGICAL EXAMPLES OF THE INVENTION

The following test demonstrates the control efficacy of mixtures or compositions of this invention on a specific pest and provides experimental evidence for synergy between indoxacarb and dimehypo. The insect control protection afforded by the present mixtures or compositions is not limited, however, to this species. The analysis of synergism or antagonism between mixtures or compositions was determined using Colby's equation. If the observed percent (%) control is higher than "p", the expected percent control, the mixture or composition has shown synergistic effects. If the observed percent control is equal to or lower than the expected percent control, the mixture or composition has shown only additive or antagonistic effects.

TEST A

For evaluating control of yellow stem borer (Scirpophaga incertulas), rice seedlings

(2-3 weeks old) were transplanted into a plastic pail 15 cm in diameter and 15 cm in height filled with soil and grown outside under shade cloth. One plastic pail was considered as one replication, four replications were used in a randomized complete block design. Test plants were at the 4-true-leaf growth stage when the experiment was initiated.

The test compounds were obtained as commercially available formulations, indoxacarb was in the suspension concentrate formulation Ammate^® SC (15% of active ingredient), and dimehypo was in the wettable powder formulation Spontan^® WP (50% of active ingredient).

The test compounds were dissolved in water, tank-mixed according to the specified test rates, and sprayed using a CC>2-assisted backpack sprayer fitted with hollow-cone nozzles to deliver 400 liters per hectare over the top of the rice plants. One day after the test plants were sprayed, yellow stem borer neonate (newly hatched larvae) were artificially infested at a rate of 20 neonates per rice hill.

Rice plants were visually assessed, plants showing symptoms of dead heart as a result of yellow stem borer feeding were counted at 6, 11 and 14 days after the rice plants were sprayed with test compounds. Data was then converted to percent dead heart control.

The test results are listed in Table A.

Table A

* means synergistic effect is observed.

Table A shows mixtures and compositions of the present invention demonstrating control of yellow stem borer (Scirpophaga incertulas), some with notable synergistic effect. As the % dead heart control cannot exceed 100%, the unexpected increase in % dead heart control can be greatest only when the separate active ingredient components alone are at application rates providing considerably less than 100% control. Synergy may not be evident at low application rates where the individual active ingredient components alone have little activity. However, in some instances high activity was observed for combinations wherein an individual active ingredient alone at the same application rate had essentially no activity. The synergism is indeed highly remarkable. The most consistent strong synergy was observed when indoxacarb was applied at greater than 7.5 g/ha (e.g., 15 or 30 g/ha). Noteworthy are weight ratios of indoxacarb to dimehypo in the mixtures and compositions of the present invention which range from 1 : 2.5 to 1 :20.

Accordingly, this invention provides not only improved compositions but also methods of their use for control of insect pests in agronomic environments. The compositions of this invention demonstrate a high controlling effect on insect pests, and consequently, their use as insecticides can reduce crop production cost and environmental load.

Claims

CLAIMS What is claimed is:

1. A mixture comprising indoxacarb and dimehypo.

2. The mixture of Claim 1 wherein the indoxacarb and dimehypo are in a weight ratio between about 1 :1 and about 1 :50.

3. The mixture of Claim 2 wherein indoxacarb and dimehypo are in a weight ratio between about 1 :5 and about 1 :30.

4. A composition for protecting a plant from an insect pest comprising an insecticidally effective amount of the mixture of Claim 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, and optionally an additional biologically effective compound or agent.

5. A method for protecting a plant from an insect pest comprising contacting the insect pest or its environment with a biologically effective amount of the mixture of Claim 1.

6. The method of Claim 5 wherein the indoxacarb and dimehypo are applied simultaneously.

7. The method of Claim 5 wherein the insect pest is a species of the order Lepidoptera.

8. The method of Claim 7 wherein the insect pest is a species selected from Sciropophaga incertulas, Sciropophaga innotata, Sesamia inferens, Chilo suppressalis, Chilo polychry sus, Cnaphalocrocis medinalis and Marasmia patnalis.

9. The method of Claim 8 wherein the insect pest is Sciropophaga incertulas.

10. The method of Claim 5 wherein the plant is a species selected from one of the families Brassicaceae, Fabaceae, Lilaceae and Poaceae.

11. The method of Claim 10 wherein the plant is one of the species Brassica carinata, Brassica oleracea, Brassica j^'uncea, Brassica nigra, Brassica napus, Brassica rapa, Phaseolus vulgaris, Phaseolus coccineus, Phaseolus acutifolius, Phaseolus lunatus, Vigna angularis, Vigna radiata, Vigna unguiculata, Allium ascalonicum, Allium cepa, Allium flstulosum, Allium ampeloprasum var. porrum, Allium sativum, Allium schoenoprasum, Ory∑a sativa and Oryza glaberrima.

12. The method of Claim 11 wherein the plant is Oryza sativa or Oryza glaberrima.