WO1999063825A1

WO1999063825A1 - Arthropodicidal carboxanilides

Info

Publication number: WO1999063825A1
Application number: PCT/US1999/012885
Authority: WO
Inventors: David Michael Leva; Stephen Frederick Mccann; Keith Dumont Wing
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1998-06-10
Filing date: 1999-06-09
Publication date: 1999-12-16
Also published as: BR9911522A; JP2002517416A; EP1085809A1; AU4553999A

Abstract

Compositions containing the compounds of Formula (I) and methods of their use as arthopodicides in non-agronomic environments and in animal health environments are disclosed.

Description

TITLE

ARTHROPODICIDAL CARBOXANILIDES

BACKGROUND OF THE INVENTION

This invention relates to compositions containing certain arthropodicidal oxadiazines and a method of their use as arthropodicides in non-agronomic environments and in animal health environments.

Arthropodicidal oxadiazines are disclosed in WO 92/11249 The control of arthropod pests is extremely important in non-agronomic environments. Arthropod damage to property and health hazards associated with arthropod infestations can cause significant increases in costs and problems for the consumer. The control of non-agronomic arthropod pests in stored food and fiber products, buildings (in, under and around household and business structures), turf and gardens is important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different modes of action. The control of arthropod pests is extremely important in animal health environments

Health hazards associated with arthropod infestations can cause significant increases in costs and problems for the consumer. The control of arthropod pests with deleterious human and/or animal health effects is important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different modes of action

SUMMARY OF THE INVENTION This invention is directed to compositions of Formula I and their use as arthropodicides in non-agronomic environments and in animal health environments:

wherein * indicates an optically active center

Preferred is 100% of (S)-methyl 7-chloro-2,5-dιhydro-2-[[(methoxycarbonyl)[4- (tπfluoromethoxy)phenyl]amιno]carbonyl]ιndeno[l,2-e][l,3,4]oxadιazιne-4a(3H)- carboxylate. Also preferred is a mixture of 99.9 to 75% (S)-methyl 7-chloro-2,5-dιhydro-2- [[(methoxycarbonyl)[4-(tπfluoromethoxy)phenyl]ammo]carbonyl]ιndeno[l,2-e][l,3,4]oxadι- azιne-4a(3H)-carboxylate with 0.1 to 25% of (R)-methyl 7-chloro-2,5-dιhydro-2- [[(methoxycarbonyl)[4-(tπfluoromethoxy)phenyl]amιno]carbonyl]ιndeno[l,2- e][l,3,4]oxadιazιne-4a(3H)-carboxylate.

Most preferred is a mixture of 75% (S)-methyl 7-chloro-2,5-dιhydro-2- [[(methoxycarbonyl)[4-(tπfluoromethoxy)phenyl]amιno]carbonyl]ιndeno[l,2- e][l,3,4]oxadιazιne-4a(3H)-carboxylate with 25% (R)-methyl 7-chloro-2,5-dιhydro-2- [[(methoxycarbonyl)[4-(tπfluoromethoxy)phenyl]amιno]carbonyl]ιndeno[l,2- e] [ 1 ,3,4]oxadιazιne-4a(3H)-carboxylate.

DETAILS OF THE INVENTION

The compounds of Formula I or can be prepared by one or more of the methods disclosed in WO 92/11249, WO 95/29171 and WO 98/05656 as shown in Scheme 1

Scheme 1

III

Formulation and Use

The compounds of this invention will generally be used in formulation with a suitable earner comprising a liquid or solid diluent or an organic solvent. Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like. Many of these can be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from about one to several hundred liters per hectare. High strength compositions are pπmaπly used as intermediates for further formulation. The formulations, broadly, contain from less than about 1% to 99% by weight of active mgredιent(s) and at least one of a) about 0.1% to 20% surfactant(s) and b) about 5% to 99% solid or liquid dιluent(s). More specifically, they will contain effective amounts of these ingredients in the following approximate proportions:

Percent By Weight

Active

Ingredient Dιluent(s) Surfactant(s)

Wettable Powders 25-90 0-74 1-10

Oil Suspensions, Emulsions, 5-50 40-95 0-15

Solutions, (including Emulsifiable

Concentrates)

Dusts 1-25 70-99 0-5 Granules, Baits and Pellets 0 01-95 5-99 0 15

High Strength Compositions 90-99 0 10 0-2

Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing Typical solid diluents are descnbed in Watk s, et al , Handbook of Insecticide Dust

Diluents and Carriers, 2nd Ed , Dorland Books, Caldwell, New Jersey Typical liquid diluents are descnbed in Maisden, Solvents Guide, 2nd Ed , Interscience, New York, 1950 McCutcheon's Detergents and Emulsφers 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 sulfosucc ates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,Λ/-dιalkyltaurates, lignm sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers Solid diluents include, for example, clays such as bentonite, montmonllonite, 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, N,N-dιmethylformamιde, dimethyl sulfoxide, N-alkylpyrrohdone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol

Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients Dusts and powders can be prepared by blending and, usually, gnnding 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 matenal upon preformed granular earners 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 descnbed in U S Patent 4,172,714 Water-dispersible and water-soluble granules can be prepared as taught in U S Patent 4,144,050, U S Patent 3,920,442 and DE 3,246,493 Tablets can be prepared as taught in U.S. Patents 5,180,587, 5,232,701 and 5,208,030. Films can be prepared as taught in GB Patent 2,095,558 and U.S Patent 3,299,566.

For further information regarding the art of formulation, see U S. Patent 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41 , U.S. Patent 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. Patent 2,891,855, Col 3, line 66 through Col. 5, line 17 and Examples 1-4; Khngman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989 In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. The Examples and Tests descnbed below use a mixture of 79% (S)-methyl 7-chloro-2,5-dιhydro-2-[[(methoxycarbonyl)[4- (tnfluoromethoxy)phenyl]amιno]carbonyl]ιndeno[l,2-e][l,3,4]oxadιazme-4a(3H)- carboxylate with 21% (R)-methyl 7-chloro-2,5-dιhydro-2-[[(methoxycarbonyl)[4- (tnfluoromethoxy)phenyl]amιno]carbonyl]ιndeno[ 1 ,2-e] [ 1 ,3,4]oxadιazιne-4a(3H)- carboxylate (this ratio is hereinafter referred to as Compound 1).

Formulation A Emulsifiable Concentrate Compound 1 5% blend of oil soluble sulfonates and polyoxyethylene ethers 4% xylene 91%

The ingredients are combined and stirred with gentle warming to speed solution. A fine screen filter is included in packaging operation to insure the absence on any extraneous undissolved matenal in the product

Formulation B Wettable Powder Compound 1 30% sodium alkylnaphthalenesulfonate 2% sodium lign sulfonate 2% synthetic amorphous silica 3% kaohnite 63%

The active ingredient, warmed to reduce viscosity, is sprayed onto the inert matenals in a blender. After gnnding m a hammer-mill, the matenal is reblended and sifted through a 50 mesh screen.

Formulation C Dust wettable powder of Formulation B 10% pyrophylhte (powder) 90% The wettable powder and the pyrophyllite diluent are thoroughly blended then packaged. The product is suitable for use as a dust.

Formulation D Granule

Compound 1 10% attapulgite granules (low volative matter, 0.71/0.30 mm; U.S.S. No. 20-50 90% sieves) The active ingredient is dissolved in a suitable solvent and sprayed onto dedusted attapulgite granules in a double cone blender. The granules are warmed to drive off solvent, cooled and packaged.

Formulation E Granule wettable powder of Formulation D 15% gypsum 69% potassium sulfate 16% The ingredients are blended in a rotating mixer and water sprayed on to accomplish granulation. When most of the material has reached the desired range of 0.1 to 0.42 mm (U.S.S. No. 18 to 40 sieves), the granules are removed, dried, and screened. Oversize material is crushed to produce additional material in the desired range. These granules contain 4.5% active ingredient. Formulation F

Solution

Compound 1 25%

N-methyl-pyrrolidone 75%

The ingredients are combined and stirred to produce a solution suitable for direct, low volume application.

Example G Aqueous Suspension

Compound 1 40% polyacrylic acid thickener 0.3% dodecyclophenol polyethylene glycol ether 0.5% disodium phosphate 1.0% monosodium phosphate 0.5% polyvinyl alcohol 1.0% water 56.7%

The ingredients are blended and ground together in a sand mill to produce particles substantially all under 5 microns in size. Formulation H Oil Suspension

Compound 1 35% blend of polyalcohol carboxylic esters and oil soluble petroleum sulfonates 6% xylene range solvent 59%

The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.

Formulation I Bait Granules Compound 1 3% blend of polyethoxylated nonylphenols and sodium dodecylbenzene sulfonates 9% ground-up corn cobs 88%

The active ingredient and surfactant blend are dissolved in a suitable solvent such as acetone and sprayed onto the ground-up corn cobs. The granules are then dried and packaged.

Compounds of Formula I can also be mixed with one or more other insecticides or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of effective control. Examples of other protectants with which compounds of this invention can be formulated are: abamectin, acephate, Bacillus popilliae, Bacillus thuήngiensis, bifenthrin, biphenate, buprofezin, carbaryl, carbofuran, chlorpyrifos, cyfluthrin, cypermethrin, deltamethrin, diazinon, diflubenzuron, emamectin, fenpropathrin, fenvalerate, fipronil, flucythrinate, tau-fluvalinate, hexaflumuron, imidacloprid, lindane, lufenuron, malathion, metaldehyde, methidathion, methoxychlor, monocrotophos, parathion-methyl, permethrin, rotenone, spinosad, tetrachlorvinphos, thiodicarb, tralomethrin, trichlorfon, and triflumuron.

In certain instances, combinations with other arthropodicides having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management.

Prefened for better control of pests (use rate or spectrum) or resistance management are mixtures of a compound of this invention with an arthropodicide selected from the group abamectin, chlorpyrifos, fipronil, hexaflumuron, imidacloprid, lufenuron, permethrin and spinosad. Specifically prefened mixtures are selected from the group: Compound 1 and abamectin; Compound 1 and chlorpyrifos; Compound 1 and fipronil; Compound 1 and hexaflumuron; Compound 1 and imidacloprid; Compound 1 and lufenuron; Compound 1 and permethrin; and Compound 1 and spinosad. Utility

Some of the compounds of this invention are characterized by favorable metabolic and/or soil residual patterns and exhibit activity against a wide spectrum of non-agronomic arthropod pests in stored food and fiber products, buildings (in, under and around household and business structures), turf and gardens.

Some of the compounds of this invention are characterized by favorable metabolic and/or soil residual patterns and exhibit activity against a wide spectrum of animal health arthropod pests that negatively affect human and/or animal health.

The compounds of this invention are active on insect pests of the order Hymenoptera including ants such as red carpenter ant (Camponotus ferrugineus), black carpenter ant (Camponotus pennsylvanicus ), Pharaoh ant (Monomorium pharaonis), little fire ant (Ochetomyrmex auropunctatus), fire ant (Solenopsis geminata), red imported fire ant (Solenopsis invicta), Argentine ant (Iridomyrmex humilis), crazy ant (Paratrechina longicornis), pavement ant (Tetramorium caespitum), cornfield ant (Lasius alienus), odorous house ant (Tapinoma sessile), carpenter bees, hornets, yellow jackets and wasps; insect pests of the order Diptera such as house flies (Musca domestica), blow flies, and other muscoid fly pests; other insect pests of the order Diptera including such species as Aedes spp, Anopheles spp., Culex spp., Eannia spp., Chrysomya spp., Gastrophilus spp., Stomoxys spp., Oestrus spp. Hypoderma spp. Tabanus spp., Tannia spp., Oscinellafrit, Phormia spp., Melophagus spp.; insect pests of the order Orthoptera such as oriental cockroach (Blatta orientalis), Asian cockroach (Blatella asahinaϊ), German cockroach (Blatella germanica), false German cockroach (Blatella asahinai), brownbanded cockroach (Supella longipalpa), American cockroach (Periplaneta americana), brown cockroach (Periplaneta brunnea), Madeira cockroach (Leucophaea maderae), house cricket (Acheta domesticus), mole crickets (Gryllotalpa spp.); migratory grasshopper (Melanoplus sanguinipes), (Melanoplus differentialis), American grasshopper (Schistocerca americana), (Schistocerca gregaria), (Locust migratoria), house cricket (Acheta domesticus); insect pests of the order Isoptera such as the eastern subterranean termite (Reticulitermes flavipes), western subterranean termite (Reticulitermes hesperus), Formosan subterranean termite (Coptotermes formosanus), western drywood termite (Incistermes immigrans), and other termites; insect pests of the order Thysanura such as silverfish (Lepisma saccharina), firebrat (Thermobia domestica); insect pests of the order Dermaptera such as European earwig (Fo cula auricularia), black earwig (Chelisoches mono); insect pests of the order Coleoptera such as Japanese beetle (Popillia japonica); insect pests of the order Lepidoptera such as webworms (Crambus spp, Herpetogramma spp.); insect pests of the order Hemiptera such as chinch bugs (Blissus spp.); insect pests of the order Homoptera such as leafhoppers (Empoasca spp.); arthropod pests of the order Siphonoptera such as Xenapsylla cheopis, Ceratophyllus spp., Ctenocephalides spp., Pulex spp., Echidnophaga gallinacea., arthropod pests of the order Ac an such as Ixodes spp., Scortpio spp., Latrodectus mactans, Dermacenter spp , Amblyomma spp.; arthropod pests of the order Mallophaga such as Tnchodectes spp , Gomocotes spp., Bovicola spp ; arthropod pests of the order Anoplura such as Pediculus spp, Linognathus spp , Haematopinus spp . Those skilled in the art will recognize that not all compounds are equally effective against all pests. The specific species for which control is exemplified are six urban insect pest species' the Amencan cockroach (Periplaneta americana), German cockroach (Blattella germanwa), brownbanded cockroaches Supella longψalpa (Serville), subterranean termites (Reticulitermes flavψes), black carpenter ant (Camponotus pennsylvamcus) workers, majors and minors and the northern house mosquito (Culex pipiens). Pest control protection afforded by the compounds of the present invention is not limited, however, to these species

Application

Control of non-agronomic arthropod pests is achieved by applying the Formula I compound of this invention, in an effective amount, to the environment of the pests including the non-agronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled Because of the diversity of habitat and behavior of these arthropod pest species, many different methods of application are employed A preferred method of application is by spraying with equipment that distnbutes the compound in the environment of the pests, on the foliage or premise, in the soil, to the plant part that is infested or needs to be protected. Alternatively, granular formulations of these toxicant compounds can be applied to or incorporated into the soil Other methods of application can also be employed including direct and residual sprays, aenal sprays, baits, foggers, aerosols, and many others The compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like which entice them to ingest or otherwise contact the compound

Control of human and/or animal health arthropod pests is achieved by applying the Formula I compounds of this invention, in an effective amount, to the environment of the pests including the animal health locus of infestation, to the area to be protected, or directly on the pests to be controlled. Because of the diversity of habitat and behavior of these arthropod pest species, many different methods of application are employed. A preferred method of application is by spraying with equipment that distnbutes the compound in the environment of the pests or directly on the pests to be controlled. Other methods of application can also be employed including direct and residual sprays, aenal sprays, granules, foggers, aerosols, impregnated slow release apparatus (flea collars, ear tags), and many others. The compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like which entice them to ingest or otherwise contact the compound. The compounds of this invention can be applied in their pure state, but most often application will be of a formulation compnsing one or more compounds with suitable earners, diluents, and surfactants and possibly in combination with a bait depending on the contemplated end use. A preferred method of application involves spraying a water dispersion or a refined oil solution of the compounds. The rate of application of the Formula I compound required for effective control will depend on such factors as the species of arthropod 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, etc. In general, application rates of 0.01 to 2 kg of active ingredient per hectare are sufficient to provide large-scale effective control of pests in non-agronomic ecosystems under normal circumstances, but as little as 0 001 kg/hectare or as much as 8 kg/hectare may be required. For non-agronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as about 0.1 mg/square meter or as much as 150 mg/square meter may be required. In general, application rates of 0.01 to 2 kg of active ingredient per hectare are sufficient to provide large-scale effective control of pests in animal health ecosystems under normal circumstances, but as little as 0 001 kg/hectare or as much as 10 kg/hectare may be required. For animal health applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as about 0.1 mg/square meter or as much as 150 mg/square meter may be required. Furthermore, effective use rates for animal health applications can range in concentration from 0.1 to 1000 ppm but as little as about 0.001 ppm or as much as 10,000 ppm.

The following Tests demonstrate the control efficacy of the compounds of Formula I for specific pests.

Test A. Bait Test for Amencan Cockroaches

Approximately 25g Laboratory Rodent Diet 5001 was placed into a plastic bag and pulvenzed. Five - 5g samples were weighed. Compound 1 was diluted in acetone to produce bait concentrations of 1000, 700 and 300 ppm w/w a.i. dry bait Three mL of each solution in acetone (4 rates) was pipetted into each respective bait sample. Each sample then received 6 mL deionized water and was thoroughly mixed. Three mL acetone plus 6 mL deionized water was pipetted into a single bait sample used as a negative control. A clear acrylic mold (dimensions were approximately ^lA" diameter x 1/8" deep) was used to create bait pellets. For each rate of Compound 1, 8 pellets were pressed into the mold Only 4 pellets were pressed for the control. Pellets were allowed to dry and then were placed into a plastic bag that was then sealed. Each bait pellet weighed approximately 100 mg dry

Two bait pellets were placed into the inside bottom of each of 4 glass petn dishes (100 mm diameter x 15mm) used for each of the 4 rates of Compound 1 tested One glass petn dish (replicate) was used as a negative control. One-dram glass vials each were filled with deionized water and plugged with cotton wicks. One vial was placed each petri dish. A total of 17 test units (reps) were set up. Adult mixed sex American cockroaches were deprived of food and water for 24 hours prior to the start of the test. Insects then were chilled and sets of 3 were placed into the glass petri dish bottoms, already containing bait and 1 dram water vials plugged with dental wicks prior to infestation. Glass petri dish covers then were placed on top of each test unit. Test units were held at room temperature in the dark for the duration of the test. Mortality results were taken at 24, 48, 72, 144 and 168 hours post infestation. All data are summarized in Table 1.

TABLE 1 AMERICAN COCKROACH BAIT TEST

Rate 24 Hr. 48 Hr. 72 Hr. 144 Hr. 168 Hr.

Test Compound ppm % Mort % Mort % Mort % Mort % Mort.

Compound 1 1000 8 50 83 100 100

Compound 1 700 0 25 50 67 83

Compound 1 300 0 0 33 75 83

Control - 0 0 0 0 0

Note - Data based upon 4 test replicates - 3 insects/replicate except control where only one test replicate was used.

Test B. American Cockroach and Brownbanded Cockroach Bait Test Ten 5.00 g samples of pulverized rodent checker from Purina Mills, PMI were placed into glass petri dishes. Compound 1 (79% S-isomer) was diluted in acetone to produce bait concentrations of 750, 500, 250 and 100 ppm (w/w a.i./dry bait). Chlorpyrifos was diluted to produce a concentration of 100 ppm. One 5.00 g bait sample prepared for use as a negative control. Three mis of each solution in acetone (4 rates each for Compound 1) were pipetted into each respective bait sample. A single rate was used with chlorpyrifos. Each sample then received 6 mis of deionized water and was thoroughly mixed. Three mis acetone plus 6 mis deionized water was pipetted into a single bait sample used as a negativecontrol. A clear acrylic mold (dimensions approximately ^lA" diameter x 1/8" deep) was used to create bait pellets. Eight pellets were pressed into the mold for each rate of Compound 1 tested plus the negative control. Each bait pellet weighed approximately 100 mg dry.

Adult mixed sex American cockroaches Periplaneta americana (Linn.) were used for testing. Insects were deprived of food and water 24 hrs. prior to test initiation. Adult mixed sex brownbanded cockroaches Supella longipalpa (Serville) also were used in this test with Compound 1 at only the 100 ppm rate. They also were deprived of food and water 24 hrs. before test initiation. Fortyfour glass petri dishes (100 mm x 15 mm) were used for this test. Four test replicates (petri dishes) were set up per rate of Compound 1. Another set of 4 dishes was used with Compound 1 at 100 ppm only with Brownbanded cockroaches. Four replicates were set up with chlorpyrifos bait at 100 ppm only as well as 4 replicates used as a negative control. Fortyfour one-dram glass vials each were filled with deionized water and plugged with cotton wicks. One vial was placed each petri dish. Bait pellets that had been pressed into the mold 24 hours before test initiation were dropped, two at a time, into each respective glass petri dish bottom. Eight bait pellets used per rate tested. Test insects then were chilled and sets of three were placed into petri dish bottoms containing bait and water vials. A glass petri dish cover then was placed on top of each test unit. All test units then were covered with a paper towel and held at room temperature in the dark for the duration of the test. Test results are summarized in Table 2.

In this test against American cockroach Compound 1 provided good control at 250 ppm 8 days post treatment. At 500 ppm it gave excellent control 6 days post treatment. Chlorpyrifos provided unacceptable control at 100 ppm, the only rate tested.

TABLE 2 AMERICAN AND BROWNBANDED COCKROACH BAIT TEST AMERICAN COCKROACH MORTALITY Rate 24 Hr. 48 Hr. 72 Hr. 144 Hr. 192 Hr. ppm %Mort %Mort %Mort %Mort %Mort COMPOUND 750 0 0 25 100 100

Compound 1

500 0 0 8 92 100

250 0 0 0 33 83

100 0 0 0 8 8

Chlorpyrifos 100 0 8 8 17 25

Y2771-14

Control — 0 0 8 8 17

Solvent

BROWNBANDED COCKROACH MORTALITY Compound 1 100 0 25 42 42 50

Note - Data based upon 4 test replicates - 3 insects/rep. Test insects were comsidered dead when they were motionless when prodded or shaken or unable to control their their movements in either an upright position or on their backs.

Test C. German and Brownbanded Cockroach and Termite Assays

Cockroach Assay Adult German cockroaches (Blattella germanica L.) and adult brownbanded cockroaches (Supella longipalpa Fabricius) were obtained through Dr. Coby Schal of North Carolina State University (Raleigh, NC). The test material was Compound 1, which was composed of 79% of the 5-isomer. The test materials were weighed out based on purity and dissolved in acetone containing 1000 ppm Triton X-155 (Sigma Chemical, St. Louis, MO). The test materials were further diluted with a sucrose solution to produce a 10% acetone: 0.01% Triton X-155: 10% sucrose solution. Serial dilutions were made with 10% sucrose: 0.01% Triton X-155 solution, while controls consisted of the 10% sucrose: 0.01% Triton X- 155 solution alone. The test solutions were placed into a dram vial (4.2 mL) and a 40 mm cotton dental wick (Richmond Dental Supply, Charlotte NC) was placed in the top of the vial. The vial was inverted and inserted into the "straw" opening of the lid of a plastic cup (270 mL) containing ten cockroaches. Each treatment had two cups. The treated cockroaches were kept at 28 + 1°C with 60-70% relative humidity and a 14 hr photoperiod. Mortality was assessed after 4 days. Cockroaches that could not right themselves were considered dead.

Termite Assay Worker termites (Reticulitermes flavipes Koller) were obtained through Dr. Rudolph

Scheffrahn of the University of Florida (Fort Lauderdale, FL). The test materials were dissolved and serially diluted in acetone. Controls consisted of acetone alone. One mL of test solution was applied to a 47 mm filter paper (MFS, Inc. Pleasonton, CA) that had been placed in a 50 mm glass Petri dish. The acetone was allowed to evaporate (ca. 1 hour) and 1.75 mL of deionized water was placed on the filter paper. Twenty-five worker termites (undifferentiated larvae of >third instar) were placed on the filter paper. The Petri dishes were placed in a covered plastic container with wet paper towels. The treated termites were kept at 28 + 1°C with nearly 100% relative humidity and in the dark. Mortality was assessed after 4 days. Termites that could not right themselves were considered dead. The dose-mortality responses of termite and cockroaches were analyzed with POLO-

PC (Russel et al., 1977) to determine LC50 and LC90 values, as well as the slope of the curve. Control mortality remained below 10% throughout these tests.

The brownbanded cockroach was slightly more tolerant of the compound compared to the German cockroach. Differences in LC50 values were approximately two-fold between the cockroach species. TABLE 3 PERCENT MORTALITIES OF COMPOUND 1 ON URBAN INSECT PESTS Percent Mortality

German Brownbanded

Cockroach Cockroach Termite

Dose Blatella Supella Reticuletermes

Compound (ppm) germanica longipalpa flavipes

Compound 1 300 100

Compound 1 100 100 50 100

Compound 1 30 67 48

Compound 1 10 35 28 100

Compound 1 3 0 0 97

Compound 1 1 0 0 90

Compound 1 0.3 0 25

Compound 1 0.1 0 6

Compound 1 0.03 4

Dursban 10 100 100

Dursban 1 10 67

Dursban 0.1 17

Control 0 2 2

TABLE 4

DOSE-MORTALITY CURVES OF COMPOUND 1 ON URBAN INSECT PESTS (data from Table 3 were used to calculate these dose-mortality curves).

Termites

Reticuletermes German Cockroach Brownbanded Cockroach flavipes Blatella germanica Supella longipalpa

Compound 1 LC50 (ppm) 0.50 (0.33-0.61) 17.0 (10.4-28.5) 46.6 (22.0-133.0) LC90 (ppm) 1.23 (0.91-2.0) 50.0 (29.5-191.3) 385.5 (134.5-8075.3) Slope ± SE 3.1 ± 0.2 2.7 ± 0.4 1.4 ± 0.2 (n = 1150) (n = 230) (n = 270)

Test D. Contact Toxicity Testing on Carpenter Ants

The contact toxicity of Compound lwas tested on carpenter ants (Camponotus pennsylvanicus) by exposing groups of ants to treated glass surfaces for a period of five days. Compound 1 was dissolved in HPLC-grade acetone as a standard stock solution and then diluted for the actual tests. The concentration of the initial Compound 1 stock solution was 1.28 mg/ml which equaled a concentration of the active ingredient (79% 5-isomer) of 1011 μg/ml. Serial dilutions were used to make test solutions with AI concentrations of 101.1 μg/ml, 10.1 μg ml and 1.0 μg/ml. These solutions were used for all contact toxicity testing with major workers. A new set of solutions was made up before the tests with minor workers. Solutions were made in the same manner, but differed slightly in concentration. Final concentrations for the Compound 1 solutions were 1005 μg/ml, 100.5 μg/ml, 10.0 μg/ml and 1.0 μg/ml. One ml of each solution was applied to the bottom of a glass crystallizing dish (125mm x 65mm, Pyrex dishes, #3140-125 Corning Glass; dish area equals 113.1 sq. cm) and gently swirled around the bottom of the dish until the acetone had evaporated. After the acetone evaporated, the sides of each dish were coated with a light layer of petroleum jelly to prevent ants from walking on the sides or escaping. Control groups were introduced onto glass surfaces treated with just the acetone solvent. Compound 1 caused high levels of mortality at application levels of 10 mg/ml through 1000 mg/ml over the five-day test period. When all of the dishes had been prepared, a group of ten ants (majors or minors) from a laboratory maintained colony was introduced into each dish and left for a period of five days. The ants were fed on a daily basis for a 10-15 minute period by placing a small vial of sugar solution in each dish. Feeding was restricted to insure the ants remained in contact with the bottom of the test dish and did not aggregate in the feeding tubes. Mortality observations were made every 24 hours over the five-day period and were conducted immediately before feeding.

Each test consisted of five test dishes for each of the two compounds (four concentrations and a control) for a total of ten dishes. Three replicates were made of each test series and major and minor workers were tested separately.

The results are presented in Tables 5 and 6. Table 5 shows the efficacy of Compound 1 on major workers. Mortality rates were high for Compound 1 with no worker survival at 48 hours in the dishes receiving the 1000 μg doses and only limited survival at the 100 μg dose. Major workers in the dishes containing the 10 μg doses showed signs of intoxication and few coordinated movements. By the end of the 5-day period, workers exposed to the 10 μg dosages showed very low survival. Workers exposed to the 1 μg dosages showed few signs of any toxic effects and continued to feed through the 5-day period. The contact toxicity of Compound 1 was similar on minor workers, with high mortality and little feeding of workers at the end of the five-day test period for the more concentrated test solutions. CONTACT TOXICITY TESTING ON CARPENTER ANTS

TABLE 5 PERCENT MORTALITY OF MAJOR WORKERS AT DIFFERENT CONCENTRATIONS OF COMPOUND 1

TABLE 6

PERCENT MORTALITY OF MINOR WORKERS AT DIFFERENT

CONCENTRATIONS OF TEST COMPOUND 1

Test E. Toxicity Testing On Northern Mosquito Larvae

The contact toxicity of Compound lwas tested on Northern Mosquito (Culex pipiens) larvae by exposing larvae to solutions of Compound 1 in 96-Deepwell microtiter plates. Three-day-old larvae were placed in each well, pre-treatment. At least 3 larvae were present in each well. All wells had a total volume of lOOOul of water. 15ul of mosquito food, made by mixing lgm of dry food with 45ml of .15% agar, was placed into each well. There were 8 reps per rate. Compound 1 was dissolved in DMSO and diluted with solvent (75/25 acetone/water) to the test concentration. Each well was treated with 25μl of compound solution. Mortality assessments were made at 4 days. TABLE 7 MORTALITY TESTS ON MOSQUITOES

Claims

CLAIMSWhat is claimed is:

1. An arthropodicidal composition comprising an arthropodicidally effective amount of a compound of Formula I and at least one of a surfactant, a solid diluent or a liquid diluent.

2. A method for controlling arthropods in non-agronomic environments comprising contacting the arthropods or their environment with an arthropodicidally effective amount of a compound of Formula I.

3. A method for controlling arthropods in animal health environments comprising contacting the arthropods or their environment with an arthropodicidally effective amount of a compound of Formula I.