WO2008021152A2 - Agronomic method - Google Patents

Agronomic method Download PDF

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Publication number
WO2008021152A2
WO2008021152A2 PCT/US2007/017673 US2007017673W WO2008021152A2 WO 2008021152 A2 WO2008021152 A2 WO 2008021152A2 US 2007017673 W US2007017673 W US 2007017673W WO 2008021152 A2 WO2008021152 A2 WO 2008021152A2
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WO
WIPO (PCT)
Prior art keywords
carboxamide
chloro
pyrazole
methyl
carbonyl
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Application number
PCT/US2007/017673
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French (fr)
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WO2008021152A3 (en
Inventor
Isaac Billy Annan
Paula Cristina Rodrigues Gouveia Marcon
Hector Eduardo Portillo
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E. I. Du Pont De Nemours And Company
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Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Publication of WO2008021152A2 publication Critical patent/WO2008021152A2/en
Publication of WO2008021152A3 publication Critical patent/WO2008021152A3/en

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/561,2-Diazoles; Hydrogenated 1,2-diazoles

Definitions

  • This invention also relates to a method wherein the carboxamide arthropodicide, its N-oxide, or a salt thereof, is formulated as a composition comprising the arthropodicide, its JV-oxide, or a salt thereof, and at least one additional component selected from the group consisting of surfactants and liquid diluents.
  • compositions comprising, “comprising,” “includes,” “including,” “has,” “having,” “contains” or “containing,” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a composition, a mixture, 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, mixture, process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or.
  • 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).
  • 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.
  • LC 50 or "LD 50” refers to the concentration or dose of a pesticide which when applied to the target pest species will result in 50 % mortality.
  • sub-lethal concentration means a concentration or dose causing about 50% or less mortality ( ⁇ LC 5 ⁇ or LD 50 ); in other words, at least about 50 % of the population are alive at one day (24 hours) after treatment application.
  • infectious disease refers to diseases of plants or animals caused by infectious agents including viruses, bacteria, fungi, mycoplasma and phytoplasma.
  • infectious plant diseases refers to diseases, which reduce crop vigor or crop yield, which are caused by plant infectious agents including viruses, bacteria, fungi and phytoplasma.
  • effective amount refers to an amount of compound effective to increase crop yield or crop vigor.
  • the nitrogen atom in Formula A is bonded to the carbonyl carbon of Formula A and also bonded to two other atoms, at least one atom of which is selected from a hydrogen atom or a carbon atom of another radical to which the carboxamide moiety is bonded.
  • X is N 7 CF, CCl, CBr or CI
  • R 3 is F, Cl, Br, C 1 -C 4 haloalkyl or C 1 -C 4 haloalkoxy;
  • R 4a is H, C 1 -C 4 alkyl, cyclopropylmethyl or 1-cyclopropylethyl;
  • R 4b is H or CH 3 ;
  • Embodiment IA The methods of Embodiment 1 wherein X is N; R 1 is CH 3 ; R 2 is Cl or CN; R 3 is Cl, Br or CF 3 ; R 4a is C t -C 4 alkyl; R «b [ s H; R 5 is Cl; and R ⁇ is H.
  • Embodiment IB The methods of Embodiment 1 wherein X is N; R 1 is CH 3 ; R 2 is Cl or CN; R 3 is Cl, Br or CF 3 ; R* a i s Me or CH(CH 3 ) 2 ; R 4 *> is H; R 5 is Cl; and R 6 is H.
  • R 12 is CH 3 or Cl
  • R 13 is C 1 -C 3 fluoroalkyl
  • R 14 is H or CH 3 ;
  • R 15 is H or CH 3 ;
  • R 13 is CF 3 , CF 2 CF 3 or CF(CF 3 ) 2 (equivalently identified as (CF 3 ) 2 CF);
  • Embodiment 2C The methods of Embodiment 2 wherein the carboxamide arthropodicide is ⁇ -fl.l-dimethyl ⁇ -Cmethylsulfony ⁇ ethylJ-S-iodo-
  • Embodiment 3 The methods described in the Summary of the Invention wherein the arthropod pest is a species in one of the orders Coleoptera, Diptera, Hemiptera,
  • Embodiment 4 The methods of Embodiment 3 wherein the arthropod pest is a species of the order Coleptera.
  • Embodiment 4A The methods of Embodiment 4 wherein the arthropod pest is
  • Embodiment 5 The methods of Embodiment 3 wherein the arthropod pest is a species of the order Diptera.
  • Embodiment 5A The methods of Embodiment 5 wherein the arthropod pest is Musca domestica.
  • Embodiment 6. The methods of Embodiment 3 wherein the arthropod pest is a species of the order Hemiptera.
  • Embodiment 6A The methods of Embodiment 6 wherein the arthropod pest is a
  • Embodiment 6B The methods of Embodiment 6 wherein the arthropod pest is Nezara viridula.
  • Embodiment 6C The methods of Embodiment 6 wherein the arthropod pest is a
  • Embodiment 7 The methods of Embodiment 3 wherein the arthropod pest is a species of the order Homoptera.
  • Embodiment 7A The methods of Embodiment 7 wherein the arthropod pest is Aphis gossypii.
  • Embodiment 7B The methods of Embodiment 7 wherein the arthropod pest is
  • Embodiment 7C The methods of Embodiment 7 wherein the arthropod pest is
  • Embodiment 7D The methods of Embodiment 7 wherein the arthropod pest is
  • Embodiment 7E The methods of Embodiment 7 wherein the arthropod pest is Myzus persicae.
  • Embodiment 7F The methods of Embodiment 7 wherein the arthropod pest is Nephotettix virescens.
  • Embodiment 7G The methods of Embodiment 7 wherein the arthropod pest is
  • Embodiment 7H The methods of Embodiment 7 wherein the arthropod pest is
  • Embodiment 8 The methods of Embodiment 3 wherein the arthropod pest is a species of the order Lepidoptera.
  • Embodiment 8 A The methods of Embodiment 8 wherein the arthropod pest is
  • Embodiment 9 The methods of Embodiment 3 wherein the arthropod pest is a species of the order Thysanoptera.
  • Embodiment 9A The methods of Embodiment 9 wherein the arthropod pest is Thrips palmi.
  • Embodiment 10 The methods described in the Summary of the Invention or any of the embodiments described herein comprising contacting an arthropod pest or its environment with a composition comprising a sub-lethal amount of a carboxamide arthropodicide, its ⁇ f-oxide, or a salt thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • Embodiment 11 The methods of Embodiment 10 wherein the composition further comprises a biologically effective amount of a sex pheromone.
  • alkyl used either alone or in compound words such as “haloalkyl” or “fluoroalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl isomers.
  • Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy isomers.
  • halogen either alone or in compound words such as “haloalkyl” includes fluorine, chlorine, bromine or iodine.
  • haloalkyl when used in compound words such as "haloalkyl” or “haloalkoxy”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different.
  • haloalkyl include F 3 C, ClCH 2 , CF 3 CH 2 and CF 3 CCl 2 .
  • haloalkoxy and the like, are defined analogously to the term “haloalkyl”.
  • haloalkoxy include CF 3 O, CCl 3 CH 2 O, CHF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • the total number of carbon atoms in a substituent group is indicated by the "Cj-C j " prefix where i and j are numbers from 1 to 4.
  • C 1 -C 4 alkyl designates methyl through butyl, including the various isomers.
  • Carboxamide arthropodicides for the method of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomers). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • These carboxamide arthropodicides may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
  • Anthranilamides of Formula 1 can be prepared as described in U.S. Patent 6,747,047, PCT Publications WO 2003/015518 and WO 2004/067528, and phthalic diamides of Formula 2 can be prepared as described in U.S. Patent 6,603,044.
  • the carboxamide arthropodicides (e.g., Formula 1) for the present method can also be in the form of ⁇ f-oxides.
  • the carboxamide arthropodicides e.g., Formula 1
  • nitrogen-containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form JV-oxides.
  • tertiary amines can form N-oxides.
  • Synthetic methods for the preparation of ⁇ f-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as r-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane.
  • MCPBA peroxy acids
  • alkyl hydroperoxides such as r-butyl hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethyldioxirane
  • salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms.
  • salts of carboxamide arthropodicides e.g., Formulae 1 or 2 are useful in the present methods (i.e. are agriculturally suitable).
  • Such salts include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • Salts can also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the carboxamide arthropodicide contains an acidic group such as a carboxylic acid or phenol.
  • the carboxamide arthropodicides according to the methods of this invention can generally be used as a formulation or a composition with a carrier suitable for agronomic or nonagronomic uses comprising at least one of a liquid diluent or a surfactant.
  • a carrier suitable for agronomic or nonagronomic uses comprising at least one of a liquid diluent or a surfactant.
  • Suitable formulations are disclosed in U.S. Patent 6,747,047, PCT Publications WO 2003/015518, WO 2004/067528 and U.S. Patent 6,603,044.
  • the formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight. Said formulated composition can then be diluted with water to the desired sub- lethal, disease transmission-disruptive application rates.
  • suitable compositions comprising a sub-lethal, disease transmission-disruptive amount of a carboxamide arthropodicide include liquid compositions comprising water, organic solvent, or oil as a liquid diluent.
  • the carboxamide arthropodicide of the invention is sometimes contacted with an arthropod pest or its environment in the form of a composition comprising in addition to the carboxamide arthropodicide at least one additional component selected from the group consisting of a surfactant and a liquid diluent.
  • a composition comprising a sub-lethal, disease transmission-disruptive amount of a carboxamide arthropodicide and at least one of a surfactant or a liquid diluent in contacted with the arthropod pest or its environment.
  • Methods of this invention can be applied to plants genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis delta-endotoxins).
  • proteins toxic to invertebrate pests such as Bacillus thuringiensis delta-endotoxins.
  • the effect of the exogenously applied sub-lethal amount of the carboxamide arthropodicide according to a method of this invention may be synergistic with the expressed toxin proteins in disrupting infectious disease transmission.
  • arthropodicides having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management.
  • General references for other arthropodicides include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2003 and The BioPesticide Manual, 2nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2001.
  • Transmission of disease by arthropod pests is disrupted in agronomic and nonagronomic applications by applying a composition comprising a carboxamide arthropodicide in a sub-lethal, disruptive amount to the environment of the pests, including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
  • Agronomic applications include protecting a field crop from disease transmission by the arthropod pest is accomplished typically by applying a composition comprising a carboxamide arthropodicide in a sub-lethal, disruptive amount to the seed of the crop before planting, to the foliage, stems, flowers and/or fruit of crop plants, or to the soil or other growth medium before or after the crop is planted.
  • the disruption of infectious disease transmission at sub-lethal doses is in itself an unexpected effect. We have also discovered that over and above any effects related to infectious disease transmission or inhibition of feeding the methods of the invention also increase crop vigor and crop yields.
  • Nonagronomic applications relate to disruption of arthropod pests in areas other than fields of crop plants.
  • Nonagronomic applications include disruption of arthropod disease transmission in ornamental plants, forests, orchards, in yards, and on turf such as lawns, golf courses and pastures.
  • Nonagronomic applications also include protecting human and animal health by disruption of the transmission of human and animal diseases by arthropod pests that are parasitic or transmit human and animal infectious diseases.
  • Such pests include, for example, chiggers, ticks, lice, mosquitoes, flies and fleas.
  • arthropod pests Disease transmission by arthropod pests is disrupted and protection of agronomic and other crops, and animal and human health is achieved by applying a composition comprising a carboxamide arthropodicide in a sub-lethal, disruptive amount to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests.
  • the present invention comprises a method for disrupting the transmission of infectious plant diseases by an arthropod pest in agronomic and/or nonagronomic applications, comprising contacting the arthropod pest or its environment with a sub-lethal, disruptive amount of a carboxamide arthropodicide, or with a composition comprising a sub-lethal, disruptive amount of a carboxamide arthropodicide.
  • the present invention comprises a method for the disruption of the transmission of infectious plant disease by foliar and soil-inhabiting arthropods and protection of agronomic and/or nonagronomic crops, comprising applying a composition comprising a carboxamide arthropodicide in a sub-lethal, disruptive amount to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the arthropod pests.
  • a method of contact is by spraying the pest and/or the environment of the pest.
  • the carboxamide arthropodicide can be effectively delivered through plant uptake by contacting the plant with a composition comprising a sub-lethal, disruptive amount of a carboxamide arthropodicide applied as a soil drench of a liquid formulation.
  • a method for disrupting the transmission of plant infectious disease by an arthropod pest comprising contacting the soil environment of the arthropod pest with a sub- lethal, disruptive amount of a carboxamide.
  • the method of this invention comprising topical application to the locus of infestation.
  • Other methods of contact include application of a carboxamide arthropodicide according to the methods of the invention by direct and residual sprays, aerial sprays, gels, seed coatings, microencapsulations, systemic uptake, baits, ear tags, boluses, foggers, fumigants, aerosols, dusts and many others.
  • the carboxamide arthropodicide according to the methods of this invention can also be impregnated into materials for fabricating arthropod control devices (e.g., insect netting).
  • Seed coatings can be applied to all types of seeds, including those from which plants genetically transformed to express specialized traits will germinate. Representative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis toxin or those expressing herbicide resistance, such as "Roundup Ready" seed.
  • the carboxamide arthropodicide according to the method of this invention can be applied at rates equal or below LC5 0 without other adjuvants, but most often application will be of a formulation comprising the carboxamide arthropodicide in combination with suitable carriers, diluents, and surfactants and possibly in combination with a food (to facilitate initial ingestion) depending on the contemplated end use.
  • One method of application involves spraying a water dispersion or refined oil solution of a carboxamide arthropodicide. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance efficacy.
  • Such sprays can be applied from spray containers such as a can, a bottle or other container, either by means of a pump or by releasing it from a pressurized container, e.g., a pressurized aerosol spray can.
  • Such spray compositions can take various forms, for example, sprays, mists, foams, fumes or fog.
  • Such spray compositions thus can further comprise propellants, foaming agents, etc. as the case may be.
  • a spray composition comprising a sub-lethal, disruptive amount of a carboxamide arthropodicide or a composition comprising a sub-lethal, disruptive amount of a carboxamide arthropodicide of the present inventions and a carrier.
  • a spray composition comprises a sub-lethal, disruptive amount of a carboxamide arthropodicide or a composition comprising a sub-lethal, disruptive amount of a carboxamide arthropodicide of the present invention and a propellant.
  • propellants include, but are not limited to, methane, ethane, propane, butane, isobutane, butene, pentane, isopentane, neopentane, pentene, hydrofluorocarbons, chlorofluorocarbons, dimethyl ether, and mixtures of the foregoing.
  • a spray composition (and a method utilizing such a spray composition dispensed from a spray container) used to control at least one arthropod pest selected from the group consisting of mosquitoes, black flies, stable flies, deer flies, horse flies, wasps, yellow jackets, hornets, ticks, spiders, ants, gnats, and the like, including individually or in combinations.
  • arthropod pest selected from the group consisting of mosquitoes, black flies, stable flies, deer flies, horse flies, wasps, yellow jackets, hornets, ticks, spiders, ants, gnats, and the like, including individually or in combinations.
  • the carboxamide arthropodicide according to the method of the present invention can be incorporated into a bait composition that is consumed by an arthropod pest (to facilitate initial ingestion) or used within a device such as a trap, bait station, and the like.
  • a bait composition can be in the form of granules which comprise (a) active ingredients, namely a sub-lethal, disruptive amount of a carboxamide arthropodicide; (b) one or more food materials; optionally (c) an attractant, and optionally (d) one or more humectants.
  • granules or bait compositions which comprise between about 0.001-0.1% active ingredients, about 40-99% food material and/or attractant; and optionally about 0.05 — 10% humectants, which are effective in controlling soil invertebrate pests at very low application rates, particularly at doses of active ingredient that are sub-lethal, and disruptive by ingestion.
  • Some food materials can function both as a food source and an attractant.
  • Food materials include carbohydrates, proteins and lipids. Examples of food materials are vegetable flour, sugar, starches, animal fat, vegetable oil, yeast extracts and milk solids.
  • attractants are odorants and flavorants, such as fruit or plant extracts, perfume, or other animal or plant component, pheromones or other agents known to attract a target arthropod pest.
  • humectants i.e. moisture retaining agents, are glycols and other polyols, glycerine and sorbitol.
  • a bait composition (and a method utilizing such a bait composition) used to disrupt disease transmission by at least one arthropod pest selected from the group consisting of ants, termites and cockroaches.
  • a device for disrupting plant disease transmission by an arthropod pest can comprise a bait composition and a housing adapted to receive the bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the arthropod pest can gain access to the bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the arthropod pest.
  • the rate of application e.g., concentration
  • concentration e.g., concentration
  • LCg Q , LC50 or LC 20 concentration causing 80, 50 or 20 % mortality
  • concentrations less than the LC 2 0 can in some circumstances significantly disrupt disease transmission by an arthropod pest, more typically concentrations in range of the LC 20 to LC 50 ⁇ used. If concentrations at the lower end of this range are found not to provide the desired level of disease transmission disruption, concentrations closer or equal to the LC 50 can be used.
  • concentrations closer or equal to the LC 50 can be used.
  • the range of concentrations between LC 20 to LC 50 is relatively small, and one skilled in the art can easily determine the sub-lethal amount providing the desired level of disruption of the transmission of infectious plant disease.
  • sub-lethal, disruptive amounts of carboxamide arthropodicides are typically found to be within the range from about 1 to about 250 g per hectare for agronomic ecosystems, but as little as 0.1 g/hectare may be needed or as much as 500 g/hectare may be required.
  • use rates of sub-lethal, disruptive amounts of carboxamide arthropodicides are typically found to be within the range from about 1 to about 50 mg/square meter, but as little as 0.1 m/square meter may be sufficient or as much as 150 mg/square meter may be required.
  • arthropod pests including arthropod species in one of the Orders Coleoptera, Diptera, Hemiptera, Homoptera, Lepidoptera and Thysanoptera, with a sublethal, disease-transmission disruptive amount of a carboxamide arthropodicide, its ⁇ f-oxide or a salt thereof.
  • Coloptera is the pest species Anthonomus eugenii.
  • Diptera is the pest species Musca domestica.
  • Hemiptera are the pest species Euschistus sp., Nezara viridula and Dychelops sp.
  • Homoptera are the pest species Aphis gossypii, Bemisia argentifolii, Diaphorina citri, Empoasca fabae, Myzus persicae, Nephotettix virescens, Nilaparvata lugens, Toxoptera citricida.
  • Lepidoptera is the pest species Spodoptera exigua.
  • Thysanoptera is the pest species Thrips palmi.
  • the method for disrupting infectious disease transmission by an arthropod pest wherein the infectious disease is a plant disease and the arthropod pest is an aphid (Order: Homoptera, Family: Aphididae) such as Amphorophora agathonica, Amphorophora senso ⁇ ata, Aphis craccivora, Aphis gossipyii, Aphis rubicola, Aphis spiraecola, Brachycaudus cardui, Brachycaudus helichrysi, Myzus hamuli, Myzus persicae, Myzus varians or Toxoptera citricida; a leafhopper (Order: Homoptera, Family: Cicadelliadae) such as Carneocephala fidgida, Colladonus montanus, Circulifer tenellus, Draeculacephala minerva, Fieberiella florii, Graphocephala atropunctata,
  • the infectious disease is a plant disease caused by a virus such as barley yellow dwarf virus, barley yellow streak mosiac virus, bean common mosaic virus, bean common mosaic necrosis virus, beet curly top virus, cassava mosaic virus, cacao swollen shoot virus, cereal yellow dwarf virus, citrus trisetza virus, cucumber mosaic virus, high plains virus, lettuce mosaic virus, pepper mottle virus, plumpox virus (sharka virus), potato Y virus, raspberry leaf curl virus, raspberry mosaic virus, sugarcane mosaic virus, tobacco etch virus, tobacco leaf curl virus (tomato yellow dwarf virus), tomato yellow leaf curl virus, tomato spotted wilt virus, wheat streak virus or wheat streak mosaic virus; a bacterium such as Erwinia stewartii, Liberobacter asiaticum, Liberobacter africanum or Xylella fastidiosa; a phytoplasma (mycoplasma-type organism) such as phytoplasmas causing diseases such as Peach
  • TESTS demonstrate the methods of disruption of transmission of plant infectious disease of this invention.
  • the disruption afforded by the methods is not limited, however, to these species of pests or the particular chemical compounds exemplified.
  • Patent 6,603,044 To the extent necessary to teach the methods of preparing the compounds employed in the invention, (and only to the extent that they are not inconsistent with the disclosure herein) these patents and patent publications are herein incorporated by reference.
  • TEST A Tomato seedlings were grown in transplant trays containing 32 cells, with one tomato seedling in each cell. When the plants reached the 2-leaf stage, treatments were applied as soil drenches by immersing the trays for 30 minutes into deep pans containing aqueous treatment compositions. Testing determined that under these conditions each tray of 32 cells absorbed 280 mL of aqueous treatment composition.
  • the treatment compositions were prepared by mixing a 5 weight % suspension concentrate formulation of Compound 1 or a 10 weight % suspension concentrate formulation of Compound 2 so that the aqueous treatment compositions contained 5 or 10 mg of Compound 1, or 1, 2.5 or 5 mg of Compound 2 in 8.75 mL of composition (the approximate volume absorbed in each cell). Each treatment composition was applied to 4 trays.
  • a further 4 trays of tomato seedlings were used as an untreated control. Seven days after the soil drench treatment four plants were removed from each tray and placed into pots. A single clip-cage was added to a leaflet on each potted plant removed from the original trays.
  • the clip-cage comprised half chambers made of plastic frames and mesh that were held under the force of a spring clip, which enabled snapping around a leaf to form an enclosure.
  • Each clip-cage was infested with 10 non-viruliferous silverleaf whitefly ⁇ Bemisia argentifolii) from a laboratory-reared colony. The number of dead adults were counted daily for the next three days. Results are listed in Table A-I.
  • the "a.i.” designation refers to amount of active ingredient applied. Over another three weeks (up to 40 days after treatment) visual inspections were conducted to look for yellowing and curling of leaves as signs of viral infection. Plant tissue was collected from plants showing these symptoms to confirm the presence of tomato yellow leaf curl virus using polymerase chain reaction (PCR) methodology. Results are listed in Table A-2. TABLE A-I — Mean adult silverleaf whitefly mortality after exposure to treatments of Compound 1 and Compound 2
  • DATl means days after first treatment
  • DAT2 means days after second treatment
  • DATl means days after first treatment
  • DAT2 means days after second treatment

Abstract

Disclosed are methods of increasing crop vigor and crop yields as well as disrupting infectious disease transmission by arthropod pests.

Description

TITLE AGRONOMIC METHOD
FIELD OF THE INVENTION
This invention relates to methods of increasing crop vigor and crop yields as well as disrupting infectious disease transmission by arthropod pests.
BACKGROUND OF THE INVENTION
With the limited amount of high quality arable land that is available for crop production in regions having suitable climate, any method that would improve the vigor and yield of crop plants in general, would provide a significant advantage. Arthropod pests are known to facilitate the transmission of a variety of diseases caused by viruses, bacteria, fungi and other pathogenic organisms. New methods are also needed to inhibit the transmission of these diseases by arthropods.
SUMMARY OF THE INVENTION
This invention pertains to a method for increasing crop growth, yield or vigor comprising treatment of crop plants in an area under cultivation with an effective amount of a carboxamide arthropodicide, its iV-oxide, or a salt thereof.
The invention pertains to a method of disrupting infectious disease transmission by an arthropod pest comprising contacting the arthropod pest or its environment with a sub-lethal, disease transmission disruptive amount of a carboxamide arthropodicide, its iV-oxide, or a salt thereof.
This invention also relates to a method wherein the carboxamide arthropodicide, its N-oxide, or a salt thereof, is formulated as a composition comprising the arthropodicide, its JV-oxide, or a salt thereof, and at least one additional component selected from the group consisting of surfactants and liquid diluents. DETAILS OF THE INVENTION
As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, a mixture, 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, mixture, 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.
The term "arthropod pest" includes insects, mites and ticks that are pests of growing or stored agronomic crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food or fiber products, livestock, houses and other buildings or injurious to public and animal health.
The term "LC50" or "LD50" refers to the concentration or dose of a pesticide which when applied to the target pest species will result in 50 % mortality. The term "sub-lethal concentration", "sub-lethal dose" or "sub-lethal amount", by this definition, means a concentration or dose causing about 50% or less mortality (<LC5ø or LD50); in other words, at least about 50 % of the population are alive at one day (24 hours) after treatment application.
The term "infectious disease" refers to diseases of plants or animals caused by infectious agents including viruses, bacteria, fungi, mycoplasma and phytoplasma. The term "infectious plant diseases" refers to diseases, which reduce crop vigor or crop yield, which are caused by plant infectious agents including viruses, bacteria, fungi and phytoplasma.
The term "disrupting disease transmission" refers to an impairment of a population of arthropod pests (relative to a population of untreated arthropod pests) to act as vectors for infectious diseases.
The term "disrupting plant disease transmission" refers to an impairment of a population of arthropod pests (relative to a population of untreated arthropod pests) to act as vectors for infectious plant diseases.
The terms "disrupting amount" and "disruptive amount" as used herein refer to an amount of compound effective to disrupt transmission of infectious disease (for example, an infectious plant disease) by an arthropod pest.
The term "effective amount" as used herein as it relates to crop yield or crop vigor refers to an amount of compound effective to increase crop yield or crop vigor.
"Crop yield" as defined herein refers to the return of crop material obtained after harvesting a plant crop. An increase in crop yield refers to an increase in crop yield relative to an untreated control crop.
"Crop vigor" refers to rate of growth or biomass accumulation of a crop plant. An "increase in vigor refers" to an increase in growth or biomass accumulation in crop plants relative to an untreated control crop. As is well known in the art, the term "carboxamide" refers to a moiety comprising a carbon, nitrogen and oxygen atom bonded in the configuration shown as Formula A. The carbon atom in Formula A is bonded to a carbon atom in a radical to which the carboxamide moiety is bonded. The nitrogen atom in Formula A is bonded to the carbonyl carbon of Formula A and also bonded to two other atoms, at least one atom of which is selected from a hydrogen atom or a carbon atom of another radical to which the carboxamide moiety is bonded.
Figure imgf000004_0001
In one embodiment the carboxamide arthropodicide of the present method contains at least two carboxamide moieties. In another embodiment the carboxamide arthropodicide contains at least two carboxamide moieties vicinally bonded to carbon atoms (i.e. in ortho arrangement) of a carbocyclic or heterocyclic ring. In a further embodiment the carbocyclic or heterocyclic ring of the at least one carboxamide arthropodicide is aromatic (i.e. satisfies the Hϋckel 4n+2 rule for aromaticity).
Embodiments of the present invention include:
Embodiment 1. The methods described in the Summary of the Invention wherein the carboxamide arthropodicide is selected from an anthranilamide (also described as anthranilic diamide) of Formula 1, an N-oxide, or a salt thereof,
Figure imgf000004_0002
wherein
X is N7 CF, CCl, CBr or CI;
RMs CH31 Cl5 Br Or F;
R2 is H, F, Cl, Br or CN;
R3 is F, Cl, Br, C1-C4 haloalkyl or C1-C4 haloalkoxy; R4a is H, C1-C4 alkyl, cyclopropylmethyl or 1-cyclopropylethyl;
R4b is H or CH3;
R5 is H, F, Cl or Br; and
R6 is H, F, Cl or Br.
Embodiment IA. The methods of Embodiment 1 wherein X is N; R1 is CH3; R2 is Cl or CN; R3 is Cl, Br or CF3; R4a is C t-C4 alkyl; R«b [s H; R5 is Cl; and R^ is H. Embodiment IB. The methods of Embodiment 1 wherein X is N; R1 is CH3; R2 is Cl or CN; R3 is Cl, Br or CF3; R*a is Me or CH(CH3)2; R4*> is H; R5 is Cl; and R6 is H.
Embodiment 1C. The method of Embodiment 1 wherein the carboxamide arthropodicide is selected from the group consisting of:
^V-[4-chloro-2-methyl-6-[[(l-methylethyl)amino]carbonyl]phenyl]-l-(3-chloro-
2-pyridinyl)-3-(trifluoromethyl)-lH-pyrazole-5-carboxamide,
Λ^-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-l-(3-chloro-
2-pyridin yl)-3-(tri fluoromethyl)- lH-pyrazole-5-carboxamide,
3-bromo-Λ^-[4-chloro-2-methyl-6-[[(l-methylethyl)amino]carbonyl]phenyl]- l-(3-chloro-2-pyridinyl)-lH-pyrazole-5-carboxamide,
3-bromo-Λ^-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-l-(3-chloro-
2-pyridinyl)-lH-pyrazole-5-carboxamide,
3-bromo-l-(3-chloro-2-pyridinyl)-7V-[4-cyano-2-methyl-6-[(methylamino)- carbonyl]phenyl]-lH-pyrazole-5-carboxamide, l-(3-chloro-2-pyridinyl)-//-[4-cyano-2-methyl-6-[(methylamino)carbonyl]- phenyl]-3-(trifluoromethyl)-lH-pyrazole-5-carboxamide,
3-bromo-l-(2-chlorophenyl)-Λ(-[4-cyano-2-methyl-6-[[(l-methylethyl)amino]- carbonyl]phenyl]-lH-pyrazole-5-carboxamide,
3-bromo-l-(2-chlorophenyl) -Λ^[4-cyano-2-methyl-6-[(methylamino)carbonyl]- phenyl]- lH-pyrazole-5-carboxamide,
3-bromo-l-(2-chlorophenyl)-N-[2,4-dichloro-6-[(methylamino)carbonyl]- phenyl]-lH-pyrazole-5-carboxamide,
3-bromo-iV-[4-chloro-2-[[(cyclopropylmethyl)amino]carbonyl]-6-methyl- phenyl]-l-(3-chloro-2-pyridinyl)-lH-pyrazole-5-carboxamide,
3-bromo-l-(3-chloro-2-pyridinyl)-N-[4-cyano-2-[[(cyclopropylmethyl)amino]- carbonyl]-6-methylphenyl]-lH-pyrazole-5-carboxamide,
3-bromo-N-[4-chloro-2-[[(l-cyclopropylethyl)amino]carbonyl]-6-methyl- phenyl]-l -(3-chloro-2-pyridinyl)-lH-pyrazole-5-carboxamide, and
3-bromo-l-(3-chloro-2-pyridinyl)-N-[4-cyano-2-[[(l-cyclopropylethyl)amino]- carbonyl] -6-methylphenyl] - lH-pyrazole-5 -carboxamide.
Embodiment 2. The methods described in the Summary of the Invention wherein the carboxamide arthropodicide is selected from a phthalic diamide of Formula 2 or a salt thereof,
Figure imgf000006_0001
wherein
R1Ms CH31 Cl5 Br Or I;
R12 is CH3 or Cl;
R13 is C1-C3 fluoroalkyl;
R14 is H or CH3;
R15 is H or CH3;
R16 is C1-C2 alky!' and n is 0, 1 or 2. Embodiment 2B. The methods of Embodiment 2 wherein R1 1 is Cl, Br or I; R12 is
CH3; R13 is CF3, CF2CF3 or CF(CF3)2 (equivalently identified as (CF3)2CF);
Rl4 is H or CH3; R1S is H or CH3; R^ is CH3; and n is 0, 1 or 2. Embodiment 2C. The methods of Embodiment 2 wherein the carboxamide arthropodicide is Λ^-fl.l-dimethyl^-Cmethylsulfony^ethylJ-S-iodo-
//J-P-methyl^-tl^^^-tetrafluoro-l-CtrifluoromethyOethyllphenyl]-
1 ,2-benzenedicarboxamide. Embodiment 3. The methods described in the Summary of the Invention wherein the arthropod pest is a species in one of the orders Coleoptera, Diptera, Hemiptera,
Homoptera, Lepidoptera, and Thysanoptera. Embodiment 4. The methods of Embodiment 3 wherein the arthropod pest is a species of the order Coleptera. Embodiment 4A. The methods of Embodiment 4 wherein the arthropod pest is
Anthonomus eugenii. Embodiment 5. The methods of Embodiment 3 wherein the arthropod pest is a species of the order Diptera.
Embodiment 5A. The methods of Embodiment 5 wherein the arthropod pest is Musca domestica. Embodiment 6. The methods of Embodiment 3 wherein the arthropod pest is a species of the order Hemiptera. Embodiment 6A. The methods of Embodiment 6 wherein the arthropod pest is a
Euschistus species. Embodiment 6B. The methods of Embodiment 6 wherein the arthropod pest is Nezara viridula. Embodiment 6C. The methods of Embodiment 6 wherein the arthropod pest is a
Dychelops species. Embodiment 7. The methods of Embodiment 3 wherein the arthropod pest is a species of the order Homoptera.
Embodiment 7A. The methods of Embodiment 7 wherein the arthropod pest is Aphis gossypii.
Embodiment 7B. The methods of Embodiment 7 wherein the arthropod pest is
Bemisia argentifolii. Embodiment 7C. The methods of Embodiment 7 wherein the arthropod pest is
Diaphorina citri. Embodiment 7D. The methods of Embodiment 7 wherein the arthropod pest is
Empoasca fabae. Embodiment 7E. The methods of Embodiment 7 wherein the arthropod pest is Myzus persicae.
Embodiment 7F. The methods of Embodiment 7 wherein the arthropod pest is Nephotettix virescens.
Embodiment 7G. The methods of Embodiment 7 wherein the arthropod pest is
Nilaparvata lugens. Embodiment 7H. The methods of Embodiment 7 wherein the arthropod pest is
Toxoptera citricida. Embodiment 8. The methods of Embodiment 3 wherein the arthropod pest is a species of the order Lepidoptera. Embodiment 8 A. The methods of Embodiment 8 wherein the arthropod pest is
Spodoptera exigua.
Embodiment 9. The methods of Embodiment 3 wherein the arthropod pest is a species of the order Thysanoptera.
Embodiment 9A. The methods of Embodiment 9 wherein the arthropod pest is Thrips palmi. Embodiment 10. The methods described in the Summary of the Invention or any of the embodiments described herein comprising contacting an arthropod pest or its environment with a composition comprising a sub-lethal amount of a carboxamide arthropodicide, its Λf-oxide, or a salt thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. Embodiment 11. The methods of Embodiment 10 wherein the composition further comprises a biologically effective amount of a sex pheromone.
In the above recitations, the term "alkyl", used either alone or in compound words such as "haloalkyl" or "fluoroalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl isomers. "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy isomers. The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl" or "haloalkoxy", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" include F3C, ClCH2, CF3CH2 and CF3CCl2. The terms "haloalkoxy", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkoxy" include CF3O, CCl3CH2O, CHF2CH2CH2O and CF3CH2O. The total number of carbon atoms in a substituent group is indicated by the "Cj-Cj" prefix where i and j are numbers from 1 to 4. For example, C1-C4 alkyl designates methyl through butyl, including the various isomers.
Carboxamide arthropodicides (e.g., Formulae 1 or 2) for the method of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomers). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. These carboxamide arthropodicides may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
Anthranilamides of Formula 1 can be prepared as described in U.S. Patent 6,747,047, PCT Publications WO 2003/015518 and WO 2004/067528, and phthalic diamides of Formula 2 can be prepared as described in U.S. Patent 6,603,044.
The carboxamide arthropodicides (e.g., Formula 1) for the present method can also be in the form of Λf-oxides. One skilled in the art will appreciate that not all nitrogen- containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form JV-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of Λf-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as r-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the preparation of TV-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748—750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18—20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press. One skilled in the art recognizes that because in the environment and under physiological conditions salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms. Thus a wide variety of salts of carboxamide arthropodicides (e.g., Formulae 1 or 2) are useful in the present methods (i.e. are agriculturally suitable). Such salts include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. Salts can also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the carboxamide arthropodicide contains an acidic group such as a carboxylic acid or phenol.
Formulation/Utility
The carboxamide arthropodicides according to the methods of this invention can generally be used as a formulation or a composition with a carrier suitable for agronomic or nonagronomic uses comprising at least one of a liquid diluent or a surfactant. Suitable formulations are disclosed in U.S. Patent 6,747,047, PCT Publications WO 2003/015518, WO 2004/067528 and U.S. Patent 6,603,044.
The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight. Said formulated composition can then be diluted with water to the desired sub- lethal, disease transmission-disruptive application rates. Examples of suitable compositions comprising a sub-lethal, disease transmission-disruptive amount of a carboxamide arthropodicide include liquid compositions comprising water, organic solvent, or oil as a liquid diluent. Weight Percent
Active Ingredient Diluent Surfactant
Water-Dispersible and Water-soluble 0.001-90 0-99.999 0-15 Granules, Tablets and Powders.
Suspensions, Emulsions, Solutions 1-50 40-99 0-50 (including Emulsifiable 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
For further information regarding the art of formulation, see T. S. Woods, "The Formulator's Toolbox - Product Forms for Modem 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 methods of this invention the carboxamide arthropodicide of the invention is sometimes contacted with an arthropod pest or its environment in the form of a composition comprising in addition to the carboxamide arthropodicide at least one additional component selected from the group consisting of a surfactant and a liquid diluent. Thus the present invention also pertains to a method wherein a composition comprising a sub-lethal, disease transmission-disruptive amount of a carboxamide arthropodicide and at least one of a surfactant or a liquid diluent in contacted with the arthropod pest or its environment.
Methods of this invention can be applied to plants genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis delta-endotoxins). The effect of the exogenously applied sub-lethal amount of the carboxamide arthropodicide according to a method of this invention may be synergistic with the expressed toxin proteins in disrupting infectious disease transmission.
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. General references for other arthropodicides include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2003 and The BioPesticide Manual, 2nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2001. Transmission of disease by arthropod pests is disrupted in agronomic and nonagronomic applications by applying a composition comprising a carboxamide arthropodicide in a sub-lethal, disruptive amount to the environment of the pests, including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. Agronomic applications include protecting a field crop from disease transmission by the arthropod pest is accomplished typically by applying a composition comprising a carboxamide arthropodicide in a sub-lethal, disruptive amount to the seed of the crop before planting, to the foliage, stems, flowers and/or fruit of crop plants, or to the soil or other growth medium before or after the crop is planted. The disruption of infectious disease transmission at sub-lethal doses is in itself an unexpected effect. We have also discovered that over and above any effects related to infectious disease transmission or inhibition of feeding the methods of the invention also increase crop vigor and crop yields.
Nonagronomic applications relate to disruption of arthropod pests in areas other than fields of crop plants. Nonagronomic applications include disruption of arthropod disease transmission in ornamental plants, forests, orchards, in yards, and on turf such as lawns, golf courses and pastures. Nonagronomic applications also include protecting human and animal health by disruption of the transmission of human and animal diseases by arthropod pests that are parasitic or transmit human and animal infectious diseases. Such pests include, for example, chiggers, ticks, lice, mosquitoes, flies and fleas.
Disease transmission by arthropod pests is disrupted and protection of agronomic and other crops, and animal and human health is achieved by applying a composition comprising a carboxamide arthropodicide in a sub-lethal, disruptive amount to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests. Therefore, the present invention comprises a method for disrupting the transmission of infectious plant diseases by an arthropod pest in agronomic and/or nonagronomic applications, comprising contacting the arthropod pest or its environment with a sub-lethal, disruptive amount of a carboxamide arthropodicide, or with a composition comprising a sub-lethal, disruptive amount of a carboxamide arthropodicide. More particularly, the present invention comprises a method for the disruption of the transmission of infectious plant disease by foliar and soil-inhabiting arthropods and protection of agronomic and/or nonagronomic crops, comprising applying a composition comprising a carboxamide arthropodicide in a sub-lethal, disruptive amount to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the arthropod pests.
One embodiment of a method of contact is by spraying the pest and/or the environment of the pest. Alternatively, according to the method of the present invention, the carboxamide arthropodicide can be effectively delivered through plant uptake by contacting the plant with a composition comprising a sub-lethal, disruptive amount of a carboxamide arthropodicide applied as a soil drench of a liquid formulation.
Of note is a method for disrupting the transmission of plant infectious disease by an arthropod pest comprising contacting the soil environment of the arthropod pest with a sub- lethal, disruptive amount of a carboxamide. Of further note is the method of this invention comprising topical application to the locus of infestation. Other methods of contact include application of a carboxamide arthropodicide according to the methods of the invention by direct and residual sprays, aerial sprays, gels, seed coatings, microencapsulations, systemic uptake, baits, ear tags, boluses, foggers, fumigants, aerosols, dusts and many others. The carboxamide arthropodicide according to the methods of this invention can also be impregnated into materials for fabricating arthropod control devices (e.g., insect netting). Seed coatings can be applied to all types of seeds, including those from which plants genetically transformed to express specialized traits will germinate. Representative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis toxin or those expressing herbicide resistance, such as "Roundup Ready" seed.
The carboxamide arthropodicide according to the method of this invention can be applied at rates equal or below LC50 without other adjuvants, but most often application will be of a formulation comprising the carboxamide arthropodicide in combination with suitable carriers, diluents, and surfactants and possibly in combination with a food (to facilitate initial ingestion) depending on the contemplated end use. One method of application involves spraying a water dispersion or refined oil solution of a carboxamide arthropodicide. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance efficacy. For nonagronomic uses such sprays can be applied from spray containers such as a can, a bottle or other container, either by means of a pump or by releasing it from a pressurized container, e.g., a pressurized aerosol spray can. Such spray compositions can take various forms, for example, sprays, mists, foams, fumes or fog. Such spray compositions thus can further comprise propellants, foaming agents, etc. as the case may be. Of note is a spray composition comprising a sub-lethal, disruptive amount of a carboxamide arthropodicide or a composition comprising a sub-lethal, disruptive amount of a carboxamide arthropodicide of the present inventions and a carrier. One embodiment of such a spray composition comprises a sub-lethal, disruptive amount of a carboxamide arthropodicide or a composition comprising a sub-lethal, disruptive amount of a carboxamide arthropodicide of the present invention and a propellant. Representative propellants include, but are not limited to, methane, ethane, propane, butane, isobutane, butene, pentane, isopentane, neopentane, pentene, hydrofluorocarbons, chlorofluorocarbons, dimethyl ether, and mixtures of the foregoing. Of note is a spray composition (and a method utilizing such a spray composition dispensed from a spray container) used to control at least one arthropod pest selected from the group consisting of mosquitoes, black flies, stable flies, deer flies, horse flies, wasps, yellow jackets, hornets, ticks, spiders, ants, gnats, and the like, including individually or in combinations.
The carboxamide arthropodicide according to the method of the present invention can be incorporated into a bait composition that is consumed by an arthropod pest (to facilitate initial ingestion) or used within a device such as a trap, bait station, and the like. Such a bait composition can be in the form of granules which comprise (a) active ingredients, namely a sub-lethal, disruptive amount of a carboxamide arthropodicide; (b) one or more food materials; optionally (c) an attractant, and optionally (d) one or more humectants. Of note are granules or bait compositions which comprise between about 0.001-0.1% active ingredients, about 40-99% food material and/or attractant; and optionally about 0.05 — 10% humectants, which are effective in controlling soil invertebrate pests at very low application rates, particularly at doses of active ingredient that are sub-lethal, and disruptive by ingestion. Some food materials can function both as a food source and an attractant. Food materials include carbohydrates, proteins and lipids. Examples of food materials are vegetable flour, sugar, starches, animal fat, vegetable oil, yeast extracts and milk solids. Examples of attractants are odorants and flavorants, such as fruit or plant extracts, perfume, or other animal or plant component, pheromones or other agents known to attract a target arthropod pest. Examples of humectants, i.e. moisture retaining agents, are glycols and other polyols, glycerine and sorbitol. Of note is a bait composition (and a method utilizing such a bait composition) used to disrupt disease transmission by at least one arthropod pest selected from the group consisting of ants, termites and cockroaches. A device for disrupting plant disease transmission by an arthropod pest can comprise a bait composition and a housing adapted to receive the bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the arthropod pest can gain access to the bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the arthropod pest.
The rate of application (e.g., concentration) of a carboxamide arthropodicide required for effectively disrupting infectious disease transmission by an arthropod pest while causing no more than about 50% mortality of the pest population 24 hours after treatment application will depend on such factors as the pest species, its size, location, season, host crop or animal, feeding behavior, ambient moisture, temperature, method of application, and the like. Under normal circumstances, the LCgQ, LC50 or LC20 (concentration causing 80, 50 or 20 % mortality) of a carboxamide arthropodicide over 24 hours is first determined for a particular pest species using the selected application conditions. Although concentrations less than the LC20 can in some circumstances significantly disrupt disease transmission by an arthropod pest, more typically concentrations in range of the LC20 to LC50 ∞^ used. If concentrations at the lower end of this range are found not to provide the desired level of disease transmission disruption, concentrations closer or equal to the LC50 can be used. The range of concentrations between LC20 to LC50 is relatively small, and one skilled in the art can easily determine the sub-lethal amount providing the desired level of disruption of the transmission of infectious plant disease.
Application rates of sub-lethal, disruptive amounts of carboxamide arthropodicides are typically found to be within the range from about 1 to about 250 g per hectare for agronomic ecosystems, but as little as 0.1 g/hectare may be needed or as much as 500 g/hectare may be required. For nonagronomic applications, use rates of sub-lethal, disruptive amounts of carboxamide arthropodicides are typically found to be within the range from about 1 to about 50 mg/square meter, but as little as 0.1 m/square meter may be sufficient or as much as 150 mg/square meter may be required.
Transmission of plant infectious disease is effectively controlled according to the methods of the present invention by contacting arthropod pests, including arthropod species in one of the Orders Coleoptera, Diptera, Hemiptera, Homoptera, Lepidoptera and Thysanoptera, with a sublethal, disease-transmission disruptive amount of a carboxamide arthropodicide, its Λf-oxide or a salt thereof.
Of particular note in the order Coloptera is the pest species Anthonomus eugenii. Of particular note in the order Diptera is the pest species Musca domestica. Of particular note in the order Hemiptera are the pest species Euschistus sp., Nezara viridula and Dychelops sp. Of particular note in the order Homoptera are the pest species Aphis gossypii, Bemisia argentifolii, Diaphorina citri, Empoasca fabae, Myzus persicae, Nephotettix virescens, Nilaparvata lugens, Toxoptera citricida. Of particular note within the order Lepidoptera is the pest species Spodoptera exigua. Of particular note within the order Thysanoptera is the pest species Thrips palmi.
Of note is the method for disrupting infectious disease transmission by an arthropod wherein the infectious disease is a plant disease.
Of note is the method for disrupting infectious disease transmission by an arthropod pest wherein the infectious disease is a plant disease and the arthropod pest is an aphid (Order: Homoptera, Family: Aphididae) such as Amphorophora agathonica, Amphorophora sensoήata, Aphis craccivora, Aphis gossipyii, Aphis rubicola, Aphis spiraecola, Brachycaudus cardui, Brachycaudus helichrysi, Myzus hamuli, Myzus persicae, Myzus varians or Toxoptera citricida; a leafhopper (Order: Homoptera, Family: Cicadelliadae) such as Carneocephala fidgida, Colladonus montanus, Circulifer tenellus, Draeculacephala minerva, Fieberiella florii, Graphocephala atropunctata, Homalodisca coagulata, Homalodisca insolita, Macrosteles quadrilineatus or a Oncometopia species; a mealybug (Order: Homoptera, Family: Pseudococcidae) such as Dysmicoccus brevipes, Ferrisia virgata, Planococcus celtis, Planococcus citri, Planococcus kenyae, Planococcoides njalensis or Pseudococcus longispinus; a psyllid (Order: Homoptera, Family: Psyllidae) such as Cacopsylla pyricola, Diaphorina citri or Trioza erytreae; a whitefly (Order: Homoptera, Family: Aleyrodidae) such as Bemisia argentifolii or Bemesia tabaci; a thrip (Order: Thysanoptera, Family: Thripidae) such as Frankliniella fusca, Frankliniella occidentalis, Frankliniella schultzei, Frankliniella tenuicornisi, Scirtothrips dorsalis, Thrips palmi, Thrips moultoni, Thrips setosus or Thrips tabaci; a beetle (Order: Coleoptera) such as Chaetocnema pulicaria (Family: Chrysomelidae), or Hylurogopinus rufipes or Scolytus multistriatus (Family: Scolytidae); or a mite (Order: Acari, Family: Eriophyidae) such as Aceria tosichella, Aceria tulipae or Petrobia latens. Note that some contemporary classification systems consider the Order of the Families Aphididae, Aleyroididae, Cicadelliadae, Pseudococcidae and Psyllidae to be Hemiptera instead of Homoptera and instead consider Homoptera or another classification to be the Suborder for these Families. Of particular note is the method for disrupting infectious disease transmission by an arthropod pest wherein the arthropod pest is an aphid, a leafhopper, a mealybug, a psyllid, a whitefly or a thrip.
Also of note is the method for disrupting infectious disease transmission by an arthropod pest wherein the infectious disease is a plant disease caused by a virus such as barley yellow dwarf virus, barley yellow streak mosiac virus, bean common mosaic virus, bean common mosaic necrosis virus, beet curly top virus, cassava mosaic virus, cacao swollen shoot virus, cereal yellow dwarf virus, citrus trisetza virus, cucumber mosaic virus, high plains virus, lettuce mosaic virus, pepper mottle virus, plumpox virus (sharka virus), potato Y virus, raspberry leaf curl virus, raspberry mosaic virus, sugarcane mosaic virus, tobacco etch virus, tobacco leaf curl virus (tomato yellow dwarf virus), tomato yellow leaf curl virus, tomato spotted wilt virus, wheat streak virus or wheat streak mosaic virus; a bacterium such as Erwinia stewartii, Liberobacter asiaticum, Liberobacter africanum or Xylella fastidiosa; a phytoplasma (mycoplasma-type organism) such as phytoplasmas causing diseases such as Peach X Disease, Pear Decline, Cherry Buckskin Disease, Coconut Lethal Yellowing, Apple Proliferation, Tomato Big Bud, Aster Yellows or Yellows of other plant species; or a fungus such as Ophiostoma ulmi. Of particular note is the method for disrupting infectious disease transmission by an arthropod pest wherein in infectious disease is cause by a virus, a bacterium or a phytoplasma, and more particularly a virus.
The following TESTS demonstrate the methods of disruption of transmission of plant infectious disease of this invention. The disruption afforded by the methods is not limited, however, to these species of pests or the particular chemical compounds exemplified.
COMPOUND TABLE 1 Compound No.
1 3-bromo-Λf- [4-ch loro-2-methyl -6- [(methyl amino)carbonyl]phenyl ] - l-(3-chloro-2-pyridinyl)-lH-pyrazole-5-carboxamide.
2 3-bromo-l-(3-chloro-2-pyridinyl)-Λf-[4-cyano-2-methyl-6-[(methylamino)- carbonyl]phenyl]-lH-pyrazole-5-carboxamide.
3 A/2-[l,l-dimethyl-2-(methylsulfonyl)ethyl]-3-iodo-N1-[2-methyl-4- [1 ,2,2,2-tetrafluoro- l-(trifluoromethyl)ethyl]phenyl]-l ,2- benzenedicarboxamide. 4 iV-[4-chloro-2-methyl-6-[[(l-methylethyl)amino]carbonyl]phenyl]- l-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-lH-pyrazole-5-carboxamide.
5 N-[4K:hloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-l-(3-chloro- 2-pyridinyl)-3-(trifluoromethyl)-lH-pyrazole-5-carboxamide.
6 3-bromo-N-[4-chloro-2-methyl-6-[[(l-methylethyl)amino]carbonyl]- phenyl]-l-(3-chloro-2-pyridinyl)-lH-pyrazole-5-carbox amide.
7 l-(3-chloro-2-pyridinyl)-iV-[4-cyano-2-methyl-6-[(methylamino)carbonyl]- phenyl]-3-(trifluoromethyl)-lH-pyrazole-5-carboxamide.
8 3-bromo-l-(2-ch]orophenyl)-N-[4-cyano-2-methyl-6-[[(l-methylethyl)- amino]carbonyl]phenyl]-lH-pyrazole-5-carboxamide.
9 3-bromo- l-(2-chlorophenyl)-iV-[4-cyano-2-methyl-6-[(methylamino)- carbonyl]phenyl]-lH-pyrazole-5-carboxamide.
10 3-bromo-l-(2-chlorophenyl)-N-[2,4-dichloro-6-[(methylamino)carbonyl]- phenyl]-lH-pyrazole-5-carboxamide.
11 3-bromo-N-[4-chloro-2-[[(cyclopropylmethyl)amino]carbonyl]-6-methyl- phenylj-l-CS-chloro^-pyridinyO-lH-pyrazole-S-carboxamide.
12 3 -bromo- 1 -(3 -ch loro-2-pyridinyl)-.N- [4-cyano-2- [ [(cyclopropylmethyl )- aminol-carbonyH-o-methylphenyll-lH-pyrazole-S-carboxamide.
13 3-bromo-N-[4-chloro-2-[[(l-cyclopropylethyl)amino]carbonyl]-6-methyl- phenyll-l-Q-chloro^-pyridinyO-lH-pyrazole-S-carboxarnide.
14 3-bromo-l-(3-chloro-2-pyridinyl)-iV-[4-cyano-2-[[(l-cyclopropylethyl)- amino]carbonyl]-6-methylphenyl]-lH-pyrazole-5-carboxamide.
Methods for preparing the compounds listed in Compound Table 1 are disclosed in
U.S. Patent 6,747,047, PCT Publications WO 2003/015518, WO 2004/067528 and U.S.
Patent 6,603,044. To the extent necessary to teach the methods of preparing the compounds employed in the invention, (and only to the extent that they are not inconsistent with the disclosure herein) these patents and patent publications are herein incorporated by reference.
BIOLOGICAL EXAMPLES OF THE INVENTION
Compound numbers in the Tests described below are identified above in Compound Table 1.
TEST A Tomato seedlings were grown in transplant trays containing 32 cells, with one tomato seedling in each cell. When the plants reached the 2-leaf stage, treatments were applied as soil drenches by immersing the trays for 30 minutes into deep pans containing aqueous treatment compositions. Testing determined that under these conditions each tray of 32 cells absorbed 280 mL of aqueous treatment composition. The treatment compositions were prepared by mixing a 5 weight % suspension concentrate formulation of Compound 1 or a 10 weight % suspension concentrate formulation of Compound 2 so that the aqueous treatment compositions contained 5 or 10 mg of Compound 1, or 1, 2.5 or 5 mg of Compound 2 in 8.75 mL of composition (the approximate volume absorbed in each cell). Each treatment composition was applied to 4 trays. A further 4 trays of tomato seedlings were used as an untreated control. Seven days after the soil drench treatment four plants were removed from each tray and placed into pots. A single clip-cage was added to a leaflet on each potted plant removed from the original trays. The clip-cage comprised half chambers made of plastic frames and mesh that were held under the force of a spring clip, which enabled snapping around a leaf to form an enclosure. Each clip-cage was infested with 10 non-viruliferous silverleaf whitefly {Bemisia argentifolii) from a laboratory-reared colony. The number of dead adults were counted daily for the next three days. Results are listed in Table A-I.
At the same time, twenty-four plants were removed from each of the trays to measure transmission of viral disease by silverleaf whitefly. The plants were placed in organdy- covered cages and silverleaf whitefly adults from a laboratory colony reared on plants infected with tomato yellow leaf curl virus (TYLCV) were released into the cages at a rate of 5 adults per plant. Cages were arranged in the greenhouse in a randomized complete block design with four replications. Ten days post-infestation (17 days after treatment) all of the trays were drenched with Admire® Pro (0.7 mg a.i. imidacloprid / plant) to kill the silverleaf whitefly nymphs. Subsequently, the test plants were treated with fertilizer. The "a.i." designation refers to amount of active ingredient applied. Over another three weeks (up to 40 days after treatment) visual inspections were conducted to look for yellowing and curling of leaves as signs of viral infection. Plant tissue was collected from plants showing these symptoms to confirm the presence of tomato yellow leaf curl virus using polymerase chain reaction (PCR) methodology. Results are listed in Table A-2. TABLE A-I — Mean adult silverleaf whitefly mortality after exposure to treatments of Compound 1 and Compound 2
Figure imgf000017_0001
* DAT means days after beginning exposure to treated plant TABLE A-2 — Percent of TYLCV-infection in tomato plants treated with various concentrations of Compound 1 and Compound 2 vs. untreated checks.
Figure imgf000018_0001
* mg a.i. / plant
The results in Table A-I show that all treatments caused less than 50% mortality 24 hours after treatment and thus had sub-lethal effects. Ordinarily a 24-hour period of exposure would be sufficient for a viruliferous silverleaf whitefly adult to infect healthy plants with TYLCV. Even though the treatments caused less than 50% mortality during the 24 hours after treatment, the results in Table A-2 show these treatments reduced transmission of TYLCV to tomato plants. TEST B
Chili plants (also known as chilli plants and chili pepper plants) were grown to the early flowering stage in field plots that were 1 meter wide by 3.5 meters long. Prior to application, measured amounts of Compound 2 as a 10 weight % oil dispersion formulation were diluted with water to provide the specified application rates. Applications were made using a Cθ2-pressurized backpack sprayer delivering 400 liters per hectares using hollow cone nozzles and 60 psi (410 kPa) pressure.
Two treatment applications were made at an 8-day interval. Populations of Thrips palmi were evaluated 7 days after each of the applications by counting the number of thrips nymphs and adults on 20 plants in each plot. Visual assessment of the percent of plants damaged by tomato spotted wilt virus (TSWV) was made at the same time. This virus causes lesions, and ultimately wilting. Results are shown in Table B. TABLE B - Efficacy of Compound 2 for control of Thrips palmi and reducing virus incidence in chili under field conditions*
Figure imgf000019_0001
* DATl means days after first treatment; DAT2 means days after second treatment.
The results in Table B show treatments with Compound 2 substantially reduced the transmission of tomato spotted wilt virus by Thrips palmi.
TEST C
Chili plants were grown to the early flowering stage in field plots that were 1 meter wide by 3 meters long. Prior to application, measured amounts of Compound 2 as a 10 weight % suspension concentrate formulation were diluted with water to provide the specified application rates. Applications were made using a CC^-pressurized backpack sprayer delivering 400 liters per hectares using hollow cone nozzles and 60 psi (410 kPa) pressure.
Two treatment applications were made at a 7-day interval. Populations of Thrips palmi were evaluated prior to the first application, 7 days after each of the two applications, and also 14 days after the second application by counting the number of thrips nymphs and adults on 5 plants in each plot before the first application and subsequently on 10 plants in each plot. Results are shown in Table C-I. Visual assessment of the percent of plants damaged by tomato spotted wilt virus (TSWV) was made at the same time as evaluations of Thrips palmi populations after the applications. Results are shown in Table C-2. TABLE C-I - Efficacy of Compound 2 for control of Thrips palmi under field conditions*
Figure imgf000019_0002
* DATl means days after first treatment; DAT2 means days after second treatment. TABLE C-2 - Efficacy of Compound 2 for reducing virus incidence in chili plants under field conditions*
Figure imgf000020_0001
* DATl means days after first treatment; DAT2 means days after second treatment.
The results in Table C-2 show treatments with Compound 2 substantially reduced the transmission of tomato spotted wilt virus by Thrips palmi.

Claims

CLAIMSWhat is claimed is:
1. A method for increasing crop yield or crop vigor comprising treatment of crop plants in an area under cultivation with an effective amount of a carboxamide arthropodicide, its N-oxide, or a salt thereof.
2. A method for disrupting infectious disease transmission by an arthropod pest comprising contacting the arthropod pest or its environment with a sub-lethal, disease transmission disruptive amount of a carboxamide arthropodicide, its N-oxide, or a salt thereof.
3. The method of either of Claims 1 or 2 wherein the carboxamide arthropodicide is selected from an anthranilamide of Formula 1, an N-oxide, or a salt thereof,
Figure imgf000021_0001
wherein
X is N, CF, CCl, CBr or CI; Rl is CH3, Cl, Br or F;
R2 is H, F, Cl, Br or CN;
R3 is F, Cl, Br, C1-C4 haloalkyl or C1-C4 haloalkoxy;
R4a is H, C1-C4 alkyl, cyclopropylmethyl or 1-cyclopropylethyl;
R4*> is H or CH3; R5 is H, F, Cl or Br; and
R6 is H, F, Cl or Br.
4. The method of Claim 3 wherein X is N; R1 is CH3; R2 is Cl or CN; R3 is Cl, Br or CF3; R4* is C1-C4 alkyl; R4b is H; R5 is Cl; and R6 is H.
5. The method of Claim 4 wherein X is N; R1 is CH3; R2 is Cl or CN; R3 is Cl, Br or CF3; R4a is Me or CH(CH3)2; R4b is H; R5 is Cl; and R6 is H.
6. The method of either of Claims 1 or 2 wherein the carboxamide arthropodicide is selected from a phthalic di amide of Formula 2 or a salt thereof,
Figure imgf000022_0001
wherein
R1Ms CH3- Q1 Br Or I; R12 is CH3 or Cl; R13 is C1-C3 fluoroalkyl;
R14 is H or CH3; R15 is H or CH3; R16 is C1-C2 alkyl; and n is 0, 1 or 2.
7. The method of Claim 6 wherein R11 is Cl, Br or I; R12 is CH3; R13 is CF3,
CF2CF3 or CF(CF3)2; R14 is H or CH3; R15 is H or CH3; R16 is CH3; and n is 0, 1 or 2.
8. The method of either of Claims 1 or 2 wherein the carboxamide arthropodicide is selected from:
Λf-[4-chloro-2-methyl-6-[[( 1 -methylethy^aminojcarbonyllphenyl]- 1 -(3-chloro-
2-pyridinyl)-3-(trifluoromethyl)-lH-pyrazole-5-carboxamide, iV-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-l-(3-chloro-
2-pyridinyl)-3-(trifluoromethyl)-lH-pyrazole-5-carboxamide,
S-bromo-^V-t^chloro^-methyl-ό-IfCl-methylethyOaminolcarbonyllphenyl]- l-(3-chloro-2-pyridinyl)-lH-pyrazole-5-carboxamide,
3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-l-(3-chloro-
2-pyridinyl)-lH-pyrazole-5-carboxamide,
3-bromo-l-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)- carbonyl]phenyl]-lH-pyrazole-5-carboxamide, l-CS-chloro^-pyridinyO-N-^-cyano^-methyl-ό-Kmethylamino^arbonyl]- phenyl]-3-(trifluoromethyl)-lH-pyrazole-5-carboxamide,
3-bromo- 1 -(2-chlorophenyl)-./V- [4-cyano-2-methyl-6-[ [( 1 -methylethyl)amino]- carbonyl]phenyl ] - 1 H-pyrazole-5-carboxamide,
3-bromo-l-(2-chlorophenyl)-N-[4-cyano-2-methyl-6-[(methy1amino)carbonyl]- phenyl]-lH-pyrazole-5-carboxamide, 3-bromo-l-(2-chlorophenyl)-7V-[2,4-dichloro-6-[(methylamino)carbonyl]- phenyl]-lH-pyrazole-5-carboxamide,
3-bromo-Λ^[4-chloro-2-[[(cyclopropylmethyl)aπuno]carbonyl]-6-methyl- phenyl]-l-(3-chloro-2-pyridinyl)-lH-pyrazole-5-carboxamide,
3-bromo-l-(3-chloro-2-pyridinyl)-7V-[4-cyano-2-[[(cyclopropylmethyl)amino]- carbonyl]-6-methylphenyl]-lH-pyrazole-5-carboxamide,
3-bromo-/V-[4-chloro-2-[[(l-cyclopropylethyl)amino]carbonyl]-6-methyl- phenyl]-l-(3-chloro-2-pyridinyl)-lH-pyτazole-5-carboxamide,
3-bromo-l-(3-chloro-2-pyridinyl)-/V-[4-cyano-2-[[(l-cyclopropylethyl)amino]- carbonyl]-6-methylphenyl]-lH-pyrazole-5-carboxamide; and iV2-[l,l-dimethyl-2-(methylsulfonyl)ethyl]-3-iodo-N1-[2-methyl-4-[l,2,2,2- tetrafluoro-l-(trifluoromethyl)ethyl]phenyl]-l,2-benzenedicarboxamide.
9. The method of Claim 2 wherein the arthropod pest is a species in one of the orders Coleoptera, Diptera, Ηemiptera, Ηomoptera, Lepidoptera, and Thysanoptera.
10. The method of Claim 2 wherein the arthropod pest is a species of the order Coleoptera.
11. The method of Claim 2 wherein the arthropod pest is a species of the order
Diptera.
12. The method of Claim 2 wherein the arthropod pest is a species of the order Ηemiptera.
13. The method of Claim 2 wherein the arthropod pest is a species of the order Ηomoptera.
14. The method of Claim 2 wherein the arthropod pest is Bemisia argentifolii.
15. The method of Claim 2 wherein the arthropod pest is a species of the order Lepidoptera.
16. The method of Claim 2 wherein the arthropod pest is a species of the order Thysanoptera.
17. The method of Claim 2 wherein the arthropod pest is Thrips palmi.
18. The method of Claim 2 wherein the infectious disease is a plant disease.
19. The method of either of Claims 1 or 2 wherein the carboxamide arthropodicide, its TV-oxide, or a salt thereof, is formulated as a composition comprising the arthropodicide, its TV-oxide, or a salt thereof, and at least one additional component selected from the group consisting of surfactants and liquid diluents.
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