WO2012092115A1 - Mesoionic pyrido [1,2 -a] pyrimidine pesticides - Google Patents

Mesoionic pyrido [1,2 -a] pyrimidine pesticides Download PDF

Info

Publication number
WO2012092115A1
WO2012092115A1 PCT/US2011/066798 US2011066798W WO2012092115A1 WO 2012092115 A1 WO2012092115 A1 WO 2012092115A1 US 2011066798 W US2011066798 W US 2011066798W WO 2012092115 A1 WO2012092115 A1 WO 2012092115A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
oph
phenyl
methyl
pyrido
Prior art date
Application number
PCT/US2011/066798
Other languages
French (fr)
Inventor
Thomas Francis. PAHUTSKI, Jr.
Original Assignee
E. I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to AU2011352379A priority Critical patent/AU2011352379B2/en
Priority to MX2013007494A priority patent/MX358389B/en
Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Priority to SG2013024237A priority patent/SG189206A1/en
Priority to KR1020137019825A priority patent/KR101897840B1/en
Priority to JP2013547567A priority patent/JP5911510B2/en
Priority to UAA201308111A priority patent/UA110953C2/en
Priority to CN201180062994.4A priority patent/CN103459387B/en
Priority to ES11808109.0T priority patent/ES2536305T3/en
Priority to EP11808109.0A priority patent/EP2658856B1/en
Priority to MA36116A priority patent/MA34830B1/en
Priority to RU2013135410/04A priority patent/RU2585616C2/en
Priority to BR112013009935A priority patent/BR112013009935B8/en
Priority to US13/876,636 priority patent/US8895738B2/en
Priority to CA2817902A priority patent/CA2817902A1/en
Publication of WO2012092115A1 publication Critical patent/WO2012092115A1/en
Priority to ZA2013/02430A priority patent/ZA201302430B/en
Priority to TNP2013000152A priority patent/TN2013000152A1/en
Priority to IL225859A priority patent/IL225859A/en
Priority to PH12013501402A priority patent/PH12013501402A1/en
Priority to US14/520,593 priority patent/US20150038329A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/14—Ectoparasiticides, e.g. scabicides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P43/00—Drugs for specific purposes, not provided for in groups A61P1/00-A61P41/00

Definitions

  • This invention relates to certain pyrimidinium compounds, their compositions suitable for agronomic and nonagronomic uses, and methods of their use for controlling invertebrate pests such as arthropods in both agronomic and nonagronomic environments.
  • invertebrate pests The control of invertebrate pests is extremely important in achieving high crop efficiency. Damage by invertebrate pests to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer.
  • the control of invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, turf, wood products, and public health is also 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 sites of action.
  • R 1 is substituted phenyl
  • R 2 is CH 2 Q and Q is an optionally substituted 5- or 6-membered heteroaromatic ring
  • R 3 and R 4 are taken together to form an optionally substituted 6-membered ring.
  • This invention is directed to compounds of Formula 1, compositions containing them and their use for controlling invertebrate pests:
  • R 1 is phenyl or pyridinyl, each optionally substituted with Q and up to 3 substituents independently selected from R 2 ;
  • each R 2 is independently halogen, cyano, SF 5 , C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio or C1-C4 haloalkylthio;
  • Q is phenyl or pyridinyl, each optionally substituted with up to 5 substituents
  • halogen independently selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy.
  • This invention provides a composition comprising a compound of Formula 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • this invention also provides a composition for controlling an invertebrate pest comprising a compound of Formula 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition further comprising at least one additional biologically active compound or agent.
  • This invention also provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula 1 (e.g., as a composition described herein).
  • a biologically effective amount of a compound of Formula 1 e.g., as a composition described herein.
  • This invention also relates to such method wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of Formula 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent.
  • This invention also provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of any of the aforesaid compositions wherein the environment is a plant.
  • This invention also provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of any of the aforesaid compositions wherein the environment is a seed.
  • This invention also provides a method for protecting a seed from an invertebrate pest comprising contacting the seed with a biologically effective amount of a compound of Formula 1 (e.g., as a composition described herein).
  • This invention also relates to the treated seed (i.e. seed contacted with a compound of Formula 1).
  • This invention also provides a method for increasing vigor of a crop plant comprising contacting the crop plant, the seed from which the crop plant is grown or the locus (e.g., growth medium) of the crop plant with a biologically effective amount of a compound of Formula 1 (e.g., as a composition described herein).
  • compositions, mixture, process or method 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 or method.
  • the term “invertebrate pest” includes arthropods, gastropods, nematodes and helminths of economic importance as pests.
  • arthropod includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans.
  • gastropod includes snails, slugs and other Stylommatophora.
  • nematode includes members of the phylum Nematoda, such as phytophagous nematodes and helminth nematodes parasitizing animals.
  • helminth includes all of the parasitic worms, such as roundworms (phylum Nematoda), heartworms (phylum Nematoda, class Secernentea), flukes (phylum Platyhelminthes, class Tematoda), acanthocephalans (phylum Acanthocephala), and tapeworms (phylum Platyhelminthes, class Cestoda).
  • invertebrate pest control means inhibition of invertebrate pest development (including mortality, feeding reduction, and/or mating disruption), and related expressions are defined analogously.
  • agronomic refers to the production of field crops such as for food and fiber and includes the growth of maize or corn, soybeans and other legumes, rice, cereal (e.g., wheat, oats, barley, rye and rice), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers and cucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruit
  • nonagronomic refers to other than field crops, such as horticultural crops
  • turf e.g., sod farm, pasture, golf course, lawn, sports field, etc.
  • wood products stored product, agro-forestry and vegetation management
  • public health i.e. human
  • animal health e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife
  • crop vigor refers to rate of growth or biomass accumulation of a crop plant.
  • vigor refers to an increase in growth or biomass accumulation in a crop plant relative to an untreated control crop plant.
  • crop yield refers to the return on crop material, in terms of both quantity and quality, obtained after harvesting a crop plant.
  • An “increase in crop yield” refers to an increase in crop yield relative to an untreated control crop plant.
  • biologically effective amount refers to the amount of a biologically active compound (e.g., a compound of Formula 1) sufficient to produce the desired biological effect when applied to (i.e. contacted with) an invertebrate pest to be controlled or its environment, or to a plant, the seed from which the plant is grown, or the locus of the plant (e.g., growth medium) to protect the plant from injury by the invertebrate pest or for other desired effect (e.g., increasing plant vigor).
  • a biologically active compound e.g., a compound of Formula 1
  • Nonagronomic applications include protecting an animal from an invertebrate parasitic pest by administering a parasiticidally effective (i.e. biologically effective) amount of a compound of the invention, typically in the form of a composition formulated for veterinary use, to the animal to be protected.
  • a parasiticidally effective (i.e. biologically effective) amount of a compound of the invention typically in the form of a composition formulated for veterinary use, to the animal to be protected.
  • parasiticidal i.e. biologically effective
  • Parasiticidally refers to observable effects on an invertebrate parasite pest to provide protection of an animal from the pest. Parasiticidal effects typically relate to diminishing the occurrence or activity of the target invertebrate parasitic pest.
  • Such effects on the pest include necrosis, death, retarded growth, diminished mobility or lessened ability to remain on or in the host animal, reduced feeding and inhibition of reproduction.
  • These effects on invertebrate parasite pests provide control (including prevention, reduction or elimination) of parasitic infestation or infection of the animal.
  • alkyl used either alone or in compound words such as “haloalkyl” includes straight-chain or branched alkyl, such as methyl, ethyl, n-propyl, /-propyl, or the different butyl isomers.
  • 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", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different.
  • haloalkyl include CF 3 , CH 2 C1, CH2CF3 and CCI2CF3.
  • haloalkoxy and “haloalkylthio” are defined analogously to the term “haloalkyl”. Examples of “haloalkoxy” include CF 3 0, CC1 3 CH 2 0, HCF 2 CH 2 CH 2 0 and CF 3 CH 2 0. Examples of “haloalkylthio” include CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S.
  • Alkoxy includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy and the different butoxy isomers.
  • alkylthio includes straight-chain or branched alkylthio moieties such as methylthio, ethylthio, and the different propylthio and butylthio isomers.
  • C j -Cj The total number of carbon atoms in a substituent group is indicated by the "C j -Cj" prefix where i and j are numbers from 1 to 4.
  • C1-C4 alkyl designates methyl through butyl.
  • radical When a radical is optionally substituted with listed substituents with the number of substituents stated (e.g., "up to 3"), then the radical may be unsubstituted or substituted with a number of substituents ranging up to the high number stated (e.g., "3"), and the attached substituents are independently selected from the substituents listed.
  • the number of optional substituents may be restricted by an expressed limitation.
  • the phrase "optionally substituted with up to 3 substituents independently selected from R 2 " means that 0, 1, 2 or 3 substituents can be present (if the number of potential connection points allows).
  • a range specified for the number of substituents exceeds the number of positions available for substituents on a ring, the actual higher end of the range is recognized to be the number of available positions.
  • the compounds of Formula 1 are mesoionic inner salts.
  • Inner salts also known in the art as “zwitterions”
  • zwitterions are electrically neutral molecules but carry formal positive and negative charges on different atoms in each valence bond structure according to valence bond theory.
  • molecular structure of the compounds of Formula 1 can be represented by the six valence bond structures shown below, each placing the formal positive and negative charges on different atoms. Because of this resonance, the compounds of Formula 1 are also described as "mesoionic".
  • Compounds of this invention can exist as one or more conformational isomers due to restricted bond rotation caused by steric hinderance.
  • a compound of Formula 1 wherein R 1 is phenyl substituted in the ortho-position with a sterically demanding alkyl group e.g., isopropyl
  • This invention comprises mixtures of conformational isomers.
  • this invention includes compounds that are enriched in one conformer relative to others.
  • Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts.
  • Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types).
  • polymorph refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice.
  • polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability.
  • a polymorph of a compound represented by Formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound represented by Formula 1.
  • Preparation and isolation of a particular polymorph of a compound represented by Formula 1 can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures.
  • salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms.
  • the salts of the compounds of Formula 1 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.
  • Embodiments of the present invention as described in the Summary of the Invention include those described below.
  • reference to "a compound of Formula 1" includes the definitions of substituents specified in the Summary of the Invention unless further defined in the Embodiments.
  • Embodiment 1 A compound of Formula 1 wherein R 1 is phenyl optionally substituted with Q and up to 3 substituents independently selected from R 2 .
  • Embodiment la A compound of Embodiment 1 wherein R 1 is phenyl optionally
  • Embodiment 2 A compound of Formula 1 wherein R 1 is pyridinyl optionally substituted with Q and up to 3 substituents independently selected from R 2 .
  • Embodiment 2a A compound of Embodiment 2 wherein R 1 is pyridinyl optionally substituted with up to 3 substituents independently selected from R 2 .
  • Embodiment 3 A compound of Formula 1 or any one of Embodiments l-2a wherein each R 2 is independently halogen, C1 -C4 alkyl, C1 -C4 haloalkyl, C1 -C4 alkoxy or C 1 -C4 haloalkoxy.
  • Embodiment 3 a A compound of Embodiment 3 wherein each R 2 is independently halogen, C 1-C2 alkyl, C 1-C2 haloalkyl, C 1-C2 alkoxy or C1-C2 haloalkoxy.
  • Embodiment 3b A compound of Embodiment 3 wherein each R 2 is independently halogen.
  • Embodiment 3c A compound of Embodiment 3 wherein each R 2 is independently C ⁇ - C 4 alkyl.
  • Embodiment 3d A compound of Embodiment 3 wherein each R 2 is independently C ⁇ - C 4 haloalkyl.
  • Embodiment 3e A compound of Embodiment 3 wherein each R 2 is independently C ⁇ - C4 alkoxy.
  • Embodiment 3f A compound of Embodiment 3 wherein each R 2 is independently C ⁇ - C4 haloalkoxy.
  • Embodiment 4 A compound of Formula 1 or any one of Embodiments 1, 2 and 3-3 f wherein Q is phenyl optionally substituted with up to 5 substituents
  • halogen independently selected from the group consisting of halogen, cyano, C1-C4 alkyl, C 1 -C4 haloalkyl, C1 -C4 alkoxy and C 1 -C4 haloalkoxy.
  • Embodiment 4a A compound of Formula 1 or any one of Embodiments 1, 2 and 3-3 f wherein Q is pyridinyl optionally substituted with up to 4 substituents independently selected from the group consisting of halogen, cyano, C1-C4 alkyl, C 1 -C4 haloalkyl, C1 -C4 alkoxy and C 1 -C4 haloalkoxy.
  • Embodiment 4b A compound of Embodiment 4 wherein Q is phenyl optionally
  • Embodiment 5 A compound of Formula 1 wherein R 1 is phenyl substituted with up to 2 substituents independently selected from the group consisting of halogen, C1 -C4 haloalkyl and C 1 -C4 haloalkoxy.
  • Embodiment 6 A compound of Formula 1 wherein R 1 is phenyl substituted with
  • Embodiment 7 A compound of Formula 1 wherein R 1 is phenyl substituted with C1 -C4 haloalkyl or C1 -C4 haloalkoxy.
  • Embodiments of this invention including Embodiments 1-7 above as well as any other embodiments described herein, can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula 1 but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1.
  • embodiments of this invention, including Embodiments 1-7 above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present invention.
  • Embodiment A A compound of Formula 1 wherein
  • R 1 is phenyl optionally substituted with Q and up to 3 substituents independently
  • Q is phenyl or pyridinyl, each optionally substituted with up to 3 substituents
  • halogen independently selected from the group consisting of halogen, cyano, C1-C4 alkyl, C 1 -C4 haloalkyl, C1 -C4 alkoxy and C 1 -C4 haloalkoxy.
  • Embodiment B A compound of Embodiment A wherein
  • R 1 is phenyl optionally substituted with up to 3 substituents independently selected from the group consisting of halogen, C 1 -C4 alkyl, C 1 -C4 haloalkyl, C1-C4 alkoxy and C 1 -C4 haloalkoxy.
  • Specific embodiments include compounds of Formula 1 selected from the group consisting of:
  • compounds of this invention are characterized by favorable metabolic and/or soil residual patterns and exhibit activity controlling a spectrum of agronomic and nonagronomic invertebrate pests.
  • compositions comprising a compound of any of the preceding Embodiments, as well as any other embodiments described herein, and any combinations thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said compositions optionally further comprising at least one additional biologically active compound or agent.
  • compositions for controlling an invertebrate pest comprising a compound (i.e. in a biologically effective amount) of any of the preceding Embodiments, as well as any other embodiments described herein, and any combinations thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said compositions optionally further comprising at least one additional biologically active compound or agent (i.e. in a biologically effective amount).
  • Embodiments of the invention also include a composition comprising a compound of any of the preceding Embodiments in the form of a soil drench liquid formulation.
  • Embodiments of the invention further include methods for controlling an invertebrate pest comprising contacting the soil with a liquid composition as a soil drench comprising a biologically effective amount of a compound of any of the preceding Embodiments.
  • Embodiments of the invention also include a spray composition for controlling an invertebrate pest comprising a compound (i.e. in a biologically effective amount) of any of the preceding Embodiments and a propellant.
  • Embodiments of the invention further include a bait composition for controlling an invertebrate pest comprising a compound (i.e. in a biologically effective amount) of any of the preceding Embodiments, one or more food materials, optionally an attractant, and optionally a humectant.
  • Embodiments of the invention also include a device for controlling an invertebrate pest comprising said bait composition and a housing adapted to receive said bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to said 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 invertebrate pest.
  • Embodiments of the invention also include methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula 1 (e.g., as a composition described herein), provided that the methods are not methods of medical treatment of a human or animal body by therapy.
  • a biologically effective amount of a compound of Formula 1 e.g., as a composition described herein
  • This invention also relates to such methods wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of Formula 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent, provided that the methods are not methods of medical treatment of a human or animal body by therapy.
  • a composition comprising a biologically effective amount of a compound of Formula 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent, provided that the methods are not methods of medical treatment of a human or animal body by therapy.
  • Embodiments of the invention also include any of the preceding embodiments wherein the invertebrate pest is an arthropod.
  • Embodiments of the invention also include any of the preceding embodiments wherein the arthropod is selected from the group consisting of insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans.
  • Embodiments of the invention also include any of the preceding embodiments wherein the arthropod is an insect.
  • Embodiments of the invention also include any of the preceding embodiments wherein the insect is in the order Hemiptera.
  • Embodiments of the invention also include any of the preceding embodiments wherein the insect is a planthopper.
  • Embodiments of the invention also include any of the preceding embodiments wherein the insect is a planthopper in the family Delphacidae.
  • Embodiments of the invention also include any of the preceding embodiments wherein the insect is a leafhopper.
  • Embodiments of the invention also include any of the preceding embodiments wherein the insect is a leafhopper in the family Cicadellida
  • Embodiments of the invention also include any of the preceding embodiments wherein the invertebrate pest is a gastropod.
  • Embodiments of the invention also include any of the preceding embodiments wherein the gastropod is selected from the group consisting of snails, slugs and other Stylommatophora.
  • Embodiments of the invention also include any of the preceding embodiments wherein the invertebrate pest is a nematode.
  • Embodiments of the invention also include any of the preceding embodiments wherein the nematode is selected from phytophagous nematodes.
  • Embodiments of the invention also include any of the preceding embodiments wherein the invertebrate pest is a helminth.
  • Embodiments of the invention also include any of the preceding embodiments wherein the helminth is selected from the group consisting of roundworms, heartworms, flukes, acanthocephalans and tapeworms.
  • Embodiments of the invention also include embodiments pertaining to the method for increasing vigor of a crop plant disclosed in the Summary of the Invention wherein the compound of Formula 1 (e.g., as a composition described herein) is selected from any one of Embodiments 1— 4b, A and B, and compounds specifically disclosed herein.
  • the compound of Formula 1 e.g., as a composition described herein
  • the compound of Formula 1 is selected from any one of Embodiments 1— 4b, A and B, and compounds specifically disclosed herein.
  • Compounds of Formula 1 can be prepared by condensation of the compound of
  • Condensing agents can be carbodiimides such as dicyclohexyl carbodiimide (see, for example, Koch, A. et al. Tetrahedron 2004, 60, 10011- 10018) or other agents well known in the art to form amide bonds with or without activating agents such as N-hydroxybenzotriazole as described in Science of Synthesis 2005, 21, 17-25 and Tetrahedron 2005, 61, 10827-10852.
  • This reaction is typically carried out in an inert organic solvent, such as dichloromethane or 1 ,2-dichloroethane, at temperatures from about 0 to about 80 °C for a period of 10 min to several days.
  • Compounds of Formula 1 can also be prepared by the condensation of the compound of Formula 2 with malonic acid esters of Formula 3b wherein R is a C 1 -C5 alkyl group as shown in Scheme 2. These reactions can be performed neat or in the presence of inert solvents as described in Bulletin of the Chemical Society of Japan 1999, 72(3), 503-509. Inert solvents include, but are not limited to, high boiling hydrocarbons such as mesitylene, tetralin or cymene, or high boiling ethers such as diphenyl ether. Typical temperatures range from 50 to 250 °C. Of note are temperatures from 150 to 200 °C, which typically provide rapid reaction times and high yields. These reactions can also be performed in microwave reactors within the same temperature ranges. Typical reaction times range from 5 minutes to several hours.
  • Compounds of Formula 3a can be prepared by a variety of methods known in the art, for example by base hydrolysis of compounds of Formula 3b.
  • Compounds of Formula 3b can be prepared by arylation of malonate esters (using compounds of formula RiX 1 wherein X 1 is CI, Br or I, examples of which are found in Tables I-24a, I-24-b and I-24c) catalyzed by palladium (J. Org. Chem 2002, 67, 541-555) or copper (Org. Lett. 2002, 4, 269-272 and Org. Lett. 2005, 7, 4693-4695).
  • compounds of Formula 3b can be prepared by the method shown in Scheme 2a (see, for example, J. Med. Chem 1982, 25(6), 745-747).
  • Esters of Formula 4 can be prepared from the corresponding acids by methods well known in the art.
  • the acids of Formula 4 wherein R is H (examples are listed in Table I-l) are readily prepared by methods known in the art, and many are commercially available.
  • Compounds of Formula 3b can also be prepared by the method shown in Scheme 2b. Reaction of nitriles of Formula 3g with dialkyl carbonates yields nitrile esters of Formula 3h, and subsequent acidic hydrolysis in the presence of an alcohol provides the compounds of Formula 3b (see, for example, Helvetica Chimica Acta 1991, 74(2), 309-314).
  • the nitriles of Formula 3g are readily prepared by methods known in the art, and many are commercially available.
  • R is C -C5 alkyl
  • Compounds of Formula 1 can also be prepared by treatment of the compound of Formula 2 with activated esters of Formula 3c wherein LvO is an activated leaving group as shown in Scheme 3.
  • LvO is an activated leaving group as shown in Scheme 3.
  • Lv preferred for ease of synthesis or reactivity are phenyl, 4-nitrophenyl or halogen-substituted phenyl (e.g., 2,4,6-trichlorophenyl, pentachlorophenyl or pentafluorophenyl) as described in Archiv der Pharmazie (Weinheim, Germany) 1991, 324, 863-866.
  • Other activated esters are well known in the art and include, but are not limited to, N-hydroxysuccinimide esters (see, for example, J. Am. Chem. Soc.
  • Typical temperatures range from 50 to 200 °C. Of note are temperatures from 50 to 150 °C, which typically provide rapid reaction times and high yields. These reactions can be performed with or without solvent, such as toluene, and in microwave reactors within the same temperature ranges. Typical reaction times range from 5 minutes to 2 hours.
  • Compounds of the Formula 3c can be prepared, for example, from compounds of Formula 3a (see, for example, J. Het. Chem. 1980, 17, 337).
  • Compounds of Formula 1 can also be prepared by condensation of the compound of Formula 2 with compounds of Formula 3d or 3e, or by condensation of the compound of Formula 2 with mixtures of compounds of Formulae 3d and 3e as shown in Scheme 4. These reactions are typically performed in an inert solvent, such as dichloromethane, and optionally in the presence of two or more equivalents of an acid acceptor (see, for example, Zeitschrift fur Naturforschung, Mol B: Anorganische Chemie, Organische Chemie 1982, 37B(2), 222-233).
  • Typical acid acceptors include, but are not limited to, triethylamine, N,N-diisopropylethylamine, pyridine and substituted pyridines, and metal hydroxides, carbonates and bicarbonates.
  • Compounds of Formula la can be prepared by condensation of the compound of Formula 2 with carbon suboxide (3f) (see, for example, J. Org. Chem. 1972, 37(9), 1422- 1425) as shown in Scheme 5.
  • the reactions are typically performed in an inert solvent such as ether and can include the use of a catalyst such as AICI3.
  • Scheme 5
  • Compounds of Formula 1 can be prepared from compounds of Formula lb and compounds of Formula 5 wherein M with R 1 forms a boronic acid, boronic acid ester or trifluoroborate salt, or M is trialkylstannyl or zinc, as shown in Scheme 6.
  • compounds of Formula 1 wherein R 1 consists of two directly bonded aromatic rings can be prepared by palladium-catalyzed coupling of the two appropriately substituted aromatic rings.
  • These palladium-catalyzed couplings between an aromatic chloride, bromide or iodide and an aromatic boronic acid or ester, or an aromatic tin or zinc reagent are well known and have been extensively described in the art.
  • Scheme 6a wherein a compound of Formula 13a or 13b is coupled with an appropriately substituted phenyl ring to provide the biphenyl compound of Formula 13c.
  • M is as defined above for Scheme 6.
  • R a is C0 2 R, and R b is C0 2 R, CN or H; or
  • R a is CN, and R b is H;
  • R is Ci-C 5 alkyl
  • the coupling reactions are typically carried out in the presence of a palladium catalyst and a base optionally under an inert atmosphere.
  • the palladium catalysts used for these coupling reactions typically comprises palladium in a formal oxidation state of either 0 (i.e. Pd(0)) or 2 (i.e. Pd(II)).
  • Pd(0) i.e. Pd(0)
  • Pd(II) i.e. Pd(II)
  • Examples of palladium-containing compounds and complexes useful as catalysts in the methods include PdCl2(PPh 3 )2 (bis(triphenylphosphine)palladium (II) dichloride), Pd(PPh 3 ) 4 (tetrakis(triphenylphosphine)- palladium(O)), Pd ⁇ HyC ⁇ (palladium(II) acetylacetonate), Pd2(dba) 3 (tris(dibenzylidene- acetone)dipalladium(O)), and [1,1 '-bis(diphenylphosphino)ferrocene]dichloropalladium(II).
  • PdCl2(PPh 3 )2 bis(triphenylphosphine)palladium (II) dichloride
  • Pd(PPh 3 ) 4 tetrakis(triphenylphosphine)- palladium(O)
  • the palladium catalyst preferably has good solubility in the liquid phase.
  • Useful solvents include, for example, water, ethers such as 1 ,2-dimethoxyethane, amides such as N,N-dimethylacetamide, and non-halogenated aromatic hydrocarbons such as toluene.
  • the coupling methods can be conducted over a wide range of temperatures, ranging from about 25 to about 200 °C. Of note are temperatures from about 60 to about 150 °C, which typically provide fast reaction times and high product yields.
  • the general methods and procedures for Stille, Negishi and Suzuki couplings with aryl iodides, bromides or chlorides and an aryl tin, aryl zinc or aryl boronic acid respectively are well known in the literature; see, for example, E. Negishi, Handbook of Organopalladium Chemistry for Organic Synthesis, Wiley-Interscience, 2002, New York, New York.
  • Compounds of Formula 1 can be prepared from compounds of Formula la (i.e. Formula 1 wherein R 1 is H) and compounds of Formula 6 wherein X 1 is CI, Br or I (preferably Br or I) as shown in Scheme 7.
  • the copper catalysts used for the present method typically comprise copper in metallic form (e.g., as a powder) or copper in a formal oxidation state of 1 (i.e. Cu(I)).
  • copper-containing compounds useful as catalysts in the method of Scheme 7 include Cu, Cul, CuBr, CuCl.
  • palladium- containing compounds useful as catalysts in the method of Scheme 7 include Pd(OAc)2-
  • Useful solvents for the method of Scheme 7 include, for example, ethers such as 1,4- dioxane, amides such as N,N-dimethylacetamide and dimethyl sulfoxide.
  • the method of Scheme 7 can be conducted over a wide range of temperatures from 25 to 200 °C. Of note are temperatures from 40 to 150 °C.
  • the method of Scheme 7 can be conducted in the presence of a ligand.
  • a wide variety of copper-binding compounds are useful as ligands for the present method. Examples of useful ligands include, but are not limited to, 1,10-phenanthroline, N,N-dimethylethylenediamine, L-proline and 2-picolinic acid.
  • the general methods and procedures for copper-catalyzed Ullmann-type coupling reactions are well known in the literature; see, for example, Xie, Ma, et al. Org. Lett. 2005, 7, 4693-4695.
  • Compounds of Formula lb can be prepared from compounds of Formula la by halogenation using, for example, liquid bromine or N-halosuccinimides of Formula 10 as shown in Scheme 11.
  • the reaction is performed in an inert solvent, more typically a halogenated solvent such as methylene chloride or 1,2-dichloroethane.
  • the reaction is typically performed at temperatures from 0 to 80 °C, more typically at ambient temperature.
  • Compounds of Formula 1 can also be prepared by alkylation of compounds of Formula 11 using appropriately substituted alkylating agents and bases such as potassium carbonate as shown in Scheme 12 (see, for example, Kappe, T. et al. Monatschefte fur Chemie 1971, 102, 412-424 and Urban, M. G.; Arnold,W. Helvetica Chimica Acta 1970, 53, 905-922).
  • Alkylating agents include, but are not limited to, alkyl chlorides, bromides, iodides and sulfonate esters.
  • bases and solvents can be employed in the method of Scheme 12, and these bases and solvents are well known in the art.
  • Compounds of Formula 11 can be prepared from 2-aminopyridine by methods analogous to those shown in Schemes 1 through 5.
  • the compound of Formula 2 is an important intermediate useful in the preparation of compounds of Formula 1.
  • the compound of Formula 2 is an embodiment of the present invention.
  • a further embodiment of the present invention is the use of the compound of Formula 2 in the preparation of compounds of Formula 1.
  • the compound of Formula 2 can also be used as its acid-addition salt (e.g., hydrochloric salt or acetic acid salt) in the coupling methods of Schemes 1-5.
  • acid-addition salt e.g., hydrochloric salt or acetic acid salt
  • a particularly useful method for the preparation of the compound of Formula 2 is shown in Scheme 13.
  • 2-aminopyridine (2a) is protected with suitable protecting groups such as, but not limited to, tert-butoxycarbonyl, acetyl or formyl to form the intermediate of Formula 2b wherein PG is a protecting group.
  • the compound of Formula 2b is then alkylated with a compound of Formula 12 (wherein X is a leaving group such as a halogen) to give an intermediate of Formula 2c.
  • the protecting group is removed to provide the compound of Formula 2.
  • Conditions for the formation and removal of protecting groups on an amine function are known in the literature (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991).
  • Another alternative method for the preparation of the compound of Formula 2 is by the reaction of an appropriate amine with the halogen-substituted compound analogous to the compound of Formula 2a (i.e. Formula 2a wherein the amino group is replaced with halogen) in the presence of a copper or palladium catalyst.
  • Table 1-2 is identical to Table I-l, except that R x is C(0)OMe.
  • Table 1-3 is identical to Table I-l, except that R x is C(0)OEt.
  • Table 1-4 is identical to Table I-l, except that R x is C(0)OPh.
  • Table 1-5 is identical to Table I-l, except that R x is C(0)OC(CH 3 ) 3 .
  • Table 1-6 is identical to Table I-l, except that R x is C(0)0(2,4,6-trichlorophenyl).
  • Table 1-7 is identical to Table I-l, except that R x is C(0)0(4-nitrophenyl).
  • Table 1-8 is identical to Table I-l, except that R x is C(0)OH and RY is C(0)OH.
  • Table I- 10 is constructed the same as Table I-l, except that R x is C(0)OH and RY is C(0)OEt.
  • Table I-l 1 identical to Table I-l, except that R x is C(0)OH and RY is C(0)OC(CH 3 ) 3 .
  • Table I- 15 is identical to Table I- 1 , except that R x is C(0)OPh and RY is C(0)OMe.
  • Table 1-16 is identical to Table I-l, except that R x is C(0)OPh and RY is C(0)OEt. TABLE 1-17
  • Table 1-17 is identical to Table I-l, except that R x is C(0)OPh and RY is C(0)OC(CH 3 ) 3 .
  • Table 1-18 is identical to Table I-l, except that R x is C(0)OPh and RY is C(0)OPh.
  • Table 1-19 is identical to Table I-l, except that R x is C(0)OPh and RY is C(0)0(2,4,6- trichloropheny 1) .
  • Table 1-20 is identical to Table I-l, except that R x is C(0)OPh and RY is C(0)0(4- nitrophenyl).
  • Table 1-21 is identical to Table I-l, except that R x is C(0)C1 and RY is C(0)C1.
  • Table 1-22 is identical to Table I-l, except that R x is C(0)OMe and RY is C(0)OMe.
  • Table 1-23 is identical to Table I-l, except that R x is C(0)OEt and RY is C(0)OEt.
  • Table 1-24 is identical to Table I-l, except that R x is C(0)OC(CH 3 ) 3 and RY is C(0)OC(CH 3 ) 3 .
  • Table 1-25 is identical to Table I-l, except that R x is C(0)0(2,4,6-trichlorophenyl) and RY is C(0)0(2,4,6-trichlorophenyl).
  • Table 1-26 is identical to Table I-l, except that R x is C(0)0(4-nitrophenyl) and RY is C(0)0(4-nitrophenyl).
  • Table 1-27 is identical to Table I-l, except that R x is C(0)(3-methyl-2-pyridinylamino) and RY is C(0)OH.
  • Table 1-28 is identical to Table I-l, except that R x is C(0)(3-methyl-2-pyridinylamino) and RY is C(0)OMe.
  • Table 1-29 is identical to Table I-l, except that R x is C(0)(3-methyl-2-pyridinylamino) and RY is C(0)OEt. TABLE 1-30
  • Table 1-30 is identical to Table I-l, except that R x is C(0)(3-methyl-2-pyridinylamino) and RY is C(0)OPh.
  • Table 1-31 is identical to Table I-l, except that R x is C(0)(3-methyl-2-pyridinylamino) and Ry is C(0)0(2,4,6-trichlorophenyl).
  • Table 1-32 is identical to Table I-l, except that R x is C(0)(3-methyl-2-pyridinylamino) and Ry is C(0)0(4-nitrophenyl).
  • Table 1-33 is identical to Table I-l, except that R x is C(0)(3-methyl-2-pyridinylamino) and Ry is C(0)OC(CH 3 ) 3 .
  • Table 1-34 is identical to Table I-l, except that the chemical structure under the Table I-l heading is replaced with the following structure, and R is CI.
  • the groups R x and Ry found in Table I-l are not relevant to Table 1-34, as the CH(R x )(Ry) moiety in the structure of Table I-l is replaced with a R group in the structure of Table 1-34.
  • the first compound in Table 1-34 is the structure shown immediately above wherein R a , R b , R c , R d and R e are H, and R is CI.
  • Table 1-35 is identical to Table 1-34, except that R is Br.
  • Table 1-36 is identical to Table 1-34, except that R is I.
  • Table 1-37 is identical to Table 1-34, except that R is CH 2 OH.
  • Table 1-38 is identical to Table 1-34, except that R is CH 2 CN.
  • Table 1-39 is identical to Table 1-34, except that R is CH 2 C1. TABLE 1-40
  • Table 1-40 is identical to Table 1-34, except that R is CH(CN)C0 2 Me.
  • Table 1-41 is identical to Table 1-34, except that R is CH(CN)C0 2 Et.
  • R is CF 3
  • R is H
  • R is Br
  • R is l
  • R is NH 2
  • R is 2-cmoro-4-(trifluoromethyl)phenyl
  • R is 2-chloro-4-cyanophenyl
  • R is H
  • R is CF 3
  • R is F
  • R is CI
  • R is Br
  • R is l
  • R is NH 2
  • R is 2-chloro-4-(trifluoromethyl)phenyl
  • Step B Preparation of N- [(5 -pyrimidinyl)methyl] -2-pyridinamine
  • reaction progress was monitored by thin layer chromatography eluting with a 10% methanol:40% dichloromethane:50% toluene solvent.
  • acetic acid (3 mL) was added dropwise, and the reaction mixture was stirred for 5 minutes.
  • Acetic acid (2 mL) and water (30 mL) were added, the reaction mixture was briefly stirred, and then ethyl acetate was added (500 mL).
  • the reaction mixture was washed with 1 N aqueous sodium hydroxide solution (300 mL), dried over magnesium sulfate, filtered, and the solvent was removed under reduced pressure at 50 °C.
  • Step C Preparation of 1 ,3-dimethyl 2-[3-(trifluoromethyl)phenyl]propanedioate
  • Dioxane 100 mL was purged with nitrogen gas for 10 minutes. Phenanthrolene (1.0 g) and copper (I) iodide (1.0 g) were added to the dioxane, the suspension was allowed to stir under a nitrogen atmosphere for 5 minutes, and then cesium carbonate (18.72 g, 57.45 mmol), dimethyl malonate (5.46 g, 50.6 mmol), and l-iodo-3-(trifluoromethyl)benzene (12.5 g, 46.0 mmol) were added. The reaction mixture was heated to reflux for 18 hours and then cooled to room temperature.
  • Step C The product of Step C was added to a solution of NaOH (25 g) in water (75 mL), and the reaction mixture was vigorously stirred under a nitrogen atmosphere at 60 °C for 8 minutes. The reaction mixture was then added to ice (100 g), and aqueous 6 N HC1 was added until a pH of 1 was reached. The solution was extracted with ethyl acetate (3 x 100 mL), and the combined organic extracts were dried over magnesium sulfate, filtered, and concentrated under reduced pressure. Dichloromethane (200 mL) was added to the resulting white solid, followed by the addition of oxalyl chloride (5 mL) and N,N-dimethylformamide (0.5 mL).
  • Step E Preparation of 2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-3 - [3 -
  • Step D To the product of Step D (8.16 g, 13.4 mmol) in toluene (100 mL) was added the product of Step B (3.31 g, 17.8 mmol). The reaction mixture was heated to 110 °C for 6 hours, during which time a yellow solid precipitated out of solution. The reaction mixture was concentrated in the presence of Celite®, and the crude product adsorbed onto Celite® was purified by silica gel chromatography eluting with a gradient of 100% ethyl acetate to 25% methanol in ethyl acetate to yield 7.36 g (58.0%>) of the title product, a compound of this invention.
  • Step A Preparation of 1 ,3-bis(l , 1 -dimethylethyl) 2-(3-iodo-5- methylphenyl)propanedioate
  • reaction mixture was then cooled to room temperature, quenched with saturated aqueous ammonium chloride solution (50 mL), and extracted twice with diethyl ether (50 mL). The organic layers were combined, dried over MgSC ⁇ , and concentrated under reduced pressure. The resulting residue was purified by chromatography on silica gel eluted with ethyl acetate in hexanes to provide the title product as an orange oil (0.62 g).
  • Step B Preparation 1, 3 -bis( 1,1 -dimethylethyl) 2-(4'-cyano-5,2'-dimethyl[l,l'- biphenyl] -3 -yl)propanedioate
  • reaction mixture was then cooled to room temperature, and filtered through a plug of silica gel eluting with 20% ethyl acetate in hexanes. Concentration of the eluant under reduced pressure provided a brown oil (430 mg) containing the crude product, which was used in the next step without further purification.
  • Step C Preparation of 3-(4'-cyano-5,2'-dimethyl[l, -biphenyl]-3-yl)-2-hydroxy-4- oxo- 1 -(5-pyrimidinylmethyl)-4H-pyrido[ 1 ,2-a]pyrimidinium inner salt
  • a mixture of N-[(5-pyrimidinyl)methyl]-2-pyridinamine (65 mg, 0.34 mmol) and l,3-bis(l,l-dimethylethyl) 2-(4'-cyano-5,2'-dimethyl[l, -biphenyl]-3-yl)propanedioate the product of Step B, 120 mg, 0.28 mmol) in /?-cymene (2 mL) and 1,2,3,4- tetrahydronaphthalene (i.e.
  • R b , R c , R d and R e are H
  • R a , R b , R d and R e are H
  • R a is OMe; R b , R c and R e are H
  • R b is Br; R a , R c and R e are H
  • R b is OMe; R a , R c and R e are H
  • R a and R e are F; R c and R d are H
  • formulation with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serves as a carrier.
  • additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serves as a carrier.
  • the formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
  • Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like, which optionally can be thickened into gels.
  • aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion and suspo-emulsion.
  • nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.
  • compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, which can be water-dispersible ("wettable") or water-soluble. Films and coatings formed from film- forming solutions or flowable suspensions are particularly useful for seed treatment.
  • Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated”). Encapsulation can control or delay release of the active ingredient.
  • An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.
  • Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water. Spray volumes can range from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into the furrow during planting. Liquid and solid formulations can be applied onto seeds of crops and other desirable vegetation as seed treatments before planting to protect developing roots and other subterranean plant parts and/or foliage through systemic uptake.
  • 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.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate.
  • Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.
  • Liquid diluents include, for example, water, N,N-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, triacetin, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl
  • Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C 6 -C 2 2), such as plant seed and fruit oils (e.g, oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof.
  • plant seed and fruit oils e.g, oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel
  • animal-sourced fats e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil
  • Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids can be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation.
  • alkylated fatty acids e.g., methylated, ethylated, butylated
  • Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
  • the solid and liquid compositions of the present invention often include one or more surfactants.
  • surfactants also known as “surface-active agents”
  • surface-active agents generally modify, most often reduce, the surface tension of the liquid.
  • surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.
  • Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which are branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide
  • Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of e
  • Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.
  • amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amine
  • Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon 's Emulsifiers and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.
  • compositions of this invention can also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which can be considered to also function as solid diluents, liquid diluents or surfactants).
  • formulation auxiliaries and additives can control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes.
  • Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes.
  • formulation auxiliaries and additives include those listed in McCutcheon 's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222.
  • the compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent.
  • Solutions, including emulsifiable concentrates can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water.
  • Active ingredient slurries, with particle diameters of up to 2,000 ⁇ can be wet milled using media mills to obtain particles with average diameters below 3 ⁇ .
  • Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 um range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques.
  • Pellets can be prepared as described in U.S. 4,172,714.
  • Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493.
  • Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030.
  • Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
  • Attapulgite granules low volatile matter, 0.71/0.30 U.S.S. No. 25-50 sieves
  • compound 7 20.00% polyvinylpyrrolidone -vinyl acetate copolymer 5.00% montan acid wax 5.00% calcium ligninsulfonate 1.00% polyoxyethylene/polyoxypropylene block copolymers 1.00% stearyl alcohol (POE 20) 2.00% polyorganosilane 0.20%> colorant red dye 0.05%> water 65.75%
  • compound 10 10.0% butyl polyoxyethylene/polypropylene block copolymer 4.0%> stearic acid/polyethylene glycol copolymer 1.0%) styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1%
  • compound 12 10.0% imidacloprid 5.0% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1%
  • invertebrate pests include invertebrates inhabiting a variety of environments such as, for example, plant foliage, roots, soil, harvested crops or other foodstuffs, building structures or animal integuments.
  • These pests include, for example, invertebrates feeding on foliage (including leaves, stems, flowers and fruits), seeds, wood, textile fibers or animal blood or tissues, and thereby causing injury or damage to, for example, growing or stored agronomic crops, forests, greenhouse crops, ornamentals, nursery crops, stored foodstuffs or fiber products, or houses or other structures or their contents, or being harmful to animal health or public health.
  • traits include tolerance to herbicides, resistance to phytophagous pests (e.g., insects, mites, aphids, spiders, nematodes, snails, plant-pathogenic fungi, bacteria and viruses), improved plant growth, increased tolerance of adverse growing conditions such as high or low temperatures, low or high soil moisture, and high salinity, increased flowering or fruiting, greater harvest yields, more rapid maturation, higher quality and/or nutritional value of the harvested product, or improved storage or process properties of the harvested products.
  • Transgenic plants can be modified to express multiple traits.
  • plants containing traits provided by genetic engineering or mutagenesis include varieties of corn, cotton, soybean and potato expressing an insecticidal Bacillus thuringiensis toxin such as YIELD GARD ® , KNOCKOUT ® , STARLINK ® , BOLLGARD ® , NuCOTN ® and NEWLEAF ® , and herbicide-tolerant varieties of corn, cotton, soybean and rapeseed such as ROUNDUP READY ® , LIBERTY LINK ® ,
  • the present compounds and compositions may interact synergistically with traits introduced by genetic engineering or modified by mutagenesis, thus enhancing phenotypic expression or effectiveness of the traits or increasing the invertebrate pest control effectiveness of the present compounds and compositions.
  • the present compounds and compositions may interact synergistically with the phenotypic expression of proteins or other natural products toxic to invertebrate pests to provide greater-than-additive control of these pests.
  • the present compounds and compositions may interact synergistically with traits improving plant growth or other aspects of crop vigor, including traits conferring resistance to environmental stress such as suboptimal moisture.
  • compositions of this invention can also optionally comprise plant nutrients, e.g., a fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium, magnesium, iron, copper, boron, manganese, zinc, and molybdenum.
  • a fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium, magnesium, iron, copper, boron, manganese, zinc, and molybdenum.
  • compositions comprising at least one fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium and magnesium.
  • Compositions of the present invention which further comprise at least one plant nutrient can be in the form of liquids or solids.
  • Solid formulations comprising a fertilizer composition can be prepared by mixing the compound or composition of the present invention with the fertilizer composition together with formulating ingredients and then preparing the formulation by methods such as granulation or extrusion.
  • solid formulations can be prepared by spraying a solution or suspension of a compound or composition of the present invention in a volatile solvent onto a previous prepared fertilizer composition in the form of dimensionally stable mixtures, e.g., granules, small sticks or tablets, and then evaporating the solvent.
  • agronomic or nonagronomic invertebrate pests include eggs, larvae and adults of the order Lepidoptera, such as armyworms, cutworms, loopers, and heliothines in the family Noctuidae (e.g., pink stem borer (Sesamia inferens Walker), corn stalk borer (Sesamia nonagrioides Lefebvre), southern armyworm (Spodoptera eridania Cramer), fall armyworm (Spodoptera fugiperda J. E.
  • Noctuidae e.g., pink stem borer (Sesamia inferens Walker), corn stalk borer (Sesamia nonagrioides Lefebvre), southern armyworm (Spodoptera eridania Cramer), fall armyworm (Spodoptera fugiperda J. E.
  • agronomic and nonagronomic pests include: eggs, adults and larvae of the order Dermaptera including earwigs from the family Forficulidae (e.g., European earwig (Forficula auricularia Linnaeus), black earwig (Chelisoches morio Fabricius)); eggs, immatures, adults and nymphs of the orders Hemiptera and Homoptera such as, plant bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g.
  • Agronomic and nonagronomic pests also include: eggs, larvae, nymphs and adults of the order Acari (mites) such as spider mites and red mites in the family Tetranychidae (e.g., European red mite ⁇ Panonychus ulmi Koch), two spotted spider mite (Tetranychus urticae Koch), McDaniel mite ⁇ Tetranychus mcdanieli McGregor)); flat mites in the family Tenuipalpidae (e.g., citrus flat mite (Brevipalpus lewisi McGregor)); rust and bud mites in the family Eriophyidae and other foliar feeding mites and mites important in human and animal health, i.e.
  • Tetranychidae e.g., European red mite ⁇ Panonychus ulmi Koch), two spotted spider mite (Tetranychus urticae Koch
  • serpentine vegetable leafminer ⁇ Liriomyza sativae Blanchard
  • midges fruit flies
  • frit flies e.g., Oscinella frit Linnaeus
  • soil maggots e.g., house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g., Fannia canicularis Linnaeus, F.
  • femoralis Stein stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g., Chrysomya spp., Phormia spp.), and other muscoid fly pests, horse flies (e.g., Tabanus spp.), bot flies (e.g., Gastrophilus spp., Oestrus spp.), cattle grubs (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.), keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g., Prosimulium spp., Simulium s
  • Hymenoptera including bees (including carpenter bees), hornets, yellow jackets, wasps, and sawflies (Neodiprion spp.; Cephus spp.); insect pests of the order Isoptera including termites in the Termitidae (e.g., Macrotermes sp., Odontotermes obesus Rambur), Kalotermitidae (e.g., Cryptotermes sp.), and Rhinotermitidae (e.g., Reticulitermes sp., Coptotermes sp., Heterotermes tenuis Hagen) families, the eastern subterranean termite (Reticulitermes flavipes Kollar), western subterranean termite (Reticulitermes hesperus Banks), Formosan subterranean termite (Coptotermes formosanus Shiraki), West Indian drywood termite (Incisitermes immigrans
  • insect pests of the order Thysanura such as silverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobia domestica Packard); insect pests of the order Mallophaga and including the head louse (Pediculus humanus capitis De Geer), body louse (Pediculus humanus Linnaeus), chicken body louse (Menacanthus stramineus Nitszch), dog biting louse (Trichodectes canis De Geer), fluff louse (Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank), short-nosed cattle louse (Haematopinus eurysternus Nitzsch), long-nosed cattle louse (Linognathus vituli Linnaeus) and other sucking and chewing parasitic lice that attack man and animals; insect pests of the order Siphonoptera including the oriental rat fle
  • Additional arthropod pests covered include: spiders in the order Araneae such as the brown recluse spider (Loxosceles reclusa Gertsch & Mulaik) and the black widow spider (Latrodectus mactans Fabricius), and centipedes in the order Scutigeromorpha such as the house centipede (Scutigera coleoptrata Linnaeus).
  • spiders in the order Araneae such as the brown recluse spider (Loxosceles reclusa Gertsch & Mulaik) and the black widow spider (Latrodectus mactans Fabricius)
  • centipedes in the order Scutigeromorpha such as the house centipede (Scutigera coleoptrata Linnaeus).
  • invertebrate pests of stored grain include larger grain borer (Prostephanus truncatus), lesser grain borer (Rhyzopertha dominica), rice weevil (Stiophilus oryzae), maize weevil (Stiophilus zeamais), cowpea weevil (Callosobruchus maculatus), red flour beetle (Tribolium castaneum), granary weevil (Stiophilus granarius), Indian meal moth (Plodia interpunctella), Mediterranean flour beetle (Ephestia kuhniella) and fiat or rusty grain beetle (Cryptolestis ferrugineus).
  • Compounds of the invention show particularly high activity against pests in the order Lepidoptera (e.g., Alabama argillacea Hiibner (cotton leaf worm), Archips argyrospila Walker (fruit tree leaf roller), A. rosana Linnaeus (European leaf roller) and other Archips species, Chilo suppressalis Walker (rice stem borer), Cnaphalocrosis medinalis Guenee (rice leaf roller), Crambus caliginosellus Clemens (corn root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Earias insulana Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoverpa armigera Hiibner (American bollworm), Helicoverpa zea Boddie (corn earworm), Heliothis virescens Fabricius (tobacco bud
  • Compounds of the invention also have significant activity on members from the order Homoptera including: Acyrthosiphon pisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer (apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solani Kaltenbach (foxglove aphid), Chaetosiphon fragaefolii Cockerell (strawberry aphid), Diuraphis noxia Kurdjumov/Mordvilko (Russian wheat aphid), Dysaphis plantaginea Paaserini (rosy apple aphid), Eriosoma lanigerum Hausmann (woolly apple aphid), Hyalopter
  • Compounds of this invention may also have activity on members from the order Hemiptera including: Acrosternum hilare Say (green stink bug), Anasa tristis De Geer (squash bug), Blissus leucopterus leucopterus Say (chinch bug), Cimex lectularius Linnaeus (bed bug) Corythuca gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-Schaffer (cotton stainer), Euchistus servus Say (brown stink bug), Euchistus variolarius Palisot de Beauvois (one-spotted stink bug), Graptosthetus spp.
  • Thysanoptera e.g., Frankliniella occidentalis Pergande (western flower thrips), Scirthothrips citri Moulton (citrus thrips), Sericothrips variabilis Beach (soybean thrips), and Thrips tabaci Lindeman (onion thrips); and the order Coleoptera (e.g., Leptinotarsa decemlineata Say (Colorado potato beetle), Epilachna varivestis Mulsant (Mexican bean beetle) and wireworms of the genera Agriotes, Athous or Limonius).
  • Thysanoptera e.g., Frankliniella occidentalis Pergande (western flower thrips), Scirthothrips citri Moulton (citrus thrips), Sericothrips variabilis Beach (soybean thrips), and Thrips tabaci Lindeman (onion thrips); and
  • Nematoda, Cestoda, Trematoda, and Acanthocephala including economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida such as but not limited to economically important agricultural pests (i.e. root knot nematodes in the genus Meloidogyne, lesion nematodes in the genus Pratylenchus, stubby root nematodes in the genus Trichodorus, etc.) and animal and human health pests (i.e.
  • compounds of this invention for controlling potato leafhopper (Empoasca fabae). Of note is use of compounds of this invention for controlling corn planthopper ⁇ Peregrinus maidis). Of note is use of compounds of this invention for controlling cotton melon aphid ⁇ Aphis gossypii). Of note is use of compounds of this invention for controlling green peach aphid (Myzus persicae). Of note is use of compounds of this invention for controlling diamondback moth (Plutella xylostella). Of note is use of compounds of this invention for controlling fall armyworm (Spodoptera frugiperda).
  • Compounds of the present invention are also useful for increasing vigor of a crop plant.
  • This method comprises contacting the crop plant (e.g., foliage, flowers, fruit or roots) or the seed from which the crop plant is grown with a compound of Formula 1 in amount sufficient to achieve the desired plant vigor effect (i.e. biologically effective amount).
  • the compound of Formula 1 is applied in a formulated composition.
  • the compound of Formula 1 is often applied directly to the crop plant or its seed, it can also be applied to the locus of the crop plant, i.e. the environment of the crop plant, particularly the portion of the environment in close enough proximity to allow the compound of Formula 1 to migrate to the crop plant.
  • the locus relevant to this method most commonly comprises the growth medium (i.e.
  • Treatment of a crop plant to increase vigor of the crop plant thus comprises contacting the crop plant, the seed from which the crop plant is grown or the locus of the crop plant with a biologically effective amount of a compound of Formula 1.
  • Increased crop vigor can result in one or more of the following observed effects: (a) optimal crop establishment as demonstrated by excellent seed germination, crop emergence and crop stand; (b) enhanced crop growth as demonstrated by rapid and robust leaf growth (e.g., measured by leaf area index), plant height, number of tillers (e.g., for rice), root mass and overall dry weight of vegetative mass of the crop; (c) improved crop yields, as demonstrated by time to flowering, duration of flowering, number of flowers, total biomass accumulation (i.e. yield quantity) and/or fruit or grain grade marketability of produce (i.e.
  • the compounds of the present invention can increase the vigor of treated plants compared to untreated plants by killing or otherwise preventing feeding of phytophagous invertebrate pests in the environment of the plants. In the absence of such control of phytophagous invertebrate pests, the pests reduce plant vigor by consuming plant tissues or sap, or transmiting plant pathogens such as viruses.
  • the compounds of the invention may increase plant vigor by modifying metabolism of plants.
  • the vigor of a crop plant will be most significantly increased by treating the plant with a compound of the invention if the plant is grown in a nonideal environment, i.e. an environment comprising one or more aspects adverse to the plant achieving the full genetic potential it would exhibit in an ideal environment.
  • the present method for increasing vigor of a crop plant wherein the crop plant is grown in an environment comprising phytophagous invertebrate pests. Also of note is the present method for increasing vigor of a crop plant wherein the crop plant is grown in an environment not comprising phytophagous invertebrate pests. Also of note is the present method for increasing vigor of a crop plant wherein the crop plant is grown an environment comprising an amount of moisture less than ideal for supporting growth of the crop plant. Of note is the present method for increasing vigor of a crop plant wherein the crop is rice. Also of note is the present method for increasing vigor of a crop plant wherein the crop is maize (corn). Also of note is the present method for increasing vigor of a crop plant wherein the crop is soybean.
  • Compounds of this invention can also be mixed with one or more other biologically active compounds or agents including insecticides, fungicides, nematocides, bactericides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agronomic and nonagronomic utility.
  • insecticides fungicides, nematocides, bactericides, acaricides, herbicides, herbicide safeners
  • growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopath
  • the present invention also pertains to a composition
  • a composition comprising a biologically effective amount of a compound of Formula 1, an N-oxide, or salt thereof, at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, and at least one additional biologically active compound or agent.
  • the other biologically active compounds or agents can be formulated together with the present compounds, including the compounds of Formula 1, to form a premix, or the other biologically active compounds or agents can be formulated separately from the present compounds, including the compounds of Formula 1, and the two formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession.
  • insecticides such as abamectin, acephate, acequinocyl, acetamiprid, acrinathrin, amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, bensultap, bifenthrin, bifenazate, bistrifiuron, borate, buprofezin, cadusafos, carbaryl, carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr, chlorfiuazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin, cyantraniliprole, cyfiumetofen, cyfiuthrin, beta-cyfluthrin, cyhalothr
  • insecticides such as abamectin, acephate
  • insecticides such as abamectin, acetamiprid, acrinathrin, amitraz, avermectin, azadirachtin, bensultap, bifenthrin, buprofezin, cadusafos, carbaryl, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyfiuthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha- cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvaler
  • One embodiment of biological agents for mixing with compounds of this invention include entomopathogenic bacteria such as Bacillus thuringiensis, and the encapsulated delta-endotoxins of Bacillus thuringiensis such as MVP® and MVPII® bioinsecticides prepared by the CellCap® process (CellCap®, MVP® and MVPII® are trademarks of Mycogen Corporation, Indianapolis, Indiana, USA); entomopathogenic fungi such as green muscardine fungus; and entomopathogenic (both naturally occurring and genetically modified) viruses including baculovirus, nucleopolyhedro virus (NPV) such as Helicoverpa zea nucleopolyhedrovirus (HzNPV), Anagrapha falcifera nucleopolyhedrovirus (AfNPV); and granulosis virus (GV) such as Cydia pomonella granulosis virus (CpGV).
  • NPV nucleopolyhedr
  • a composition of the present invention can further comprise a biologically effective amount of at least one additional invertebrate pest control active ingredient having a similar spectrum of control but belonging to a different chemical class or having a different site of action.
  • additional biologically active compounds or agents include, but are not limited to, sodium channel modulators such as bifenthrin, cypermethrin, cyhalothrin, lambda- cyhalothrin, cyfluthrin, beta-cyfluthrin, deltamethrin, dimefluthrin, esfenvalerate, fenvalerate, indoxacarb, metofluthrin, profluthrin, pyrethrin and tralomethrin; cholinesterase inhibitors such as chlorpyrifos, methomyl, oxamyl, thiodicarb and triazamate; neonicotinoids such as acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid and thiamethoxam; insecticidal macrocyclic lactones such as spinetoram,
  • biologically active compounds or agents with which compounds of this invention can be formulated are: fungicides such as l-[4-[4-[5-(2,6-difluorophenyl)- 4,5 -dihydro-3 -isoxazolyl] -2-thiazolyl] - 1 -piperidinyl]-2- [5 -methyl-3 -(trifluoromethyl)- 1H- pyrazol-l-yl]ethanone, acibenzolar, aldimorph, amisulbrom, azaconazole, azoxystrobin, benalaxyl, benomyl, benthiavalicarb, benthiavalicarb-isopropyl, binomial, biphenyl, bitertanol, blasticidin-S, Bordeaux mixture (Tribasic copper sulfate), boscalid/nicobifen, bromuconazole, bupirimate, buthiobate, car
  • fungicides and compositions comprising fungicides such as l-[4-[4-[5- (2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-l-piperidinyl]-2-[5-methyl-3- (trifluoromethyl)-lH-pyrazol-l-yl]ethanone, azoxystrobin, copper hydroxide, cymoxanil, cyproconazole, difenoconazole, famoxadone, fenoxanil, ferimzone, flusilazole, flutolanil, fthalide, furametpyr, hexaconazole, isoprothiolane, isotianil, kasugamycin, mancozeb, metominostrobin, orysastrobin, pencycuron, penthiopyrad, picoxystrobin, probenazole, prop
  • combinations of a compound of this invention with other biologically active (particularly invertebrate pest control) compounds or agents can result in a greater-than-additive (i.e. synergistic) effect. Reducing the quantity of active ingredients released in the environment while ensuring effective pest control is always desirable.
  • synergism of invertebrate pest control active ingredients occurs at application rates giving agronomically satisfactory levels of invertebrate pest control, such combinations can be advantageous for reducing crop production cost and decreasing environmental load.
  • a greater-than-additive effect increasing crop plant vigor may also be observed.
  • Compounds of this invention and compositions thereof can be applied to plants genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis delta-endotoxins). Such an application may provide a broader spectrum of plant protection and be advantageous for resistance management.
  • the effect of the exogenously applied invertebrate pest control compounds of this invention may be synergistic with the expressed toxin proteins.
  • the weight ratio of these various mixing partners (in total) to the compound of Formula 1, an N- oxide, or salt thereof is typically between about 1 :3000 and about 3000: 1.
  • weight ratios between about 1 :300 and about 300: 1 for example ratios between about 1 :30 and about 30: 1).
  • One skilled in the art can easily determine through simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity. It will be evident that including these additional components can expand the spectrum of invertebrate pests controlled beyond the spectrum controlled by the compound of Formula 1 alone.
  • Table A lists specific combinations of a compound of Formula 1 with other invertebrate pest control agents illustrative of the mixtures, compositions and methods of the present invention.
  • the first column of Table A lists the specific invertebrate pest control agents (e.g., "Abamectin" in the first line).
  • the second column of Table A lists the mode of action (if known) or chemical class of the invertebrate pest control agents.
  • the third column of Table A lists embodiment(s) of ranges of weight ratios for rates at which a compound of Formula 1 can be applied relative to an invertebrate pest control agent (e.g., "50:1 to 1 :50" of a compound of Formula 1 relative to abamectin by weight).
  • the first line of Table A specifically discloses the combination of a compound of Formula 1 with abamectin can be applied in a weight ratio between 50: 1 to 1 :50.
  • the remaining lines of Table A are to be construed similarly.
  • Table A lists specific combinations of a compound of Formula 1 with other invertebrate pest control agents illustrative of the mixtures, compositions and methods of the present invention and includes additional embodiments of weight ratio ranges for application rates.
  • Azadirachtin ecdysone agonists 100 1 to 1 120
  • Cyromazine chitin synthesis inhibitors 400 1 to 1 :50
  • Deltamethrin sodium channel modulators 50 1 to 1 :400 Invertebrate Pest Mode of Action or Chemical Class Typical Control Agent Weight Ratio
  • Fenoxycarb juvenile hormone mimics 500:1 to 1:100
  • Hydramethylnon mitochondrial electron transport inhibitors 150:1 to 1:250 are Hydramethylnon mitochondrial electron transport inhibitors 150:1 to 1:250
  • Methoprene juvenile hormone mimics 500:1 to 1:100
  • Pyriproxyfen juvenile hormone mimics 500:1 to 1:100 Invertebrate Pest Mode of Action or Chemical Class Typical Control Agent Weight Ratio
  • Tebufenozide ecdysone agonists 500 1 to 1 250
  • Thiosultap-sodium 150 1 to 1 100
  • NPV e.g., Gemstar biological agents 50: 1 to 1 : 10
  • composition of the present invention wherein the at least one additional biologically active compound or agent is selected from the Invertebrate Pest Control Agents listed in Table A above.
  • the weight ratios of a compound, including a compound of Formula 1, an N-oxide, or salt thereof, to the additional invertebrate pest control agent typically are between 1000:1 and 1 : 1000, with one embodiment being between 500: 1 and 1 :500, another embodiment being between 250:1 and 1 :200 and another embodiment being between 100:1 and 1 :50.
  • Tables Bl to B19 are embodiments of specific compositions comprising a compound of Formula 1 (compound numbers (Cmpd. No.) refer to compounds in Index Table A) and an additional invertebrate pest control agent.
  • Table B2 is identical to Table B 1 , except that each reference to compound 1 in the column headed "Cmpd. No.” is replaced by a reference to compound 2.
  • the first mixture in Table B2 is designated B2-1 and is a mixture of compound 2 and the additional invertebrate pest control agent abamectin.
  • Table B3 is identical to Table B 1 , except that each reference to compound 1 in the column headed "Cmpd. No.” is replaced by a reference to compound 3.
  • the first mixture in Table B3 is designated B3-1 and is a mixture of compound 3 and the additional invertebrate pest control agent abamectin.
  • Table B4 is identical to Table B 1 , except that each reference to compound 1 in the column headed "Cmpd. No.” is replaced by a reference to compound 4.
  • the first mixture in Table B4 is designated B4-1 and is a mixture of compound 4 and the additional invertebrate pest control agent abamectin.
  • Table B5 is identical to Table B 1 , except that each reference to compound 1 in the column headed "Cmpd. No.” is replaced by a reference to compound 5.
  • the first mixture in Table B5 is designated B5-1 and is a mixture of compound 5 and the additional invertebrate pest control agent abamectin.
  • Table B6 is identical to Table B 1 , except that each reference to compound 1 in the column headed "Cmpd. No.” is replaced by a reference to compound 6.
  • the first mixture in Table B6 is designated B6-1 and is a mixture of compound 6 and the additional invertebrate pest control agent abamectin.
  • Table B7 is identical to Table B 1 , except that each reference to compound 1 in the column headed "Cmpd. No.” is replaced by a reference to compound 7.
  • the first mixture in Table B7 is designated B7-1 and is a mixture of compound 7 and the additional invertebrate pest control agent abamectin.
  • Table B8 is identical to Table Bl, except that each reference to compound 1 in the column headed "Cmpd. No.” is replaced by a reference to compound 8.
  • the first mixture in Table B8 is designated B8-1 and is a mixture of compound 8 and the additional invertebrate pest control agent abamectin.
  • Table B9 is identical to Table B 1 , except that each reference to compound 1 in the column headed "Cmpd. No.” is replaced by a reference to compound 9.
  • the first mixture in Table B9 is designated B9-1 and is a mixture of compound 9 and the additional invertebrate pest control agent abamectin.
  • Table BIO is identical to Table Bl, except that each reference to compound 1 in the column headed "Cmpd. No.” is replaced by a reference to compound 10.
  • the first mixture in Table BIO is designated BlO-1 and is a mixture of compound 10 and the additional invertebrate pest control agent abamectin.
  • Table Bl 1 is identical to Table Bl, except that each reference to compound 1 in the column headed "Cmpd. No.” is replaced by a reference to compound 11.
  • the first mixture in Table Bl 1 is designated Bl 1-1 and is a mixture of compound 11 and the additional invertebrate pest control agent abamectin.
  • Table B12 is identical to Table Bl, except that each reference to compound 1 in the column headed "Cmpd. No.” is replaced by a reference to compound 12.
  • the first mixture in Table B12 is designated B12-1 and is a mixture of compound 12 and the additional invertebrate pest control agent abamectin.
  • Table B13 is identical to Table Bl, except that each reference to compound 1 in the column headed "Cmpd. No.” is replaced by a reference to compound 13.
  • the first mixture in Table B13 is designated B13-1 and is a mixture of compound 13 and the additional invertebrate pest control agent abamectin.
  • Table B14 is identical to Table Bl, except that each reference to compound 1 in the column headed "Cmpd. No.” is replaced by a reference to compound 14.
  • the first mixture in Table B14 is designated B14-1 and is a mixture of compound 14 and the additional invertebrate pest control agent abamectin.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Agronomy & Crop Science (AREA)
  • Environmental Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Medicinal Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Tropical Medicine & Parasitology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Catching Or Destruction (AREA)
  • Pretreatment Of Seeds And Plants (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)

Abstract

Disclosed are compounds of Formula 1, wherein R1? is phenyl or pyridinyl, each optionally substituted with Q and up to 3 substituents independently selected from R2; each R2 is independently halogen, cyano, SF5 C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio or C1-C4 haloalkylthio; and Q is phenyl or pyridinyl, each optionally substituted with up to 5 substituents independently selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy. Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound or a composition of the invention. Further disclosed are methods for increasing vigor of a crop plant comprising contacting the crop plant, the seed from which the crop plant is grown or the locus of the crop plant with a biologically effective amount of a compound or composition of the invention.

Description

TITLE
MESOIONIC PYRIDO [1,2 -A] PYRIMIDINE PESTICIDES
FIELD OF THE INVENTION
This invention relates to certain pyrimidinium compounds, their compositions suitable for agronomic and nonagronomic uses, and methods of their use for controlling invertebrate pests such as arthropods in both agronomic and nonagronomic environments.
BACKGROUND OF THE INVENTION
The control of invertebrate pests is extremely important in achieving high crop efficiency. Damage by invertebrate pests to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, turf, wood products, and public health is also 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 sites of action.
PCT Patent Publication WO 09/099929 discloses certain mesoionic pyrimidinium compounds of Formula i as insecticid
Figure imgf000002_0001
wherein, inter alia, X and Y are O, R1 is substituted phenyl, R2 is CH2Q and Q is an optionally substituted 5- or 6-membered heteroaromatic ring, and R3 and R4 are taken together to form an optionally substituted 6-membered ring.
SUMMARY OF THE INVENTION
This invention is directed to compounds of Formula 1, compositions containing them and their use for controlling invertebrate pests:
Figure imgf000003_0001
1
wherein
R1 is phenyl or pyridinyl, each optionally substituted with Q and up to 3 substituents independently selected from R2;
each R2 is independently halogen, cyano, SF5, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio or C1-C4 haloalkylthio; and
Q is phenyl or pyridinyl, each optionally substituted with up to 5 substituents
independently selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy.
This invention provides a composition comprising a compound of Formula 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. In one embodiment, this invention also provides a composition for controlling an invertebrate pest comprising a compound of Formula 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition further comprising at least one additional biologically active compound or agent.
This invention also provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula 1 (e.g., as a composition described herein). This invention also relates to such method wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of Formula 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent.
This invention also provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of any of the aforesaid compositions wherein the environment is a plant.
This invention also provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of any of the aforesaid compositions wherein the environment is a seed. This invention also provides a method for protecting a seed from an invertebrate pest comprising contacting the seed with a biologically effective amount of a compound of Formula 1 (e.g., as a composition described herein). This invention also relates to the treated seed (i.e. seed contacted with a compound of Formula 1).
This invention also provides a method for increasing vigor of a crop plant comprising contacting the crop plant, the seed from which the crop plant is grown or the locus (e.g., growth medium) of the crop plant with a biologically effective amount of a compound of Formula 1 (e.g., as a composition described herein).
DETAILS OF THE INVENTION
As used herein, the terms "comprises", "comprising", "includes", "including", "has",
"having", "contains", "containing", "characterized by" or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process or method 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 or method.
The transitional phrase "consisting of excludes any element, step or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consisting of appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
The transitional phrase "consisting essentially of is used to define a composition or method that includes materials, steps, features, components or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term "consisting essentially of occupies a middle ground between "comprising" and "consisting of.
Where applicants have defined an invention or a portion thereof with an open-ended term such as "comprising", it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the terms "consisting essentially of or "consisting of.
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.
As referred to in this disclosure, the term "invertebrate pest" includes arthropods, gastropods, nematodes and helminths of economic importance as pests. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans. The term "gastropod" includes snails, slugs and other Stylommatophora. The term "nematode" includes members of the phylum Nematoda, such as phytophagous nematodes and helminth nematodes parasitizing animals. The term "helminth" includes all of the parasitic worms, such as roundworms (phylum Nematoda), heartworms (phylum Nematoda, class Secernentea), flukes (phylum Platyhelminthes, class Tematoda), acanthocephalans (phylum Acanthocephala), and tapeworms (phylum Platyhelminthes, class Cestoda).
In the context of this disclosure "invertebrate pest control" means inhibition of invertebrate pest development (including mortality, feeding reduction, and/or mating disruption), and related expressions are defined analogously.
The term "agronomic" refers to the production of field crops such as for food and fiber and includes the growth of maize or corn, soybeans and other legumes, rice, cereal (e.g., wheat, oats, barley, rye and rice), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers and cucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruit
(e.g., berries and cherries) and other specialty crops (e.g., canola, sunflower and olives).
The term "nonagronomic" refers to other than field crops, such as horticultural crops
(e.g., greenhouse, nursery or ornamental plants not grown in a field), residential, agricultural, commercial and industrial structures, turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.), wood products, stored product, agro-forestry and vegetation management, public health (i.e. human) and animal health (e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife) applications.
The term "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 a crop plant relative to an untreated control crop plant. The term "crop yield" refers to the return on crop material, in terms of both quantity and quality, obtained after harvesting a crop plant.
An "increase in crop yield" refers to an increase in crop yield relative to an untreated control crop plant.
The term "biologically effective amount" refers to the amount of a biologically active compound (e.g., a compound of Formula 1) sufficient to produce the desired biological effect when applied to (i.e. contacted with) an invertebrate pest to be controlled or its environment, or to a plant, the seed from which the plant is grown, or the locus of the plant (e.g., growth medium) to protect the plant from injury by the invertebrate pest or for other desired effect (e.g., increasing plant vigor).
Nonagronomic applications include protecting an animal from an invertebrate parasitic pest by administering a parasiticidally effective (i.e. biologically effective) amount of a compound of the invention, typically in the form of a composition formulated for veterinary use, to the animal to be protected. As referred to in the present disclosure and claims, the terms "parasiticidal" and "parasiticidally" refers to observable effects on an invertebrate parasite pest to provide protection of an animal from the pest. Parasiticidal effects typically relate to diminishing the occurrence or activity of the target invertebrate parasitic pest. Such effects on the pest include necrosis, death, retarded growth, diminished mobility or lessened ability to remain on or in the host animal, reduced feeding and inhibition of reproduction. These effects on invertebrate parasite pests provide control (including prevention, reduction or elimination) of parasitic infestation or infection of the animal.
In the above recitations, the term "alkyl", used either alone or in compound words such as "haloalkyl" includes straight-chain or branched alkyl, such as methyl, ethyl, n-propyl, /-propyl, or the different butyl 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", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" include CF3, CH2C1, CH2CF3 and CCI2CF3. The terms "haloalkoxy" and "haloalkylthio" are defined analogously to the term "haloalkyl". Examples of "haloalkoxy" include CF30, CC13CH20, HCF2CH2CH20 and CF3CH20. Examples of "haloalkylthio" include CC13S, CF3S, CC13CH2S and C1CH2CH2CH2S.
"Alkoxy" includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy and the different butoxy isomers.
The term "alkylthio" includes straight-chain or branched alkylthio moieties such as methylthio, ethylthio, and the different propylthio and butylthio isomers.
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.
When a radical is optionally substituted with listed substituents with the number of substituents stated (e.g., "up to 3"), then the radical may be unsubstituted or substituted with a number of substituents ranging up to the high number stated (e.g., "3"), and the attached substituents are independently selected from the substituents listed.
The number of optional substituents may be restricted by an expressed limitation. For example, the phrase "optionally substituted with up to 3 substituents independently selected from R2" means that 0, 1, 2 or 3 substituents can be present (if the number of potential connection points allows). When a range specified for the number of substituents exceeds the number of positions available for substituents on a ring, the actual higher end of the range is recognized to be the number of available positions.
The compounds of Formula 1 are mesoionic inner salts. "Inner salts", also known in the art as "zwitterions", are electrically neutral molecules but carry formal positive and negative charges on different atoms in each valence bond structure according to valence bond theory. Furthermore the molecular structure of the compounds of Formula 1 can be represented by the six valence bond structures shown below, each placing the formal positive and negative charges on different atoms. Because of this resonance, the compounds of Formula 1 are also described as "mesoionic". Although for sake of simplicity, the molecular structure of Formula 1 is depicted as a single valence bond structure herein, this particular valence bond structure is to be understood as representative of all six valence bond structures (depicted following this paragraph) relevant to bonding in molecules of compounds of Formula 1. Therefore reference to Formula 1 herein relates to all six applicable valence bond structures and other (e.g., molecular orbital theory) structures unless otherwise specified.
Figure imgf000007_0001
Compounds of this invention can exist as one or more conformational isomers due to restricted bond rotation caused by steric hinderance. For example, a compound of Formula 1 wherein R1 is phenyl substituted in the ortho-position with a sterically demanding alkyl group (e.g., isopropyl) may exist as two rotamers due to restricted rotation about the R1- pyrimidinium ring bond. This invention comprises mixtures of conformational isomers. In addition, this invention includes compounds that are enriched in one conformer relative to others.
Compounds selected from Formula 1 typically exist in more than one form, and Formula 1 thus includes all crystalline and non-crystalline forms of the compounds that Formula 1 represents. Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts. Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types). The term "polymorph" refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability. One skilled in the art will appreciate that a polymorph of a compound represented by Formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound represented by Formula 1. Preparation and isolation of a particular polymorph of a compound represented by Formula 1 can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures.
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 the compounds of Formula 1 are useful for control of invertebrate pests and animal parasites (i.e. are suitable for animal health use). The salts of the compounds of Formula 1 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.
Embodiments of the present invention as described in the Summary of the Invention include those described below. In the following Embodiments reference to "a compound of Formula 1" includes the definitions of substituents specified in the Summary of the Invention unless further defined in the Embodiments.
Embodiment 1. A compound of Formula 1 wherein R1 is phenyl optionally substituted with Q and up to 3 substituents independently selected from R2.
Embodiment la. A compound of Embodiment 1 wherein R1 is phenyl optionally
substituted with up to 3 substituents independently selected from R2. Embodiment 2. A compound of Formula 1 wherein R1 is pyridinyl optionally substituted with Q and up to 3 substituents independently selected from R2. Embodiment 2a. A compound of Embodiment 2 wherein R1 is pyridinyl optionally substituted with up to 3 substituents independently selected from R2.
Embodiment 3. A compound of Formula 1 or any one of Embodiments l-2a wherein each R2 is independently halogen, C1 -C4 alkyl, C1 -C4 haloalkyl, C1 -C4 alkoxy or C 1 -C4 haloalkoxy.
Embodiment 3 a. A compound of Embodiment 3 wherein each R2 is independently halogen, C 1-C2 alkyl, C 1-C2 haloalkyl, C 1-C2 alkoxy or C1-C2 haloalkoxy. Embodiment 3b. A compound of Embodiment 3 wherein each R2 is independently halogen.
Embodiment 3c. A compound of Embodiment 3 wherein each R2 is independently C^- C4 alkyl.
Embodiment 3d. A compound of Embodiment 3 wherein each R2 is independently C^- C4 haloalkyl.
Embodiment 3e. A compound of Embodiment 3 wherein each R2 is independently C^- C4 alkoxy.
Embodiment 3f. A compound of Embodiment 3 wherein each R2 is independently C^- C4 haloalkoxy.
Embodiment 4. A compound of Formula 1 or any one of Embodiments 1, 2 and 3-3 f wherein Q is phenyl optionally substituted with up to 5 substituents
independently selected from the group consisting of halogen, cyano, C1-C4 alkyl, C 1 -C4 haloalkyl, C1 -C4 alkoxy and C 1 -C4 haloalkoxy.
Embodiment 4a. A compound of Formula 1 or any one of Embodiments 1, 2 and 3-3 f wherein Q is pyridinyl optionally substituted with up to 4 substituents independently selected from the group consisting of halogen, cyano, C1-C4 alkyl, C 1 -C4 haloalkyl, C1 -C4 alkoxy and C 1 -C4 haloalkoxy.
Embodiment 4b. A compound of Embodiment 4 wherein Q is phenyl optionally
substituted with up to 3 substituents independently selected from the group consisting of cyano and C1 -C4 alkyl.
Embodiment 5. A compound of Formula 1 wherein R1 is phenyl substituted with up to 2 substituents independently selected from the group consisting of halogen, C1 -C4 haloalkyl and C 1 -C4 haloalkoxy.
Embodiment 6. A compound of Formula 1 wherein R1 is phenyl substituted with
halogen, C 1 -C4 haloalkyl or C1 -C4 haloalkoxy.
Embodiment 7. A compound of Formula 1 wherein R1 is phenyl substituted with C1 -C4 haloalkyl or C1 -C4 haloalkoxy. Embodiments of this invention, including Embodiments 1-7 above as well as any other embodiments described herein, can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula 1 but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1. In addition, embodiments of this invention, including Embodiments 1-7 above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present invention.
Combinations of Embodiments 1-7 are illustrated by:
Embodiment A. A compound of Formula 1 wherein
R1 is phenyl optionally substituted with Q and up to 3 substituents independently
selected from R2; and
Q is phenyl or pyridinyl, each optionally substituted with up to 3 substituents
independently selected from the group consisting of halogen, cyano, C1-C4 alkyl, C 1 -C4 haloalkyl, C1 -C4 alkoxy and C 1 -C4 haloalkoxy.
Embodiment B. A compound of Embodiment A wherein
R1 is phenyl optionally substituted with up to 3 substituents independently selected from the group consisting of halogen, C 1 -C4 alkyl, C 1 -C4 haloalkyl, C1-C4 alkoxy and C 1 -C4 haloalkoxy.
Specific embodiments include compounds of Formula 1 selected from the group consisting of:
2-hydroxy-4-oxo-3 -phenyl- 1 -(5-pyrimidinylmethyl)-4H-pyrido[ 1 ,2- ajpyrimidinium inner salt (i.e. compound 1 of Index Table A);
3 -(4-fluorophenyl)-2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H-pyrido [ 1 ,2- ajpyrimidinium inner salt (i.e. compound 2 of Index Table A);
2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-3 - [3 -(trifluoromethyl)phenyl] -4H- pyrido[l,2-a]pyrimidinium inner salt (i.e. compound 3 of Index Table A);
2-hydroxy-3-(2-methoxyphenyl)-4-oxo- 1 -(5-pyrimidinylmethyl)-4H-pyrido[ 1 ,2- ajpyrimidinium inner salt (i.e. compound 4 of Index Table A);
2- hydroxy-3 -(3 -methoxyphenyl)-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H-pyrido [ 1 ,2- ajpyrimidinium inner salt (i.e. compound 5 of Index Table A);
3- (2,4-difluorophenyl)-2-hydroxy-4-oxo-l-(5-pyrimidinylmethyl)-4H- pyrido[l,2-a]pyrimidinium inner salt (i.e. compound 6 of Index Table A);
2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-3 - [3 -(trifluoromethoxy)phenyl] -4H- pyrido[l,2-a]pyrimidinium inner salt (i.e. compound 7 of Index Table A);
3 -(2-bromophenyl)-2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H-pyrido [1,2- ajpyrimidinium inner salt (i.e. compound 8 of Index Table A);
3 -(2-fluorophenyl)-2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H-pyrido [ 1 ,2- ajpyrimidinium inner salt (i.e. compound 9 of Index Table A); 3-[2-fluoro-5-(trifluoromethyl)phenyl]-2-hydroxy-4-oxo- 1 -(5- pyrimidinylmethyl)-4H-pyrido[l,2-a]pyrimidinium inner salt (i.e. compound 10
of Index Table A);
2- hydroxy-3 -(3 -methylphenyl)-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H-pyrido [1,2- ajpyrimidinium inner salt (i.e. compound 11 of Index Table A);
3- [4-fluoro-3-(trifluoromethyl)phenyl]-2-hydroxy-4-oxo- 1 -(5- pyrimidinylmethyl)-4H-pyrido[l,2-a]pyrimidinium inner salt (i.e. compound 12
of Index Table A);
3 -(4-chloro-2-fluorophenyl)-2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H- pyrido[l,2-a]pyrimidinium inner salt (i.e. compound 13 of Index Table A);
3 -(2-chlorophenyl)-2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H-pyrido [1,2- ajpyrimidinium inner salt(i.e. compound 14 of Index Table A);
3-[3-chloro-5-(trifluoromethyl)phenyl]-2-hydroxy-4-oxo- 1 -(5- pyrimidinylmethyl)-4H-pyrido[l,2-a]pyrimidinium inner salt (i.e. compound 15
of Index Table A);
3 -(3 ,5 -dichlorophenyl)-2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H- pyrido[l,2-a]pyrimidinium inner salt (i.e. compound 16 of Index Table A);
3 -(3 ,5 -dichloro-4-fluorophenyl)-2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H- pyrido[l,2-a]pyrimidinium inner salt (i.e. compound 17 of Index Table A);
3-(4'-cyano-5,2'-dimethyl[l, -biphenyl]-3-yl)-2-hydroxy-4-oxo-l-(5- pyrimidinylmethyl)-4H-pyrido[l,2-a]pyrimidinium inner salt (i.e. compound 18
of Index Table A); and
3 -(3 -chlorophenyl)-2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H-pyrido [1,2- ajpyrimidinium inner salt(i.e. compound 19 of Index Table A).
Of note is that compounds of this invention are characterized by favorable metabolic and/or soil residual patterns and exhibit activity controlling a spectrum of agronomic and nonagronomic invertebrate pests.
Of particular note, for reasons of invertebrate pest control spectrum and economic importance, protection of agronomic crops from damage or injury caused by invertebrate pests by controlling invertebrate pests are embodiments of the invention. Compounds of this invention because of their favorable translocation properties or systemicity in plants also protect foliar or other plant parts which are not directly contacted with a compound of Formula 1 or a composition comprising the compound.
Also noteworthy as embodiments of the present invention are compositions comprising a compound of any of the preceding Embodiments, as well as any other embodiments described herein, and any combinations thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said compositions optionally further comprising at least one additional biologically active compound or agent.
Further noteworthy as embodiments of the present invention are compositions for controlling an invertebrate pest comprising a compound (i.e. in a biologically effective amount) of any of the preceding Embodiments, as well as any other embodiments described herein, and any combinations thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said compositions optionally further comprising at least one additional biologically active compound or agent (i.e. in a biologically effective amount).
Embodiments of the invention also include a composition comprising a compound of any of the preceding Embodiments in the form of a soil drench liquid formulation. Embodiments of the invention further include methods for controlling an invertebrate pest comprising contacting the soil with a liquid composition as a soil drench comprising a biologically effective amount of a compound of any of the preceding Embodiments.
Embodiments of the invention also include a spray composition for controlling an invertebrate pest comprising a compound (i.e. in a biologically effective amount) of any of the preceding Embodiments and a propellant. Embodiments of the invention further include a bait composition for controlling an invertebrate pest comprising a compound (i.e. in a biologically effective amount) of any of the preceding Embodiments, one or more food materials, optionally an attractant, and optionally a humectant. Embodiments of the invention also include a device for controlling an invertebrate pest comprising said bait composition and a housing adapted to receive said bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to said 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 invertebrate pest.
Embodiments of the invention also include methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula 1 (e.g., as a composition described herein), provided that the methods are not methods of medical treatment of a human or animal body by therapy.
This invention also relates to such methods wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of Formula 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent, provided that the methods are not methods of medical treatment of a human or animal body by therapy. Embodiments of the invention also include any of the preceding embodiments wherein the invertebrate pest is an arthropod. Embodiments of the invention also include any of the preceding embodiments wherein the arthropod is selected from the group consisting of insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans. Embodiments of the invention also include any of the preceding embodiments wherein the arthropod is an insect. Embodiments of the invention also include any of the preceding embodiments wherein the insect is in the order Hemiptera. Embodiments of the invention also include any of the preceding embodiments wherein the insect is a planthopper. Embodiments of the invention also include any of the preceding embodiments wherein the insect is a planthopper in the family Delphacidae. Embodiments of the invention also include any of the preceding embodiments wherein the insect is a leafhopper. Embodiments of the invention also include any of the preceding embodiments wherein the insect is a leafhopper in the family Cicadellidae.
Embodiments of the invention also include any of the preceding embodiments wherein the invertebrate pest is a gastropod. Embodiments of the invention also include any of the preceding embodiments wherein the gastropod is selected from the group consisting of snails, slugs and other Stylommatophora.
Embodiments of the invention also include any of the preceding embodiments wherein the invertebrate pest is a nematode. Embodiments of the invention also include any of the preceding embodiments wherein the nematode is selected from phytophagous nematodes.
Embodiments of the invention also include any of the preceding embodiments wherein the invertebrate pest is a helminth. Embodiments of the invention also include any of the preceding embodiments wherein the helminth is selected from the group consisting of roundworms, heartworms, flukes, acanthocephalans and tapeworms.
Embodiments of the invention also include embodiments pertaining to the method for increasing vigor of a crop plant disclosed in the Summary of the Invention wherein the compound of Formula 1 (e.g., as a composition described herein) is selected from any one of Embodiments 1— 4b, A and B, and compounds specifically disclosed herein.
One or more of the following methods and variations as described in Schemes 1-13 can be used to prepare the compounds of Formula 1. The definition of R1 in the compounds of Formulae 1-13 below are as defined above in the Summary of the Invention unless otherwise noted. Formulae la and lb are various subsets of Formula 1, and all substituents for Formulae la and le are as defined above for Formula 1 unless otherwise indicated. Ambient or room temperature is defined as about 20-25 °C.
Compounds of Formula 1 can be prepared by condensation of the compound of
Formula 2 with optionally substituted malonic acids of Formula 3a in the presence of condensing agents as shown in Scheme 1. Condensing agents can be carbodiimides such as dicyclohexyl carbodiimide (see, for example, Koch, A. et al. Tetrahedron 2004, 60, 10011- 10018) or other agents well known in the art to form amide bonds with or without activating agents such as N-hydroxybenzotriazole as described in Science of Synthesis 2005, 21, 17-25 and Tetrahedron 2005, 61, 10827-10852. This reaction is typically carried out in an inert organic solvent, such as dichloromethane or 1 ,2-dichloroethane, at temperatures from about 0 to about 80 °C for a period of 10 min to several days.
Scheme 1
Figure imgf000014_0001
Compounds of Formula 1 can also be prepared by the condensation of the compound of Formula 2 with malonic acid esters of Formula 3b wherein R is a C 1 -C5 alkyl group as shown in Scheme 2. These reactions can be performed neat or in the presence of inert solvents as described in Bulletin of the Chemical Society of Japan 1999, 72(3), 503-509. Inert solvents include, but are not limited to, high boiling hydrocarbons such as mesitylene, tetralin or cymene, or high boiling ethers such as diphenyl ether. Typical temperatures range from 50 to 250 °C. Of note are temperatures from 150 to 200 °C, which typically provide rapid reaction times and high yields. These reactions can also be performed in microwave reactors within the same temperature ranges. Typical reaction times range from 5 minutes to several hours.
Scheme 2
Figure imgf000014_0002
Compounds of Formula 3a can be prepared by a variety of methods known in the art, for example by base hydrolysis of compounds of Formula 3b.
Compounds of Formula 3b can be prepared by arylation of malonate esters (using compounds of formula RiX1 wherein X1 is CI, Br or I, examples of which are found in Tables I-24a, I-24-b and I-24c) catalyzed by palladium (J. Org. Chem 2002, 67, 541-555) or copper (Org. Lett. 2002, 4, 269-272 and Org. Lett. 2005, 7, 4693-4695). Alternatively, compounds of Formula 3b can be prepared by the method shown in Scheme 2a (see, for example, J. Med. Chem 1982, 25(6), 745-747).
Scheme 2a
Figure imgf000015_0001
OR
4 (R is Ci-C5 alkyl, 3b (R is C C5 alkyl,
phenyl or phenyl or
2,4,6 -trichlorophenyl) 2,4,6 -trichlorophenyl)
Esters of Formula 4 can be prepared from the corresponding acids by methods well known in the art. The acids of Formula 4 wherein R is H (examples are listed in Table I-l) are readily prepared by methods known in the art, and many are commercially available.
Compounds of Formula 3b can also be prepared by the method shown in Scheme 2b. Reaction of nitriles of Formula 3g with dialkyl carbonates yields nitrile esters of Formula 3h, and subsequent acidic hydrolysis in the presence of an alcohol provides the compounds of Formula 3b (see, for example, Helvetica Chimica Acta 1991, 74(2), 309-314). The nitriles of Formula 3g are readily prepared by methods known in the art, and many are commercially available.
Scheme 2b
Figure imgf000015_0002
3h
R is C -C5 alkyl
Compounds of Formula 1 can also be prepared by treatment of the compound of Formula 2 with activated esters of Formula 3c wherein LvO is an activated leaving group as shown in Scheme 3. Examples of Lv preferred for ease of synthesis or reactivity are phenyl, 4-nitrophenyl or halogen-substituted phenyl (e.g., 2,4,6-trichlorophenyl, pentachlorophenyl or pentafluorophenyl) as described in Archiv der Pharmazie (Weinheim, Germany) 1991, 324, 863-866. Other activated esters are well known in the art and include, but are not limited to, N-hydroxysuccinimide esters (see, for example, J. Am. Chem. Soc. 2002, 124, 6872-6878). Typical temperatures range from 50 to 200 °C. Of note are temperatures from 50 to 150 °C, which typically provide rapid reaction times and high yields. These reactions can be performed with or without solvent, such as toluene, and in microwave reactors within the same temperature ranges. Typical reaction times range from 5 minutes to 2 hours.
Scheme 3
Figure imgf000016_0001
Compounds of the Formula 3c can be prepared, for example, from compounds of Formula 3a (see, for example, J. Het. Chem. 1980, 17, 337).
Compounds of Formula 1 can also be prepared by condensation of the compound of Formula 2 with compounds of Formula 3d or 3e, or by condensation of the compound of Formula 2 with mixtures of compounds of Formulae 3d and 3e as shown in Scheme 4. These reactions are typically performed in an inert solvent, such as dichloromethane, and optionally in the presence of two or more equivalents of an acid acceptor (see, for example, Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie 1982, 37B(2), 222-233). Typical acid acceptors include, but are not limited to, triethylamine, N,N-diisopropylethylamine, pyridine and substituted pyridines, and metal hydroxides, carbonates and bicarbonates.
Scheme 4
Figure imgf000016_0002
Compounds of Formula la can be prepared by condensation of the compound of Formula 2 with carbon suboxide (3f) (see, for example, J. Org. Chem. 1972, 37(9), 1422- 1425) as shown in Scheme 5. The reactions are typically performed in an inert solvent such as ether and can include the use of a catalyst such as AICI3. Scheme 5
Figure imgf000017_0001
Compounds of Formula 1 can be prepared from compounds of Formula lb and compounds of Formula 5 wherein M with R1 forms a boronic acid, boronic acid ester or trifluoroborate salt, or M is trialkylstannyl or zinc, as shown in Scheme 6.
Scheme 6
Figure imgf000017_0002
In a similar manner, compounds of Formula 1 wherein R1 consists of two directly bonded aromatic rings (e.g., a phenyl ring bonded to a second phenyl ring, a phenyl ring bonded to a pyridinyl ring, or a pyridinyl ring bonded to a second pyridinyl ring) can be prepared by palladium-catalyzed coupling of the two appropriately substituted aromatic rings. These palladium-catalyzed couplings between an aromatic chloride, bromide or iodide and an aromatic boronic acid or ester, or an aromatic tin or zinc reagent, are well known and have been extensively described in the art. For example, see Scheme 6a, wherein a compound of Formula 13a or 13b is coupled with an appropriately substituted phenyl ring to provide the biphenyl compound of Formula 13c. M is as defined above for Scheme 6. Scheme 6a
(i)
(ϋ)
Figure imgf000018_0001
an gan s
13b
Ra is C02R, and Rb is C02R, CN or H; or
Ra is CN, and Rb is H; and
R is Ci-C5 alkyl
These coupling reactions are typically carried out in the presence of a palladium catalyst and a base optionally under an inert atmosphere. The palladium catalysts used for these coupling reactions typically comprises palladium in a formal oxidation state of either 0 (i.e. Pd(0)) or 2 (i.e. Pd(II)). A wide variety of such palladium-containing compounds and complexes are useful as catalysts for these reactions. Examples of palladium-containing compounds and complexes useful as catalysts in the methods include PdCl2(PPh3)2 (bis(triphenylphosphine)palladium (II) dichloride), Pd(PPh3)4 (tetrakis(triphenylphosphine)- palladium(O)), Pd^HyC^ (palladium(II) acetylacetonate), Pd2(dba)3 (tris(dibenzylidene- acetone)dipalladium(O)), and [1,1 '-bis(diphenylphosphino)ferrocene]dichloropalladium(II). These coupling methods are generally conducted in a liquid phase, and therefore the palladium catalyst preferably has good solubility in the liquid phase. Useful solvents include, for example, water, ethers such as 1 ,2-dimethoxyethane, amides such as N,N-dimethylacetamide, and non-halogenated aromatic hydrocarbons such as toluene.
The coupling methods can be conducted over a wide range of temperatures, ranging from about 25 to about 200 °C. Of note are temperatures from about 60 to about 150 °C, which typically provide fast reaction times and high product yields. The general methods and procedures for Stille, Negishi and Suzuki couplings with aryl iodides, bromides or chlorides and an aryl tin, aryl zinc or aryl boronic acid respectively are well known in the literature; see, for example, E. Negishi, Handbook of Organopalladium Chemistry for Organic Synthesis, Wiley-Interscience, 2002, New York, New York. Compounds of Formula 1 can be prepared from compounds of Formula la (i.e. Formula 1 wherein R1 is H) and compounds of Formula 6 wherein X1 is CI, Br or I (preferably Br or I) as shown in Scheme 7.
Scheme 7
Figure imgf000019_0001
These reactions are typically carried out in the presence of a copper or palladium catalyst preferably under an inert atmosphere. The copper catalysts used for the present method typically comprise copper in metallic form (e.g., as a powder) or copper in a formal oxidation state of 1 (i.e. Cu(I)). Examples of copper-containing compounds useful as catalysts in the method of Scheme 7 include Cu, Cul, CuBr, CuCl. Examples of palladium- containing compounds useful as catalysts in the method of Scheme 7 include Pd(OAc)2- Useful solvents for the method of Scheme 7 include, for example, ethers such as 1,4- dioxane, amides such as N,N-dimethylacetamide and dimethyl sulfoxide.
The method of Scheme 7 can be conducted over a wide range of temperatures from 25 to 200 °C. Of note are temperatures from 40 to 150 °C. The method of Scheme 7 can be conducted in the presence of a ligand. A wide variety of copper-binding compounds are useful as ligands for the present method. Examples of useful ligands include, but are not limited to, 1,10-phenanthroline, N,N-dimethylethylenediamine, L-proline and 2-picolinic acid. The general methods and procedures for copper-catalyzed Ullmann-type coupling reactions are well known in the literature; see, for example, Xie, Ma, et al. Org. Lett. 2005, 7, 4693-4695.
Compounds of Formula lb can be prepared from compounds of Formula la by halogenation using, for example, liquid bromine or N-halosuccinimides of Formula 10 as shown in Scheme 11. Typically the reaction is performed in an inert solvent, more typically a halogenated solvent such as methylene chloride or 1,2-dichloroethane. The reaction is typically performed at temperatures from 0 to 80 °C, more typically at ambient temperature. Scheme 11
Figure imgf000020_0001
Compounds of Formula 1 can also be prepared by alkylation of compounds of Formula 11 using appropriately substituted alkylating agents and bases such as potassium carbonate as shown in Scheme 12 (see, for example, Kappe, T. et al. Monatschefte fur Chemie 1971, 102, 412-424 and Urban, M. G.; Arnold,W. Helvetica Chimica Acta 1970, 53, 905-922). Alkylating agents include, but are not limited to, alkyl chlorides, bromides, iodides and sulfonate esters. A wide variety of bases and solvents can be employed in the method of Scheme 12, and these bases and solvents are well known in the art.
Scheme 12
Figure imgf000020_0002
Compounds of Formula 11 can be prepared from 2-aminopyridine by methods analogous to those shown in Schemes 1 through 5.
As shown in Schemes 1-5, the compound of Formula 2 is an important intermediate useful in the preparation of compounds of Formula 1. The compound of Formula 2 is an embodiment of the present invention. A further embodiment of the present invention is the use of the compound of Formula 2 in the preparation of compounds of Formula 1.
One skilled in the art will recognize that the compound of Formula 2 can also be used as its acid-addition salt (e.g., hydrochloric salt or acetic acid salt) in the coupling methods of Schemes 1-5.
A particularly useful method for the preparation of the compound of Formula 2 is shown in Scheme 13. In the method of Scheme 13, 2-aminopyridine (2a) is protected with suitable protecting groups such as, but not limited to, tert-butoxycarbonyl, acetyl or formyl to form the intermediate of Formula 2b wherein PG is a protecting group. The compound of Formula 2b is then alkylated with a compound of Formula 12 (wherein X is a leaving group such as a halogen) to give an intermediate of Formula 2c. The protecting group is removed to provide the compound of Formula 2. Conditions for the formation and removal of protecting groups on an amine function are known in the literature (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991).
Figure imgf000021_0001
An alternative method for the preparation of the compound of Formula 2 is by the reductive amination of the appropriate carbonyl compound. This method is shown in Steps A and B of Synthesis Example 1.
Another alternative method for the preparation of the compound of Formula 2 is by the reaction of an appropriate amine with the halogen-substituted compound analogous to the compound of Formula 2a (i.e. Formula 2a wherein the amino group is replaced with halogen) in the presence of a copper or palladium catalyst.
Compounds of Formula 1 having R1 substituents other than those particularly noted for Schemes 1 through 13 can be prepared by general methods known in the art of synthetic organic chemistry, including methods analogous to those described for Schemes 1 to 13.
Examples of intermediates useful in the preparation of compounds of this invention are shown in Tables I-l through 1-43. The following abbreviations are used in the Tables which follow: Me means methyl, Et means ethyl, Pr means propyl, Ph means phenyl, C(0)0(2,4,6- trichlorophenyl) means
Figure imgf000021_0002
C(0)0(4-nitrophenyl) means
Figure imgf000022_0001
, and
C(0)(3 -methyl-2-pyridinylamino) means
Figure imgf000022_0002
TABLE 1-1
Figure imgf000022_0003
Figure imgf000023_0001
2-fluoro-4-cyanophenyl
2-fluoro-4-chlorophenyl 2-methyl-4-chlorophenyl 2-fluoro-4-(CF3)phenyl
2.4- bis(CF3)phenyl 2-fluoro-4-bromophenyl 2-chloro-4-fluorophenyl 2-(CF3)-4- fluorophenyl 2-methyl-4-(CF3)phenyl 2-chloro-4-(CF3)phenyl 2-(CF3)-4-chlorophenyl
2.5- difluorophenyl 2-fluoro-5-(CF3)phenyl 2 - fluoro- 5 - chlorophenyl
2,5-dichlorophenyl 2-fluoro-5-(OCF3)phenyl 2-chloro-5-(CF3)phenyl
2-fluoro-4-cyanophenyl 2 - fluoro-4- chlorophenyl 2-methyl-4-chlorophenyl 2-fluoro-4-(CF3)phenyl
2.4- bis(CF3)phenyl 2-fluoro-4-bromophenyl 2 - chloro-4- fluorophenyl 2-(CF3)-4- fluorophenyl 2-methyl-4-(CF3)phenyl 2-chloro-4-(CF3)phenyl 2 - (CF3 ) -4-chlorophenyl
2.5- difluorophenyl
2 -fluoro- 5 - (CF3 )phenyl 2 - fluoro- 5 - chlorophenyl
2,5-dichlorophenyl 2-fluoro-5-(OCF3)phenyl 2-chloro-5-(CF3)phenyl
Figure imgf000024_0001
Figure imgf000025_0001
R
Figure imgf000026_0001
CI; Rb, Rd and Re are H
4-chlorophenyl 2-fluoro-4-cyanophenyl
4-(CF3)phenyl 2 - fluoro-4- chlorophenyl
4-cyanophenyl 2-methyl-4-chlorophenyl
4-bromophenyl 2-fluoro-4-(CF3)phenyl
6-chloro-3 -pyridinyl 2,4-bis(CF3)phenyl
6-fluoro-3-pyridinyl 2-fluoro-4-bromophenyl
6-(CF3)-3-pyridinyl 2 - chloro- 4 - fluorophenyl
4,6-dichloro-3 -pyridinyl 2-(CF3)-4- fluorophenyl
2-fluoro-6-chloro-3 -pyridinyl 2-methyl-4-(CF3)phenyl
2,6-dichloro-3 -pyridinyl 2-chloro-4-(CF3 )phenyl
2-bromo-5-chloro-4-pyridinyl 2 - (CF3 ) -4-chlorophenyl
3 -bromo-5-fluorophenyl 2,5-difluorophenyl
3-chloro-5-fluorophenyl 2 -fluoro- 5 - (CF3 )phenyl
3 -fluoro-4-chlorophenyl 2 - fluoro- 5 - chlorophenyl
2,4-dichlorophenyl 2,5-dichlorophenyl
2,4-difluorophenyl 2-fluoro-5-(OCF3)phenyl
2-chloro-5-(CF3)phenyl
Figure imgf000026_0002
Figure imgf000027_0001
Figure imgf000028_0001
OMe; Rb, Rc and Re are H
4-chlorophenyl 2-fluoro-4-cyanophenyl
4-(CF3)phenyl 2-fluoro-4-chlorophenyl
4-cyanophenyl 2-methyl-4-chlorophenyl
4-bromophenyl 2-fluoro-4-(CF3)phenyl
6-chloro-3 -pyridinyl 2,4-bis(CF3)phenyl
6-fluoro-3-pyridinyl 2-fluoro-4-bromophenyl
6-(CF3 )-3 -pyridinyl 2-chloro-4-fluorophenyl
4,6-dichloro-3 -pyridinyl 2-(CF3)-4- fluorophenyl
2-fluoro-6-chloro-3 -pyridinyl 2-methyl-4-(CF3)phenyl
2,6-dichloro-3 -pyridinyl 2-chloro-4-(CF3)phenyl
2-bromo-5-chloro-4-pyridinyl 2-(CF3)-4-chlorophenyl
3 -bromo-5-fluorophenyl 2,5-difluorophenyl
3-chloro-5-fluorophenyl 2-fluoro-5-(CF3)phenyl
3 -fluoro-4-chlorophenyl 2 - fluoro- 5 - chlorophenyl
2,4-dichlorophenyl 2,5-dichlorophenyl
2,4-difluorophenyl 2-fluoro-5-(OCF3)phenyl
2-chloro-5- CF3)phenyl
Figure imgf000029_0001
Figure imgf000029_0002
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
TABLE 1-2
Table 1-2 is identical to Table I-l, except that Rx is C(0)OMe.
TABLE 1-3
Table 1-3 is identical to Table I-l, except that Rx is C(0)OEt.
TABLE 1-4
Table 1-4 is identical to Table I-l, except that Rx is C(0)OPh.
TABLE 1-5
Table 1-5 is identical to Table I-l, except that Rx is C(0)OC(CH3)3.
TABLE 1-6
Table 1-6 is identical to Table I-l, except that Rx is C(0)0(2,4,6-trichlorophenyl).
TABLE 1-7
Table 1-7 is identical to Table I-l, except that Rx is C(0)0(4-nitrophenyl).
TABLE 1-8
Table 1-8 is identical to Table I-l, except that Rx is C(0)OH and RY is C(0)OH.
TABLE 1-9
Table 1-9 identical to Table I-l, except that Rx is C(0)OH and RY is C(0)OMe.
TABLE I- 10
Table I- 10 is constructed the same as Table I-l, except that Rx is C(0)OH and RY is C(0)OEt.
TABLE I-l 1
Table I-l 1 identical to Table I-l, except that Rx is C(0)OH and RY is C(0)OC(CH3)3.
TABLE 1-12
Table 1-12 identical to Table I-l, except that Rx is C(0)OH and RY is C(0)OPh.
TABLE 1-13
Table 1-13 identical to Table I-l, except that Rx is C(0)OH and RY is C(0)0(2,4,6- trichloropheny 1) .
TABLE 1-14
Table 1-14 identical to Table I-l, except that Rx is C(0)OH and RY is C(0)0(4-nitrophenyl).
TABLE 1-15
Table I- 15 is identical to Table I- 1 , except that Rx is C(0)OPh and RY is C(0)OMe.
TABLE 1-16
Table 1-16 is identical to Table I-l, except that Rx is C(0)OPh and RY is C(0)OEt. TABLE 1-17
Table 1-17 is identical to Table I-l, except that Rx is C(0)OPh and RY is C(0)OC(CH3)3.
TABLE 1-18
Table 1-18 is identical to Table I-l, except that Rx is C(0)OPh and RY is C(0)OPh.
TABLE 1-19
Table 1-19 is identical to Table I-l, except that Rx is C(0)OPh and RY is C(0)0(2,4,6- trichloropheny 1) .
TABLE 1-20
Table 1-20 is identical to Table I-l, except that Rx is C(0)OPh and RY is C(0)0(4- nitrophenyl).
TABLE 1-21
Table 1-21 is identical to Table I-l, except that Rx is C(0)C1 and RY is C(0)C1.
TABLE 1-22
Table 1-22 is identical to Table I-l, except that Rx is C(0)OMe and RY is C(0)OMe.
TABLE 1-23
Table 1-23 is identical to Table I-l, except that Rx is C(0)OEt and RY is C(0)OEt.
TABLE 1-24
Table 1-24 is identical to Table I-l, except that Rx is C(0)OC(CH3)3 and RY is C(0)OC(CH3)3.
TABLE 1-25
Table 1-25 is identical to Table I-l, except that Rx is C(0)0(2,4,6-trichlorophenyl) and RY is C(0)0(2,4,6-trichlorophenyl).
TABLE 1-26
Table 1-26 is identical to Table I-l, except that Rx is C(0)0(4-nitrophenyl) and RY is C(0)0(4-nitrophenyl).
TABLE 1-27
Table 1-27 is identical to Table I-l, except that Rx is C(0)(3-methyl-2-pyridinylamino) and RY is C(0)OH.
TABLE 1-28
Table 1-28 is identical to Table I-l, except that Rx is C(0)(3-methyl-2-pyridinylamino) and RY is C(0)OMe.
TABLE 1-29
Table 1-29 is identical to Table I-l, except that Rx is C(0)(3-methyl-2-pyridinylamino) and RY is C(0)OEt. TABLE 1-30
Table 1-30 is identical to Table I-l, except that Rx is C(0)(3-methyl-2-pyridinylamino) and RY is C(0)OPh.
TABLE 1-31
Table 1-31 is identical to Table I-l, except that Rx is C(0)(3-methyl-2-pyridinylamino) and Ry is C(0)0(2,4,6-trichlorophenyl).
TABLE 1-32
Table 1-32 is identical to Table I-l, except that Rx is C(0)(3-methyl-2-pyridinylamino) and Ry is C(0)0(4-nitrophenyl).
TABLE 1-33
Table 1-33 is identical to Table I-l, except that Rx is C(0)(3-methyl-2-pyridinylamino) and Ry is C(0)OC(CH3)3.
TABLE 1-34
Table 1-34 is identical to Table I-l, except that the chemical structure under the Table I-l heading is replaced with the following structure, and R is CI. The groups Rx and Ry found in Table I-l are not relevant to Table 1-34, as the CH(Rx)(Ry) moiety in the structure of Table I-l is replaced with a R group in the structure of Table 1-34.
Figure imgf000042_0001
For example, the first compound in Table 1-34 is the structure shown immediately above wherein Ra, Rb, Rc, Rd and Re are H, and R is CI.
TABLE 1-35
Table 1-35 is identical to Table 1-34, except that R is Br.
TABLE 1-36
Table 1-36 is identical to Table 1-34, except that R is I.
TABLE 1-37
Table 1-37 is identical to Table 1-34, except that R is CH2OH.
TABLE 1-38
Table 1-38 is identical to Table 1-34, except that R is CH2CN.
TABLE 1-39
Table 1-39 is identical to Table 1-34, except that R is CH2C1. TABLE 1-40
Table 1-40 is identical to Table 1-34, except that R is CH(CN)C02Me.
TABLE 1-41
Table 1-41 is identical to Table 1-34, except that R is CH(CN)C02Et.
Figure imgf000043_0001
R is CF3
gy ΕΞ gy
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH
H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt
C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh
C(0)OH C(0)(3 -methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3
C(0)OMe C(0)(3 -methyl-2-pyridinylamino) C(0)C1 C(0)C1
C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe
C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt
C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh
C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3
C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh
C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh
C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH
C(0)0(4-nitrophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OMe
C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt
C(0)0(2,4,6-trichlorophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3
R is H
gy ΕΞ gy
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH
H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt
C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh
C(0)OH C(0)(3 -methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3 g_i RY g_L gy
C(0)OMe C(0)(3-methyl-2-pyridmylamino) C(0)C1 C(0)C1
C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe
C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt
C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh
C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3
C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh
C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh
C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH
C(0)0(4-nitrophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OMe
C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt
C(0)0(2,4,6-trichlorophenyl) C(0)(3-methyl-2-pyridmylamino) H C(0)OPh
H C(0)OC(CH3)3 is CI
g__ gy g__ gy
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH
H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt
C(0)OH C(0)0(2,4,6-trichlorop enyl) C(0)OH C(0)OPh
C(0)OH C(0)(3 -methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3
C(0)OMe C(0)(3-methyl-2-pyridinylamino) C(0)C1 C(0)C1
C(0)OEt C(0)(3 -methyl-2-pyridmylamino) C(0)OMe C(0)OMe
C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt
C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh
C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3
C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh
C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh
C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH
C(0)0(4-nitrophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OMe
C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt
C(0)0(2,4,6-trichlorophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3
R is Br
gy g__ gy
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH
H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt Εϋ El ΕΞ EZ C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh C(0)OH C(0)(3 -methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3 C(0)OMe C (O) ( 3 -methy 1-2 -pyridinyl am ino) C(0)C1 C(0)C1 C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh C(0)OPh C(0)(3-methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3 C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH C(0)0(4-nitrophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OMe C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt C(0)0(2,4,6-trichlorophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3
R is l
ΕΞ gy ΕΞ EZ H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh C(0)OH C(0)(3 -methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3 C(0)OMe C(0)(3 -methyl-2-pyridinylamino) C(0)C1 C(0)C1 C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3 C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh C(0)OC(CH3)3 C(0)(3-methyl-2-pyridinylamino) C(0)OEt C(0)OPh C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH C(0)0(4-nitrophenyl) C(0)(3-methyl-2-pyridmylamino) H C(0)OMe C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt C(0)0(2,4,6-trichlorophenyl) C (O) (3 -methy 1 -2 -pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3
R is NH2
S_i El Εϋ RY
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH gy gy
H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt
C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh
C(0)OH C(0)(3-methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3
C(0)OMe C(0)(3 -methyl-2-pyridinylamino) C(0)C1 C(0)C1
C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe
C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt
C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh
C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3
C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh
C(0)OC(CH3)3 C(0)(3-methyl-2-pyridinylamino) C(0)OEt C(0)OPh
C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH
C(0)0(4-nitrophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OMe
C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt
C(0)0(2,4,6-trichlorophenyl) C (O) (3 -methyl- 2 -pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3
R is 2-cmoro-4-(trifluoromethyl)phenyl
g_i gy g__ gy
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH
H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt
C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh
C(0)OH C(0)(3 -methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3
C(0)OMe C(0)(3 -methyl-2-pyridinylamino) C(0)C1 C(0)C1
C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe
C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt
C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh
C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3
C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh
C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh
C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH
C(0)0(4-nitrophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OMe
C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt
C(0)0(2,4,6-trichlorophenyl) C(0)(3-methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3 R is 2-fluoro-5-(trifluoromethyl)phenyl
gy g_i gy
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH
H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt
C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh
C(0)OH C(0)(3 -methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3
C(0)OMe C(0)(3 -methyl-2-pyridinylamino) C(0)C1 C(0)C1
C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe
C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt
C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh
C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3
C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh
C(0)OC(CH3)3 C(0)(3-methyl-2-pyridinylamino) C(0)OEt C(0)OPh
C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH
C(0)0(4-nitrophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OMe
C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt
C(0)0(2,4,6-trichlorophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3
R is 2-chloro-4-cyanophenyl
gy gy
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH
H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt
C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh
C(0)OH C(0)(3 -methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3
C(0)OMe C(0)(3-methyl-2-pyridinylamino) C(0)C1 C(0)C1
C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe
C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt
C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh
C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3
C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh
C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh
C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH
C(0)0(4-nitrophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OMe
C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt
C(0)0(2,4,6-trichlorophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3 R is 2-fluoro-4-cyanophenyl
gy E2_ EX
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH
H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt
C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh
C(0)OH C(0)(3 -methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3
C(0)OMe C(0)(3 -methyl-2-pyridinylamino) C(0)C1 C(0)C1
C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe
C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt
C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh
C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3
C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh
C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh
C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH
C(0)0(4-nitrophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OMe
C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt
C(0)0(2,4,6-trichlorophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3
TABLE 1-43
Figure imgf000048_0001
R is H
R* gy Εϋ EX
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH
H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt
C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh
C(0)OH C(0)(3 -methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3
C(0)OMe C(0)(3 -methyl-2-pyridinylamino) C(0)C1 C(0)C1
C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe
C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt
C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh
C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3 ΕΞ RY Εϋ E
C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH C(0)0(4-nitrophenyl) C(0)(3-methyl-2-pyridinylamino) H C(0)OMe C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt C(0)0(2,4,6-trichlorophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3
R is CF3
ΕΞ gy Ei gy H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh C(0)OH C(0)(3 -methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3 C(0)OMe C(0)(3 -methyl-2-pyridinylamino) C(0)C1 C(0)C1 C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OP C(0)OPh C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3 C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH C(0)0(4-nitrophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OMe C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt C(0)0(2,4,6-trichlorophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3
R is F
RX El Β2_ EZ H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt C(0)OH C(0)0(2,4,6-tiichlorophenyl) C(0)OH C(0)OPh C(0)OH C(0)(3 -methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3 C(0)OMe C(0)(3-methyl-2-pyridinylamino) C(0)C1 C(0)C1 C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt ΕΞ El EH B
C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh
C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3
C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh
C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh
C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH
C(0)0(4-nitrophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OMe
C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt
C(0)0(2,4,6-trichlorophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3
R is CI
ΕΞ El Εϋ E
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH
H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt
C(0)OH C(0)0(2,4,6-tiichlorophenyl) C(0)OH C(0)OPh
C(0)OH C(0)(3 -methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3
C(0)OMe C(0)(3-methyl-2-pyridinylamino) C(0)C1 C(0)C1
C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe
C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt
C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh
C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3
C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh
C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh
C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH
C(0)0(4-nitrophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OMe
C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt
C(0)0(2,4,6-trichlorophenyl) C(0)(3-methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3
R is Br
ΕΞ ∑ R* RY
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH
H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt
C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh
C(0)OH C(0)(3 -methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3
C(0)OMe C(0)(3 -methyl-2-pyridinylamino) C(0)C1 C(0)C1 gy g_i gy
C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3 C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH C(0)0(4-nitrophenyl) C(0)(3-methyl-2-pyridmylamino) H C(0)OMe C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt C(0)0(2,4,6-trichlorophenyl) C(0)(3-methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3
R is l
gy g__ gy
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh C(0)OH C(0)(3-methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3 C(0)OMe C(0)(3-methyl-2-pyridinylamino) C(0)C1 C(0)C1 C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh C(0)OPh C(0)(3-methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3 C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH C(0)0(4-nitrophenyl) C(0)(3-methyl-2-pyridinylamino) H C(0)OMe C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt C(0)0(2,4,6-trichlorophenyl) C(0)(3-methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3
R is NH2
gy g__ gy
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh gy R^ RY
C(0)OH C(0)(3-methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3
C(0)OMe C(0)(3 -methyl-2-pyridinylamino) C(0)C1 C(0)C1
C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe
C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt
C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh
C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3
C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh
C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh
C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH
C(0)0(4-nitrophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OMe
C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt
C(0)0(2,4,6-trichlorophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3
R is 2-chloro-4-(trifluoromethyl)phenyl
gy Si gy
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH
H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt
C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh
C(0)OH C(0)(3-methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3
C(0)OMe C(0 ) ( 3 -methyl- 2-pyridinyl am ino) C(0)C1 C(0)C1
C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe
C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt
C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh
C(0)OPh C(0)(3-methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3
C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh
C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh
C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH
C(0)0(4-nitrophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OMe
C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt
C(0)0(2,4,6-trichlorophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3 is 2-fluoro-5-(trifluoromethyl)phenyl
gy R gy
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH
H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe RY Βϋ RY
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt
C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh
C(0)OH C(0)(3-methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3
C(0)OMe C(0)(3-methyl-2-pyridinylamino) C(0)C1 C(0)C1
C(0)OEt C(0)(3-methyl-2-pyridinylamino) C(0)OMe C(0)OMe
C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt
C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh
C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3
C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh
C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh
C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH
C(0)0(4-nitrophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OMe
C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt
C(0)0(2,4,6-trichlorophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3s 2-chloro-4-cyanophenyl
R_i Ry Βϋ EX
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH
H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt
C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh
C(0)OH C(0)(3-methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3
C(0)OMe C(0)(3 -methyl-2-pyridinylamino) C(0)C1 C(0)C1
C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe
C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt
C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh
C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3
C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh
C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh
C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH
C(0)0(4-nitrophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OMe
C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt
C(0)0(2,4,6-trichlorophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3 R is 2-fluoro-4-cyanophenyl
gy g__ gy
H C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OH
H C(0)0(4-nitrophenyl) C(0)OH C(0)OMe
C(0)OH C(0)0(4-nitrophenyl) C(0)OH C(0)OEt
C(0)OH C(0)0(2,4,6-trichlorophenyl) C(0)OH C(0)OPh
C(0)OH C(0)(3 -methyl-2-pyridinylamino) C(0)OH C(0)OC(CH3)3
C(0)OMe C(0)(3 -methyl-2-pyridinylamino) C(0)C1 C(0)C1
C(0)OEt C(0)(3 -methyl-2-pyridinylamino) C(0)OMe C(0)OMe
C(0)OPh C(0)0(4-nitrophenyl) C(0)OEt C(0)OEt
C(0)OPh C(0)0(2,4,6-trichlorophenyl) C(0)OPh C(0)OPh
C(0)OPh C(0)(3 -methyl-2-pyridinylamino) C(0)OC(CH3)3 C(0)OC(CH3)3
C(0)OC(CH3)3 C(0)OPh C(0)OMe C(0)OPh
C(0)OC(CH3)3 C(0)(3 -methyl-2-pyridinylamino) C(0)OEt C(0)OPh
C(0)0(4-nitrophenyl) C(0)0(4-nitrophenyl) H C(0)OH
C(0)0(4-nitrophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OMe
C(0)0(2,4,6-trichlorophenyl) C(0)0(2,4,6-trichlorophenyl) H C(0)OEt
C(0)0(2,4,6-trichlorophenyl) C(0)(3 -methyl-2-pyridinylamino) H C(0)OPh
H C(0)OC(CH3)3
It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula 1 may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula 1. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula 1.
One skilled in the art will also recognize that compounds of Formula 1 and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.
Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Synthesis Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Steps in the following Synthesis Examples illustrate a procedure for each step in an overall synthetic transformation, and the starting material for each step may not have necessarily been prepared by a particular preparative run whose procedure is described in other Examples or Steps. Ambient or room temperature is defined as about 20-25 °C. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. ¾ NMR spectra are reported in ppm downfield from tetramethylsilane; "s" means singlet, "d" means doublet, "dd" means doublet of doublets, "ddd" means doublet of doublet of doublets, "t" means triplet, "m" means multiplet, and "br s" means broad singlet. Compound numbers refer to compounds in Index Table A.
SYNTHESIS EXAMPLE 1
Preparation of 2-hydroxy-4-oxo- 1 -(5-pyrimidinylmethyl)-3-[3-(trifluoromethyl)phenyl]-4H- pyrido[ 1 ,2-a]pyrimidinium inner salt (compound 3)
Step A: Preparation of N-(5-pyrimidinylmethylene)-2-pyridinamine
A solution of 2-aminopyridine (11.314 g, 120.3 mmole) and pyrimidine-5- carboxaldehyde (14.0 g, 129.6 mmole) in chloroform (300 mL) was stirred at room temperature for 15 minutes. The volatiles were then removed under reduced pressure (1 hour at 75 °C) to yield a yellow solid. The crude solid was dissolved in chloroform (300 mL), and the solution was stirred for 15 minutes. The volatiles were then removed under reduced pressure (1 hour at 75 °C) to yield a yellow solid. The crude solid was again dissolved in chloroform (300 mL), the solution was stirred for 15 minutes, and the volatiles were removed under reduced pressure (1 hour at 85 °C) to yield a yellow solid. This solid was dried in a vacuum oven overnight at 80 °C to yield 22.090 g (99.8%) of the title compound. lU NMR (CDC13) δ 9.26-9.32 (m, 4Η), 8.52 (d, 1Η), 7.82 (t, 1Η), 7.42 (d, 1Η), 7.26 (t, 1Η).
Step B : Preparation of N- [(5 -pyrimidinyl)methyl] -2-pyridinamine
Powdered 98%> sodium borohydride (2.868 g, 75.5 mmole) was added to solution of methanol (80 mL) and tetrahydrofuran (400 mL), and the mixture was stirred vigorously for 5 minutes. The product of Step A (13.9 g, 75.5 mmole) was dissolved in tetrahydrofuran (400 mL), and the resulting solution was added dropwise to the sodium borohydride suspension at a constant rate of approximately 33 mL/minute. The appearance of the reaction mixture changed from a light yellow slightly cloudy suspension to a clear red solution. Reaction progress was monitored by thin layer chromatography eluting with a 10% methanol:40% dichloromethane:50% toluene solvent. Upon reaction completion, acetic acid (3 mL) was added dropwise, and the reaction mixture was stirred for 5 minutes. Acetic acid (2 mL) and water (30 mL) were added, the reaction mixture was briefly stirred, and then ethyl acetate was added (500 mL). The reaction mixture was washed with 1 N aqueous sodium hydroxide solution (300 mL), dried over magnesium sulfate, filtered, and the solvent was removed under reduced pressure at 50 °C. The resulting crude oil was dissolved in dichloromethane (50 mL), and the solution was eluted through a plug of silica gel (100 g) with ethyl acetate (3 L). The eluant was concentrated to a yellow-orange oil which slowly crystallized to provide 8.909 g (63.4%) of the title product as a pale yellow solid. lH NMR (CDC13) δ 9.12 (s, 1H), 8.76 (s, 2H), 8.10 (d, 1H), 7.42 (t, 1H), 6.64 (t, 1H), 6.42 (d, 1H), 4.99 (br s, NH), 4.61 (d, 2H).
Step C: Preparation of 1 ,3-dimethyl 2-[3-(trifluoromethyl)phenyl]propanedioate
Dioxane (100 mL) was purged with nitrogen gas for 10 minutes. Phenanthrolene (1.0 g) and copper (I) iodide (1.0 g) were added to the dioxane, the suspension was allowed to stir under a nitrogen atmosphere for 5 minutes, and then cesium carbonate (18.72 g, 57.45 mmol), dimethyl malonate (5.46 g, 50.6 mmol), and l-iodo-3-(trifluoromethyl)benzene (12.5 g, 46.0 mmol) were added. The reaction mixture was heated to reflux for 18 hours and then cooled to room temperature. Aqueous 1 N HC1 was added to the reaction mixture, the layers were separated, and the aqueous layer was extracted with ethyl acetate (3 x 100 mL). The combined organic layers were dried over magnesium sulfate and filtered. Celite® diatomaceous filter aid (5 g) was added to the filtrate, and the resulting suspension was concentrated under reduced pressure at 50 °C to yield a solid consisting of the crude product adsorbed onto Celite®. This solid was purified by silica gel chromatography eluting with a gradient of 100% hexanes to 25% ethyl acetate in hexanes to yield 7.36 g (58.0%) of the title product. !H NMR (CDC13) δ 7.59-7.65 (m, 3H), 7.49 (t, 1H), 4.70 (s, 1H), 3.76 (s, 6H). Step D: Preparation of bis(2,4,6-trichlorophenyl) 2-[3- (trifluoromethyl)phenyl]propanedioate
The product of Step C was added to a solution of NaOH (25 g) in water (75 mL), and the reaction mixture was vigorously stirred under a nitrogen atmosphere at 60 °C for 8 minutes. The reaction mixture was then added to ice (100 g), and aqueous 6 N HC1 was added until a pH of 1 was reached. The solution was extracted with ethyl acetate (3 x 100 mL), and the combined organic extracts were dried over magnesium sulfate, filtered, and concentrated under reduced pressure. Dichloromethane (200 mL) was added to the resulting white solid, followed by the addition of oxalyl chloride (5 mL) and N,N-dimethylformamide (0.5 mL). The reaction mixture was stirred at room temperature for 2 hours, followed by the addition of 2,4,6-trichlorophenol (10.528 g, 53.32 mmol). After stirring overnight at room temperature, the reaction mixture was concentrated under reduced pressure. Methanol was added to the resulting residue, and a solid slowly precipitated from the solution. The solid was collected by filtration to provide 8.161 g (50.43%>) of the title product as a solid. lH NMR (CDCI3) δ 7.91 (s, 1H), 7.83 (d, 1H), 7.70 (d, 1H), 7.59 (t, 1H), 7.37 (s, 4H), 5.38 (s, 1H).
Step E : Preparation of 2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-3 - [3 -
(trifluoromethyl)phenyl]-4H-pyrido[l,2-a]pyrimidinium inner salt
To the product of Step D (8.16 g, 13.4 mmol) in toluene (100 mL) was added the product of Step B (3.31 g, 17.8 mmol). The reaction mixture was heated to 110 °C for 6 hours, during which time a yellow solid precipitated out of solution. The reaction mixture was concentrated in the presence of Celite®, and the crude product adsorbed onto Celite® was purified by silica gel chromatography eluting with a gradient of 100% ethyl acetate to 25% methanol in ethyl acetate to yield 7.36 g (58.0%>) of the title product, a compound of this invention.
SYNTHESIS EXAMPLE 2
Preparation of 3-(4'-cyano-5,2'-dimethyl[ 1 , 1 '-biphenyl]-3-yl)-2-hydroxy-4-oxo- 1 -(5- pyrimidinylmethyl)-4H-pyrido[l,2-a]pyrimidinium inner salt (compound 18)
Step A: Preparation of 1 ,3-bis(l , 1 -dimethylethyl) 2-(3-iodo-5- methylphenyl)propanedioate
Copper iodide (332 mg, 1.74 mmol), cesium carbonate (5.6 g, 17.4 mmol), and picolinic acid (429 mg, 3.49 mmol) were added to a dried flask under a nitrogen atmosphere. A solution of 3,5-diiodotoluene (3 g, 8.7 mmol) in dioxane (10 mL) was added, followed by the addition of di-fert-butyl malonate (1.3 mL, 8.7 mmol). The atmosphere inside the flask was removed under vacuum and replaced with nitrogen gas; this process was repeated a total of three times. The reaction mixture was then heated to 80 °C and stirred for 24 hours. The reaction mixture was then cooled to room temperature, quenched with saturated aqueous ammonium chloride solution (50 mL), and extracted twice with diethyl ether (50 mL). The organic layers were combined, dried over MgSC^, and concentrated under reduced pressure. The resulting residue was purified by chromatography on silica gel eluted with ethyl acetate in hexanes to provide the title product as an orange oil (0.62 g).
!H NMR (CDCl3) δ 7.50 (dd 2H), 7.15 (s, 1H), 4.30 (s, 1H), 2.30 (s, 3H), 1.47 (m, 18H).
Step B: Preparation 1, 3 -bis( 1,1 -dimethylethyl) 2-(4'-cyano-5,2'-dimethyl[l,l'- biphenyl] -3 -yl)propanedioate
A mixture of 1, 3 -bis( 1,1 -dimethylethyl) 2-(3-iodo-5-methylphenyl)propanedioate (the product of Step A, 320 mg, 0.74 mmol), 4-cyano-2-methylphenylboronic acid (178 mg, 1.11 mmol), sodium carbonate (78 mg, 0.74 mmol), bis(triphenylphosphine)palladium(II) dichloride (52 mg, 0.074 mmol), dioxane (5 mL), and water (1 mL) was heated to 80 °C and stirred for 20 minutes. The reaction mixture was then cooled to room temperature, and filtered through a plug of silica gel eluting with 20% ethyl acetate in hexanes. Concentration of the eluant under reduced pressure provided a brown oil (430 mg) containing the crude product, which was used in the next step without further purification.
!H NMR (CDCI3) δ 7.70-7.10 (m, 6H), 4.436 (s, 1H), 2.402 (s, 3H), 2.289 (s, 3H), 1.469 (s, 18H).
Step C: Preparation of 3-(4'-cyano-5,2'-dimethyl[l, -biphenyl]-3-yl)-2-hydroxy-4- oxo- 1 -(5-pyrimidinylmethyl)-4H-pyrido[ 1 ,2-a]pyrimidinium inner salt A mixture of N-[(5-pyrimidinyl)methyl]-2-pyridinamine (65 mg, 0.34 mmol) and l,3-bis(l,l-dimethylethyl) 2-(4'-cyano-5,2'-dimethyl[l, -biphenyl]-3-yl)propanedioate (the product of Step B, 120 mg, 0.28 mmol) in /?-cymene (2 mL) and 1,2,3,4- tetrahydronaphthalene (i.e. tetralin, 1 mL) was heated to 178 °C and stirred for 1.5 hours. The reaction mixture was then cooled to room temperature, and purified by chromatography on silica gel eluted with 20% methanol in ethyl acetate to provide 40 mg (25%) of the title compound, a compound of this invention, as a yellow solid.
!H NMR ((CD3)2CO) δ 9.5 (dd, 1H), 9.05 (s, 1H), 8.95 (d, 2H), 8.35 (m, 1H) , 7.95 (dd, 1H), 7.80 (d, 1H), 7.75 (s, 1H), 7.70 (s, 1H), 7.65 (m, 1H), 7.55 (m, 1H), 7.45 (dd, 1H), 7.0 (d, 1H), 5.75 (s, 2H), 2.06 (d, 6H).
By the procedures described herein together with methods known in the art, the following compounds of Tables 1 and 2 can be prepared. The following abbreviations are used in Table 1 : Me means methyl, Et means ethyl, Pr means propyl and Bu means butyl.
Figure imgf000058_0001
Rb, Rc, Rd and Re are H
Ra Ra Ra Ra
H OCF3 4-cyanophenyl 2-iluoro-4-(CF3)phenyl
F OCHF2 4-bromophenyl 2,4-bis(CF3)phenyl
Figure imgf000059_0001
Ra, Rb, Rd and Re are H
R R£ R£ R£
H OCF3 4-cyanophenyl 2-fluoro-4-(CF3)phenyl
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
la is CI; Rb, Rc and Re are H
Figure imgf000063_0002
Figure imgf000064_0001
Figure imgf000065_0001
O-z'-Pr 4-(C 3 p eny -met y- -c orop eny
Ra is OMe; Rb, Rc and Re are H
2-fluoro-4-(CF3 )phenyl
2.4- bis(CF3)phenyl 2-fluoro-4-bromophenyl 2-chloro-4-fluorophenyl 2-(CF3)-4- fluorophenyl 2-methyl-4-(CF3 )phenyl 2-chloro-4-(CF3)phenyl 2-(CF3)-4-chlorophenyl
2.5- difluorophenyl
2 - fluoro- 5 - (CF3 )phenyl 2 - fluoro- 5 - chlorophenyl
2,5-dichlorophenyl 2-fluoro-5-(OCF3)phenyl 2-chloro-5-(CF3)phenyl
Figure imgf000065_0002
Figure imgf000066_0001
O-z'-Pr 4-(C 3 p eny -met y- -c orop eny
2-fluoro-4-(CF3 )phenyl
2.4- bis(CF3)phenyl 2-fluoro-4-bromophenyl 2-chloro-4-fluorophenyl 2-(CF3)-4- fluorophenyl 2-methyl-4-(CF3 )phenyl 2-chloro-4-(CF3)phenyl 2-(CF3)-4-chlorophenyl
2.5- difluorophenyl
2 - fluoro- 5 - (CF3 )phenyl 2 - fluoro- 5 - chlorophenyl
2,5-dichlorophenyl 2-fluoro-5-(OCF3)phenyl 2-chloro-5-(CF3)phenyl
Figure imgf000066_0002
Figure imgf000067_0001
Figure imgf000068_0001
2-fluoro-4-(CF3)phenyl
2.4- bis(CF3)phenyl 2-fluoro-4-bromophenyl 2-chloro-4-fluorophenyl 2-(CF3)-4-fluorophenyl 2-methyl-4-(CF3)phenyl 2-chloro-4-(CF3)phenyl 2-(CF3)-4-chlorophenyl
2.5- difluorophenyl
2 - fluoro- 5 - (CF3 )phenyl 2 - fluoro- 5 - chlorophenyl
2 ,5 -di chlorophenyl 2-fluoro-5-(OCF3)phenyl 2 - chloro- 5 - (CF3 )phenyl
Figure imgf000069_0001
Rb is Br; Ra, Rc and Re are H
2-fluoro-4-(CF3)phenyl
2.4- bis(CF3)phenyl 2-fluoro-4-bromophenyl 2-chloro-4-fluorophenyl 2-(CF3)-4-fluorophenyl 2-methyl-4-(CF3)phenyl 2-chloro-4-(CF3)phenyl 2-(CF3)-4-chlorophenyl
2.5- difluorophenyl
2 - fluoro- 5 - (CF3 )phenyl 2 - fluoro- 5 - chlorophenyl
2,5-dichlorophenyl 2-fluoro-5-(OCF3)phenyl 2 - chloro- 5 - (CF3 )phenyl
Figure imgf000069_0002
Rb is OCF ; Ra, Rc and Re are H
2-fluoro-4-(CF3)phenyl
2.4- bis(CF3)phenyl 2-fluoro-4-bromophenyl 2-chloro-4-fluorophenyl 2-(CF3 )-4- fluorophenyl 2-methyl-4-(CF3)phenyl 2-chloro-4-(CF3)phenyl 2-(CF3)-4-chlorophenyl
2.5- difluorophenyl
2 - fluoro- 5 - (CF3 )phenyl 2 - fluoro- 5 - chlorophenyl
2 ,5 -di chlorophenyl 2-fluoro-5-(OCF3)phenyl 2 - chloro- 5 - (CF3 )phenyl
Figure imgf000070_0001
Rb is OMe; Ra, Rc and Re are H
2-fluoro-4-(CF3)phenyl
2.4- bis(CF3)phenyl 2-fluoro-4-bromophenyl 2-chloro-4-fluorophenyl 2-(CF3)-4-fluorophenyl 2-methyl-4-(CF3)phenyl 2-chloro-4-(CF3)phenyl 2-(CF3)-4-chlorophenyl
2.5- difluorophenyl
2 - fluoro- 5 - (CF3 )phenyl 2 - fluoro- 5 - chlorophenyl
2,5-dichlorophenyl 2-fluoro-5-(OCF3)phenyl 2 - chloro- 5 - (CF3 )phenyl
Figure imgf000070_0002
2-fluoro-4-(CF3)phenyl
2,4-bis(CF3)phenyl
2-fluoro-4-bromophenyl
2-chloro-4-fluorophenyl
2-(CF3)-4-fluorophenyl
2-methyl-4-(CF3)phenyl
2-chloro-4-(CF3)phenyl
2-(CF3)-4-chlorophenyl
2,5-difluorophenyl
2 - fluoro- 5 - (CF3 )pheny 1
2 - fluoro - 5 - chlorophenyl
2,5-dichlorophenyl
2-fluoro-5-(OCF3)phenyl
2-chloro-5-(CF3)phenyl
2-fluoro-4-(CF3)phenyl
2,4-bis(CF3)phenyl
2-fluoro-4-bromophenyl
2-chloro-4-fluorophenyl
2-(CF3)-4-fluorophenyl
2-methyl-4-(CF3)phenyl
2-chloro-4-(CF3)phenyl
2-(CF3)-4-chlorophenyl
2,5-difluorophenyl
2 - fluoro- 5 - (CF3 )pheny 1
2 - fluoro- 5 - chlorophenyl
2,5-dichlorophenyl
2-fluoro-5-(OCF3)phenyl
2 - chloro- 5 - (CF3 )phenyl
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
O-z'-Pr 4-(C 3 p eny -met y- -c orop eny
Figure imgf000074_0002
Figure imgf000075_0001
Ra and Re are F; Rc and Rd are H
Figure imgf000076_0002
Figure imgf000076_0001
si Ei
2-fluoro-4-pyridinyl 2-chloro-4-pyridinyl 2-bromo-4-pyridinyl 2-(trifluoromethyl)-4-pyridinyl 6-fluoro-2-pyridinyl 6-chloro-2-pyridinyl 6-bromo-2-pyridinyl 6-(trifluoromethyl)-2-pyridinyl 4-fluoro-2-pyridinyl 4-chloro-2-pyridinyl 4-bromo-2-pyridinyl 4-(trifluoromethyl)-2-pyridinyl A compound of this invention will generally be used as an invertebrate pest control active ingredient in a composition, i.e. formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serves as a carrier. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like, which optionally can be thickened into gels. The general types of aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion and suspo-emulsion. The general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.
The general types of solid compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, which can be water-dispersible ("wettable") or water-soluble. Films and coatings formed from film- forming solutions or flowable suspensions are particularly useful for seed treatment. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient. An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.
Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water. Spray volumes can range from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into the furrow during planting. Liquid and solid formulations can be applied onto seeds of crops and other desirable vegetation as seed treatments before planting to protect developing roots and other subterranean plant parts and/or foliage through systemic uptake.
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. Weight Percent
Active
Ingredient Diluent Surfactant
Water-Dispersible and Water- 0.001-90 0-99.999 0-15
soluble Granules, Tablets and
Powders
Oil Dispersions, Suspensions, 1-50 40-99 0-50
Emulsions, Solutions
(including Emulsifiable
Concentrates)
Dusts 1-25 70-99 0-5
Granules and Pellets 0.001-95 5-99.999 0-15
High Strength Compositions 90-99 0-10 0-2
Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.
Liquid diluents include, for example, water, N,N-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, triacetin, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactate esters, dibasic esters and γ-butyrolactone, and alcohols, which can be linear, branched, saturated or unsaturated, such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzyl alcohol. Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C6-C22), such as plant seed and fruit oils (e.g, oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids can be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
The solid and liquid compositions of the present invention often include one or more surfactants. When added to a liquid, surfactants (also known as "surface-active agents") generally modify, most often reduce, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in a surfactant molecule, surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.
Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which are branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenol (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, graft or comb polymers and star polymers; polyethylene glycols (pegs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar-derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.
Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides such as N,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkyl naphthalene; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their derivatives such as dialkyl sulfosuccinate salts.
Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.
Also useful for the present compositions are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon 's Emulsifiers and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.
Compositions of this invention can also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which can be considered to also function as solid diluents, liquid diluents or surfactants). Such formulation auxiliaries and additives can control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes. Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of formulation auxiliaries and additives include those listed in McCutcheon 's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222.
The compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water. Active ingredient slurries, with particle diameters of up to 2,000 μιη can be wet milled using media mills to obtain particles with average diameters below 3 μιη. Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 um range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry 's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
For further information regarding the art of formulation, see T. S. Woods, "The Formulator's Toolbox - Product Forms for Modern Agriculture" in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; Hance et al, Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.
In the following Examples, all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Table A. Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except where otherwise indicated. Example A
High Strength Concentrate
compound 1
silica aerogel
synthetic amorphous fine silica
Example B
Wettable Powder
compound 2
dodecylphenol polyethylene glycol ether sodium ligninsulfonate
sodium silicoaluminate
montmorillonite (calcined)
Example C
Granule
compound 3
attapulgite granules (low volatile matter, 0.71/0.30 U.S.S. No. 25-50 sieves)
Example D
Extruded Pellet
compound 4
anhydrous sodium sulfate
crude calcium ligninsulfonate
sodium alkylnaphthalenesulfonate
calcium/magnesium bentonite
Example E
Emulsifiable Concentrate
compound 5
polyoxyethylene sorbitol hexoleate
C6-C10 fatty acid methyl ester
Example F
Microemulsion
compound 6
polyvinylpyrrolidone -vinyl acetate copolymer alkylpolyglycoside
glyceryl monooleate
water Example G
Seed Treatment
compound 7 20.00% polyvinylpyrrolidone -vinyl acetate copolymer 5.00% montan acid wax 5.00% calcium ligninsulfonate 1.00% polyoxyethylene/polyoxypropylene block copolymers 1.00% stearyl alcohol (POE 20) 2.00% polyorganosilane 0.20%> colorant red dye 0.05%> water 65.75%
Example H
Fertilizer Stick
compound 8 2.50%> pyrrolidone-styrene copolymer 4.80%> tristyrylphenyl 16-ethoxylate 2.30% talc 0.80% corn starch 5.00% slow-release fertilizer 36.00%> kaolin 38.00% water 10.60%
Example I
Suspension Concentrate
compound 9 35% butyl polyoxyethylene/polypropylene block copolymer 4.0%> stearic acid/polyethylene glycol copolymer 1.0%) styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0%> silicone based defoamer 0.1 % l,2-benzisothiazolin-3-one 0.1% water 53.7%
Example J
Emulsion in Water
compound 10 10.0% butyl polyoxyethylene/polypropylene block copolymer 4.0%> stearic acid/polyethylene glycol copolymer 1.0%) styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1%
1 ,2-benzisothiazolin-3-one 0.1% aromatic petroleum based hydrocarbon 20.0 water 58.7%
Example K
Oil Dispersion
compound 11 25% polyoxyethylene sorbitol hexaoleate 15% organically modified bentonite clay 2.5% fatty acid methyl ester 57.5%
Example L
Suspoemulsion
compound 12 10.0% imidacloprid 5.0% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1%
1 ,2-benzisothiazolin-3-one 0.1% aromatic petroleum based hydrocarbon 20.0% water 53.7%
Compounds of this invention exhibit activity against a wide spectrum of invertebrate pests. These pests include invertebrates inhabiting a variety of environments such as, for example, plant foliage, roots, soil, harvested crops or other foodstuffs, building structures or animal integuments. These pests include, for example, invertebrates feeding on foliage (including leaves, stems, flowers and fruits), seeds, wood, textile fibers or animal blood or tissues, and thereby causing injury or damage to, for example, growing or stored agronomic crops, forests, greenhouse crops, ornamentals, nursery crops, stored foodstuffs or fiber products, or houses or other structures or their contents, or being harmful to animal health or public health. Those skilled in the art will appreciate that not all compounds are equally effective against all growth stages of all pests. These present compounds and compositions are thus useful agronomically for protecting field crops from phytophagous invertebrate pests, and also nonagronomically for protecting other horticultural crops and plants from phytophagous invertebrate pests. This utility includes protecting crops and other plants (i.e. both agronomic and nonagronomic) that contain genetic material introduced by genetic engineering (i.e. transgenic) or modified by mutagenesis to provide advantageous traits. Examples of such traits include tolerance to herbicides, resistance to phytophagous pests (e.g., insects, mites, aphids, spiders, nematodes, snails, plant-pathogenic fungi, bacteria and viruses), improved plant growth, increased tolerance of adverse growing conditions such as high or low temperatures, low or high soil moisture, and high salinity, increased flowering or fruiting, greater harvest yields, more rapid maturation, higher quality and/or nutritional value of the harvested product, or improved storage or process properties of the harvested products. Transgenic plants can be modified to express multiple traits. Examples of plants containing traits provided by genetic engineering or mutagenesis include varieties of corn, cotton, soybean and potato expressing an insecticidal Bacillus thuringiensis toxin such as YIELD GARD®, KNOCKOUT®, STARLINK®, BOLLGARD®, NuCOTN® and NEWLEAF®, and herbicide-tolerant varieties of corn, cotton, soybean and rapeseed such as ROUNDUP READY®, LIBERTY LINK®,
ΊΜΓ, STS and CLEARFIELD , as well as crops expressing N-acetyltransferase (GAT) to provide resistance to glyphosate herbicide, or crops containing the HRA gene providing resistance to herbicides inhibiting acetolactate synthase (ALS). The present compounds and compositions may interact synergistically with traits introduced by genetic engineering or modified by mutagenesis, thus enhancing phenotypic expression or effectiveness of the traits or increasing the invertebrate pest control effectiveness of the present compounds and compositions. In particular, the present compounds and compositions may interact synergistically with the phenotypic expression of proteins or other natural products toxic to invertebrate pests to provide greater-than-additive control of these pests. Also the present compounds and compositions may interact synergistically with traits improving plant growth or other aspects of crop vigor, including traits conferring resistance to environmental stress such as suboptimal moisture.
Compositions of this invention can also optionally comprise plant nutrients, e.g., a fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium, magnesium, iron, copper, boron, manganese, zinc, and molybdenum. Of note are compositions comprising at least one fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium and magnesium. Compositions of the present invention which further comprise at least one plant nutrient can be in the form of liquids or solids. Of note are solid formulations in the form of granules, small sticks or tablets. Solid formulations comprising a fertilizer composition can be prepared by mixing the compound or composition of the present invention with the fertilizer composition together with formulating ingredients and then preparing the formulation by methods such as granulation or extrusion. Alternatively solid formulations can be prepared by spraying a solution or suspension of a compound or composition of the present invention in a volatile solvent onto a previous prepared fertilizer composition in the form of dimensionally stable mixtures, e.g., granules, small sticks or tablets, and then evaporating the solvent.
Examples of agronomic or nonagronomic invertebrate pests include eggs, larvae and adults of the order Lepidoptera, such as armyworms, cutworms, loopers, and heliothines in the family Noctuidae (e.g., pink stem borer (Sesamia inferens Walker), corn stalk borer (Sesamia nonagrioides Lefebvre), southern armyworm (Spodoptera eridania Cramer), fall armyworm (Spodoptera fugiperda J. E. Smith), beet armyworm (Spodoptera exigua Hiibner), cotton leafworm (Spodoptera littoralis Boisduval), yellowstriped armyworm (Spodoptera ornithogaUi Guenee), black cutworm (Agrotis ipsilon Hufnagel), velvetbean caterpillar (Anticarsia gemmatalis Hiibner), green fruitworm (Lithophane antennata Walker), cabbage armyworm (Barathra brassicae Linnaeus), soybean looper (Pseudoplusia includens Walker), cabbage looper (Trichoplusia ni Hiibner), tobacco budworm (Heliothis virescens Fabricius)); borers, casebearers, webworms, coneworms, cabbageworms and skeletonizers from the family Pyralidae (e.g., European corn borer (Ostrinia nubilalis Hiibner), navel orangeworm (Amyelois transitella Walker), corn root webworm (Crambus caliginosellus Clemens), sod webworms (Pyralidae: Crambinae) such as sod worm (Herpetogramma licarsisalis Walker), sugarcane stem borer (Chilo infuscatellus Snellen), tomato small borer (Neoleucinodes elegantalis Guenee), green leafroller (Cnaphalocerus medinalis), grape leaffolder (Desmia funeralis Hiibner), melon worm (Diaphania nitidalis Stoll), cabbage center grub (Helluala hydralis Guenee), yellow stem borer (Scirpophaga incertulas Walker), early shoot borer (Scirpophaga infuscatellus Snellen), white stem borer (Scirpophaga innotata Walker), top shoot borer (Scirpophaga nivella Fabricius), dark- headed rice borer (Chilo polychrysus Meyrick), cabbage cluster caterpillar (Crocidolomia binotalis English)); leafrollers, budworms, seed worms, and fruit worms in the family Tortricidae (e.g., codling moth (Cydia pomonella Linnaeus), grape berry moth (Endopiza viteana Clemens), oriental fruit moth (Grapholita molesta Busck), citrus false codling moth (Cryptophlebia leucotreta Meyrick), citrus borer (Ecdytolopha aurantiana Lima), redbanded leafroller (Argyrotaenia velutinana Walker), obliquebanded leafroller (Choristoneura rosaceana Harris), light brown apple moth (Epiphyas postvittana Walker), European grape berry moth (Eupoecilia ambiguella Hiibner), apple bud moth (Pandemis pyrusana Kearfott), omnivorous leafroller (Platynota stultana Walsingham), barred fruit-tree tortrix (Pandemis cerasana Hiibner), apple brown tortrix (Pandemis heparana Denis & Schiffermuller)); and many other economically important lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth (Lymantria dispar Linnaeus), peach fruit borer {Carposina niponensis Walsingham), peach twig borer (Anarsia lineatella Zeller), potato tuberworm (Phthorimaea operculella Zeller), spotted teniform leafminer (Lithocolletis blancardella Fabricius), Asiatic apple leafminer (Lithocolletis ringoniella Matsumura), rice leaffolder (Lerodea eufala Edwards), apple leafminer (Leucoptera scitella Zeller)); eggs, nymphs and adults of the order Blattodea including cockroaches from the families Blattellidae and Blattidae (e.g., oriental cockroach (Blatta orientalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo), German cockroach (Blattella germanica Linnaeus), brownbanded cockroach (Supella longipalpa Fabricius), American cockroach (Periplaneta americana Linnaeus), brown cockroach (Periplaneta brunnea Burmeister), Madeira cockroach (Leucophaea maderae Fabricius)), smoky brown cockroach (Periplaneta fuliginosa Service), Australian Cockroach (Periplaneta australasiae Fabr.), lobster cockroach (Nauphoeta cinerea Olivier) and smooth cockroach (Symploce pallens Stephens)); eggs, foliar feeding, fruit feeding, root feeding, seed feeding and vesicular tissue feeding larvae and adults of the order Coleoptera including weevils from the families Anthribidae, Bruchidae, and Curculionidae (e.g., boll weevil (Anthonomus grandis Boheman), rice water weevil (Lissorhoptrus oryzophilus Kuschel), granary weevil (Sitophilus granarius Linnaeus), rice weevil (Sitophilus oryzae Linnaeus)), annual bluegrass weevil (Listronotus maculicollis Dietz), bluegrass billbug (Sphenophorus parvulus Gyllenhal), hunting billbug (Sphenophorus venatus vestitus), Denver billbug (Sphenophorus cicatristriatus Fahraeus)); flea beetles, cucumber beetles, rootworms, leaf beetles, potato beetles, and leafminers in the family Chrysomelidae (e.g., Colorado potato beetle (Leptinotarsa decemlineata Say), western corn rootworm (Diabrotica virgifera virgifera LeConte)); chafers and other beetles from the family Scarabaeidae (e.g., Japanese beetle (Popillia japonica Newman), oriental beetle (Anomala orientalis Waterhouse, Exomala orientalis (Waterhouse) Baraud), northern masked chafer (Cyclocephala borealis Arrow), southern masked chafer (Cyclocephala immaculata Olivier or C lurida Bland), dung beetle and white grub (Aphodius spp.), black turfgrass ataenius (Ataenius spretulus Haldeman), green June beetle (Cotinis nitida Linnaeus), Asiatic garden beetle (Maladera castanea Arrow), May/June beetles (Phyllophaga spp.) and European chafer (Rhizotrogus majalis Razoumowsky)); carpet beetles from the family Dermestidae; wireworms from the family Elateridae; bark beetles from the family Scolytidae and flour beetles from the family Tenebrionidae.
In addition, agronomic and nonagronomic pests include: eggs, adults and larvae of the order Dermaptera including earwigs from the family Forficulidae (e.g., European earwig (Forficula auricularia Linnaeus), black earwig (Chelisoches morio Fabricius)); eggs, immatures, adults and nymphs of the orders Hemiptera and Homoptera such as, plant bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g. Empoasca spp.) from the family Cicadellidae, bed bugs (e.g., Cimex lectularius Linnaeus) from the family Cimicidae, planthoppers from the families Fulgoroidae and Delphacidae, treehoppers from the family Membracidae, psyllids from the family Psyllidae, whiteflies from the family Aleyrodidae, aphids from the family Aphididae, phylloxera from the family Phylloxeridae, mealybugs from the family Pseudococcidae, scales from the families Coccidae, Diaspididae and Margarodidae, lace bugs from the family Tingidae, stink bugs from the family Pentatomidae, chinch bugs (e.g., hairy chinch bug (Blissus leucopterus hirtus Montandon) and southern chinch bug {Blissus insularis Barber)) and other seed bugs from the family Lygaeidae, spittlebugs from the family Cercopidae squash bugs from the family Coreidae, and red bugs and cotton stainers from the family Pyrrhocoridae.
Agronomic and nonagronomic pests also include: eggs, larvae, nymphs and adults of the order Acari (mites) such as spider mites and red mites in the family Tetranychidae (e.g., European red mite {Panonychus ulmi Koch), two spotted spider mite (Tetranychus urticae Koch), McDaniel mite {Tetranychus mcdanieli McGregor)); flat mites in the family Tenuipalpidae (e.g., citrus flat mite (Brevipalpus lewisi McGregor)); rust and bud mites in the family Eriophyidae and other foliar feeding mites and mites important in human and animal health, i.e. dust mites in the family Epidermoptidae, follicle mites in the family Demodicidae, grain mites in the family Glycyphagidae; ticks in the family Ixodidae, commonly known as hard ticks (e.g., deer tick {Ixodes scapularis Say), Australian paralysis tick {Ixodes holocyclus Neumann), American dog tick {Dermacentor variabilis Say), lone star tick {Amblyomma americanum Linnaeus)) and ticks in the family Argasidae, commonly known as soft ticks (e.g., relapsing fever tick {Ornithodoros turicata), common fowl tick {Argas radiatus)); scab and itch mites in the families Psoroptidae, Pyemotidae, and Sarcoptidae; eggs, adults and immatures of the order Orthoptera including grasshoppers, locusts and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differ entialis Thomas), American grasshoppers (e.g., Schistocerca americana Drury), desert locust {Schistocerca gregaria Forskal), migratory locust {Locusta migratoria Linnaeus), bush locust {Zonocerus spp.), house cricket {Acheta domesticus Linnaeus), mole crickets (e.g., tawny mole cricket {Scapteriscus vicinus Scudder) and southern mole cricket {Scapteriscus borellii Giglio-Tos)); eggs, adults and immatures of the order Diptera including leafminers (e.g., Liriomyza spp. such as serpentine vegetable leafminer {Liriomyza sativae Blanchard)), midges, fruit flies (Tephritidae), frit flies (e.g., Oscinella frit Linnaeus), soil maggots, house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g., Fannia canicularis Linnaeus, F. femoralis Stein), stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g., Chrysomya spp., Phormia spp.), and other muscoid fly pests, horse flies (e.g., Tabanus spp.), bot flies (e.g., Gastrophilus spp., Oestrus spp.), cattle grubs (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.), keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g., Prosimulium spp., Simulium spp.), biting midges, sand flies, sciarids, and other Nematocera; eggs, adults and immatures of the order Thysanoptera including onion thrips (Thrips tabaci Lindeman), flower thrips {Frankliniella spp.), and other foliar feeding thrips; insect pests of the order Hymenoptera including ants of the Family Formicidae including the Florida carpenter ant (Camponotus floridanus Buckley), red carpenter ant (Camponotus ferrugineus Fabricius), black carpenter ant (Camponotus pennsylvanicus De Geer), white-footed ant (Technomyrmex albipes fr. Smith), big headed ants (Pheidole sp.), ghost ant (Tapinoma melanocephalum Fabricius); Pharaoh ant (Monomorium pharaonis Linnaeus), little fire ant (Wasmannia auropunctata Roger), fire ant (Solenopsis geminata Fabricius), red imported fire ant (Solenopsis invicta Buren), Argentine ant (Iridomyrmex humilis Mayr), crazy ant (Paratrechina longicornis Latreille), pavement ant (Tetramorium caespitum Linnaeus), cornfield ant (Lasius alienus Forster) and odorous house ant (Tapinoma sessile Say). Other Hymenoptera including bees (including carpenter bees), hornets, yellow jackets, wasps, and sawflies (Neodiprion spp.; Cephus spp.); insect pests of the order Isoptera including termites in the Termitidae (e.g., Macrotermes sp., Odontotermes obesus Rambur), Kalotermitidae (e.g., Cryptotermes sp.), and Rhinotermitidae (e.g., Reticulitermes sp., Coptotermes sp., Heterotermes tenuis Hagen) families, the eastern subterranean termite (Reticulitermes flavipes Kollar), western subterranean termite (Reticulitermes hesperus Banks), Formosan subterranean termite (Coptotermes formosanus Shiraki), West Indian drywood termite (Incisitermes immigrans Snyder), powder post termite (Cryptotermes brevis Walker), drywood termite (Incisitermes snyderi Light), southeastern subterranean termite (Reticulitermes virginicus Banks), western drywood termite (Incisitermes minor Hagen), arboreal termites such as Nasutitermes sp. and other termites of economic importance; insect pests of the order Thysanura such as silverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobia domestica Packard); insect pests of the order Mallophaga and including the head louse (Pediculus humanus capitis De Geer), body louse (Pediculus humanus Linnaeus), chicken body louse (Menacanthus stramineus Nitszch), dog biting louse (Trichodectes canis De Geer), fluff louse (Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank), short-nosed cattle louse (Haematopinus eurysternus Nitzsch), long-nosed cattle louse (Linognathus vituli Linnaeus) and other sucking and chewing parasitic lice that attack man and animals; insect pests of the order Siphonoptera including the oriental rat flea (Xenopsylla cheopis Rothschild), cat flea (Ctenocephalides felis Bouche), dog flea (Ctenocephalides canis Curtis), hen flea (Ceratophyllus gallinae Schrank), sticktight flea (Echidnophaga gallinacea Westwood), human flea (Pulex irritans Linnaeus) and other fleas afflicting mammals and birds. Additional arthropod pests covered include: spiders in the order Araneae such as the brown recluse spider (Loxosceles reclusa Gertsch & Mulaik) and the black widow spider (Latrodectus mactans Fabricius), and centipedes in the order Scutigeromorpha such as the house centipede (Scutigera coleoptrata Linnaeus). Examples of invertebrate pests of stored grain include larger grain borer (Prostephanus truncatus), lesser grain borer (Rhyzopertha dominica), rice weevil (Stiophilus oryzae), maize weevil (Stiophilus zeamais), cowpea weevil (Callosobruchus maculatus), red flour beetle (Tribolium castaneum), granary weevil (Stiophilus granarius), Indian meal moth (Plodia interpunctella), Mediterranean flour beetle (Ephestia kuhniella) and fiat or rusty grain beetle (Cryptolestis ferrugineus).
Compounds of the invention show particularly high activity against pests in the order Lepidoptera (e.g., Alabama argillacea Hiibner (cotton leaf worm), Archips argyrospila Walker (fruit tree leaf roller), A. rosana Linnaeus (European leaf roller) and other Archips species, Chilo suppressalis Walker (rice stem borer), Cnaphalocrosis medinalis Guenee (rice leaf roller), Crambus caliginosellus Clemens (corn root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Earias insulana Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoverpa armigera Hiibner (American bollworm), Helicoverpa zea Boddie (corn earworm), Heliothis virescens Fabricius (tobacco budworm), Herpetogramma licarsisalis Walker (sod webworm), Lobesia botrana Denis & Schiffermuller (grape berry moth), Pectinophora gossypiella Saunders (pink bollworm), Phyllocnistis citrella Stainton (citrus leafminer), Pieris brassicae Linnaeus (large white butterfly), Pieris rapae Linnaeus (small white butterfly), Plutella xylostella Linnaeus (diamondback moth), Spodoptera exigua Hiibner (beet armyworm), Spodoptera litura Fabricius (tobacco cutworm, cluster caterpillar), Spodoptera frugiperda J. E. Smith (fall armyworm), Trichoplusia ni Hiibner (cabbage looper) and Tuta absoluta Meyrick (tomato leafminer)).
Compounds of the invention also have significant activity on members from the order Homoptera including: Acyrthosiphon pisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer (apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solani Kaltenbach (foxglove aphid), Chaetosiphon fragaefolii Cockerell (strawberry aphid), Diuraphis noxia Kurdjumov/Mordvilko (Russian wheat aphid), Dysaphis plantaginea Paaserini (rosy apple aphid), Eriosoma lanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffroy (mealy plum aphid), Lipaphis erysimi Kaltenbach (turnip aphid), Metopolophium dirrhodum Walker (cereal aphid), Macrosiphum euphorbiae Thomas (potato aphid), Myzus persicae Sulzer (peach-potato aphid, green peach aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigus spp. (root aphids and gall aphids), Rhopalosiphum maidis Fitch (corn leaf aphid), Rhopalosiphum padi Linnaeus (bird cherry-oat aphid), Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius (English grain aphid), Therioaphis maculata Buckton (spotted alfalfa aphid), Toxoptera aurantii Boyer de Fonscolombe (black citrus aphid), and Toxoptera citricida Kirkaldy (brown citrus aphid); Adelges spp. (adelgids); Phylloxera devastatrix Pergande (pecan phylloxera); Bemisia tabaci Gennadius (tobacco whitefiy, sweetpotato whitefly), Bemisia argentifolii Bellows & Perring (silverleaf whitefly), Dialeurodes citri Ashmead (citrus whitefly) and Trialeurodes vaporariorum Westwood (greenhouse whitefly); Empoasca fabae Harris (potato leafhopper), Laodelphax striatellus Fallen (smaller brown planthopper), Macrolestes quadrilineatus Forbes (aster leafhopper), Nephotettix cinticeps Uhler (green leafhopper), Nephotettix nigropictus Stal (rice leafhopper), Nilaparvata lugens Stal (brown planthopper), Peregrinus maidis Ashmead (corn planthopper), Sogatella furcifera Horvath (white-backed planthopper), Sogatodes orizicola Muir (rice delphacid), Typhlocyba pomaria McAtee white apple leafhopper, Erythroneoura spp. (grape leafhoppers); Magicidada septendecim Linnaeus (periodical cicada); leery a purchasi Maskell (cottony cushion scale), Quadraspidiotus perniciosus Comstock (San Jose scale); Planococcus citri Risso (citrus mealybug); Pseudococcus spp. (other mealybug complex); Cacopsylla pyricola Foerster (pear psylla), Trioza diospyri Ashmead (persimmon psylla).
Compounds of this invention may also have activity on members from the order Hemiptera including: Acrosternum hilare Say (green stink bug), Anasa tristis De Geer (squash bug), Blissus leucopterus leucopterus Say (chinch bug), Cimex lectularius Linnaeus (bed bug) Corythuca gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-Schaffer (cotton stainer), Euchistus servus Say (brown stink bug), Euchistus variolarius Palisot de Beauvois (one-spotted stink bug), Graptosthetus spp. (complex of seed bugs), Leptoglossus corculus Say (leaf- footed pine seed bug), Lygus lineolaris Palisot de Beauvois (tarnished plant bug), Nezara viridula Linnaeus (southern green stink bug), Oebalus pugnax Fabricius (rice stink bug), Oncopeltus fasciatus Dallas (large milkweed bug), Pseudatomoscelis seriatus Reuter (cotton fleahopper). Other insect orders controlled by compounds of the invention include Thysanoptera (e.g., Frankliniella occidentalis Pergande (western flower thrips), Scirthothrips citri Moulton (citrus thrips), Sericothrips variabilis Beach (soybean thrips), and Thrips tabaci Lindeman (onion thrips); and the order Coleoptera (e.g., Leptinotarsa decemlineata Say (Colorado potato beetle), Epilachna varivestis Mulsant (Mexican bean beetle) and wireworms of the genera Agriotes, Athous or Limonius).
Compounds of the present invention also have activity on members of the Classes
Nematoda, Cestoda, Trematoda, and Acanthocephala including economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida such as but not limited to economically important agricultural pests (i.e. root knot nematodes in the genus Meloidogyne, lesion nematodes in the genus Pratylenchus, stubby root nematodes in the genus Trichodorus, etc.) and animal and human health pests (i.e. all economically important flukes, tapeworms, and roundworms, such as Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs, Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.). Note that some contemporary classification systems place Homoptera as a suborder within the order Hemiptera.
Of note is use of compounds of this invention for controlling potato leafhopper (Empoasca fabae). Of note is use of compounds of this invention for controlling corn planthopper {Peregrinus maidis). Of note is use of compounds of this invention for controlling cotton melon aphid {Aphis gossypii). Of note is use of compounds of this invention for controlling green peach aphid (Myzus persicae). Of note is use of compounds of this invention for controlling diamondback moth (Plutella xylostella). Of note is use of compounds of this invention for controlling fall armyworm (Spodoptera frugiperda).
Of note is use of compounds of this invention for controlling southern green stink bug
(Nezara viridula), western tarnished plant bug (Lygus hesperus), rice water weevil (Lissorhoptrus oryzophilus), rice brown planthopper (Nilaparvata lugens), rice green leafhopper (Nephotettix virescens) and striped rice borer (Chilo suppressalis).
Compounds of the present invention are also useful for increasing vigor of a crop plant. This method comprises contacting the crop plant (e.g., foliage, flowers, fruit or roots) or the seed from which the crop plant is grown with a compound of Formula 1 in amount sufficient to achieve the desired plant vigor effect (i.e. biologically effective amount). Typically the compound of Formula 1 is applied in a formulated composition. Although the compound of Formula 1 is often applied directly to the crop plant or its seed, it can also be applied to the locus of the crop plant, i.e. the environment of the crop plant, particularly the portion of the environment in close enough proximity to allow the compound of Formula 1 to migrate to the crop plant. The locus relevant to this method most commonly comprises the growth medium (i.e. medium providing nutrients to the plant), typically soil in which the plant is grown. Treatment of a crop plant to increase vigor of the crop plant thus comprises contacting the crop plant, the seed from which the crop plant is grown or the locus of the crop plant with a biologically effective amount of a compound of Formula 1.
Increased crop vigor can result in one or more of the following observed effects: (a) optimal crop establishment as demonstrated by excellent seed germination, crop emergence and crop stand; (b) enhanced crop growth as demonstrated by rapid and robust leaf growth (e.g., measured by leaf area index), plant height, number of tillers (e.g., for rice), root mass and overall dry weight of vegetative mass of the crop; (c) improved crop yields, as demonstrated by time to flowering, duration of flowering, number of flowers, total biomass accumulation (i.e. yield quantity) and/or fruit or grain grade marketability of produce (i.e. yield quality); (d) enhanced ability of the crop to withstand or prevent plant disease infections and arthropod, nematode or mollusk pest infestations; and (e) increased ability of the crop to withstand environmental stresses such as exposure to thermal extremes, suboptimal moisture or phytotoxic chemicals. The compounds of the present invention can increase the vigor of treated plants compared to untreated plants by killing or otherwise preventing feeding of phytophagous invertebrate pests in the environment of the plants. In the absence of such control of phytophagous invertebrate pests, the pests reduce plant vigor by consuming plant tissues or sap, or transmiting plant pathogens such as viruses. Even in the absence of phytophagous invertebrate pests, the compounds of the invention may increase plant vigor by modifying metabolism of plants. Generally, the vigor of a crop plant will be most significantly increased by treating the plant with a compound of the invention if the plant is grown in a nonideal environment, i.e. an environment comprising one or more aspects adverse to the plant achieving the full genetic potential it would exhibit in an ideal environment.
Of note is the present method for increasing vigor of a crop plant wherein the crop plant is grown in an environment comprising phytophagous invertebrate pests. Also of note is the present method for increasing vigor of a crop plant wherein the crop plant is grown in an environment not comprising phytophagous invertebrate pests. Also of note is the present method for increasing vigor of a crop plant wherein the crop plant is grown an environment comprising an amount of moisture less than ideal for supporting growth of the crop plant. Of note is the present method for increasing vigor of a crop plant wherein the crop is rice. Also of note is the present method for increasing vigor of a crop plant wherein the crop is maize (corn). Also of note is the present method for increasing vigor of a crop plant wherein the crop is soybean.
Compounds of this invention can also be mixed with one or more other biologically active compounds or agents including insecticides, fungicides, nematocides, bactericides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agronomic and nonagronomic utility. Thus the present invention also pertains to a composition comprising a biologically effective amount of a compound of Formula 1, an N-oxide, or salt thereof, at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, and at least one additional biologically active compound or agent. For mixtures of the present invention, the other biologically active compounds or agents can be formulated together with the present compounds, including the compounds of Formula 1, to form a premix, or the other biologically active compounds or agents can be formulated separately from the present compounds, including the compounds of Formula 1, and the two formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession.
Examples of such biologically active compounds or agents with which compounds of this invention can be formulated are insecticides such as abamectin, acephate, acequinocyl, acetamiprid, acrinathrin, amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, bensultap, bifenthrin, bifenazate, bistrifiuron, borate, buprofezin, cadusafos, carbaryl, carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr, chlorfiuazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin, cyantraniliprole, cyfiumetofen, cyfiuthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda- cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, difiubenzuron, dimefiuthrin, dimehypo, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, fionicamid, fiubendiamide, fiucythrinate, flufenerim, fiufenoxuron, fluvalinate, tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide, hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidal soaps, isofenphos, lufenuron, malathion, meperfiuthrin, metafiumizone, metaldehyde, methamidophos, methidathion, methiocarb, methomyl, methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide, nitenpyram, nithiazine, novaluron, novifiumuron, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profiuthrin, propargite, protrifenbute, pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl, pyrifiuquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulprofos, sulfoxafior, tebufenozide, tebufenpyrad, teflubenzuron, tefiuthrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethylfiuthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate, trichlorfon, trifiumuron, Bacillus thuringiensis delta-endotoxins, entomopathogenic bacteria, entomopathogenic viruses and entomopathogenic fungi.
Of note are insecticides such as abamectin, acetamiprid, acrinathrin, amitraz, avermectin, azadirachtin, bensultap, bifenthrin, buprofezin, cadusafos, carbaryl, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyfiuthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha- cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenothiocarb, fenoxycarb, fenvalerate, fipronil, fionicamid, fiubendiamide, fiufenoxuron, fluvalinate, formetanate, fosthiazate, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, metafiumizone, methiocarb, methomyl, methoprene, methoxyfenozide, nitenpyram, nithiazine, novaluron, oxamyl, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxafior, tebufenozide, tetramethrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate, trifiumuron, Bacillus thuringiensis delta-endotoxins, all strains of Bacillus thuringiensis and all strains of Nucleo polyhydrosis viruses.
One embodiment of biological agents for mixing with compounds of this invention include entomopathogenic bacteria such as Bacillus thuringiensis, and the encapsulated delta-endotoxins of Bacillus thuringiensis such as MVP® and MVPII® bioinsecticides prepared by the CellCap® process (CellCap®, MVP® and MVPII® are trademarks of Mycogen Corporation, Indianapolis, Indiana, USA); entomopathogenic fungi such as green muscardine fungus; and entomopathogenic (both naturally occurring and genetically modified) viruses including baculovirus, nucleopolyhedro virus (NPV) such as Helicoverpa zea nucleopolyhedrovirus (HzNPV), Anagrapha falcifera nucleopolyhedrovirus (AfNPV); and granulosis virus (GV) such as Cydia pomonella granulosis virus (CpGV).
Of particular note is such a combination where the other invertebrate pest control active ingredient belongs to a different chemical class or has a different site of action than the compound of Formula 1. In certain instances, a combination with at least one other invertebrate pest control active ingredient having a similar spectrum of control but a different site of action will be particularly advantageous for resistance management. Thus, a composition of the present invention can further comprise a biologically effective amount of at least one additional invertebrate pest control active ingredient having a similar spectrum of control but belonging to a different chemical class or having a different site of action. These additional biologically active compounds or agents include, but are not limited to, sodium channel modulators such as bifenthrin, cypermethrin, cyhalothrin, lambda- cyhalothrin, cyfluthrin, beta-cyfluthrin, deltamethrin, dimefluthrin, esfenvalerate, fenvalerate, indoxacarb, metofluthrin, profluthrin, pyrethrin and tralomethrin; cholinesterase inhibitors such as chlorpyrifos, methomyl, oxamyl, thiodicarb and triazamate; neonicotinoids such as acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid and thiamethoxam; insecticidal macrocyclic lactones such as spinetoram, spinosad, abamectin, avermectin and emamectin; GABA (γ-aminobutyric acid)-gated chloride channel antagonists such as avermectin or blockers such as ethiprole and fipronil; chitin synthesis inhibitors such as buprofezin, cyromazine, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron and triflumuron; juvenile hormone mimics such as diofenolan, fenoxycarb, methoprene and pyriproxyfen; octopamine receptor ligands such as amitraz; molting inhibitors and ecdysone agonists such as azadirachtin, methoxyfenozide and tebufenozide; ryanodine receptor ligands such as ryanodine, anthranilic diamides such as chlorantraniliprole, cyantraniliprole and flubendiamide; nereistoxin analogs such as cartap; mitochondrial electron transport inhibitors such as chlorfenapyr, hydramethylnon and pyridaben; lipid biosynthesis inhibitors such as spirodiclofen and spiromesifen; cyclodiene insecticides such as dieldrin or endosulfan; pyrethroids; carbamates; insecticidal ureas; and biological agents including nucleopolyhedro viruses (NPV), members of Bacillus thuringiensis, encapsulated delta-endotoxins of Bacillus thuringiensis, and other naturally occurring or genetically modified insecticidal viruses.
Further examples of biologically active compounds or agents with which compounds of this invention can be formulated are: fungicides such as l-[4-[4-[5-(2,6-difluorophenyl)- 4,5 -dihydro-3 -isoxazolyl] -2-thiazolyl] - 1 -piperidinyl]-2- [5 -methyl-3 -(trifluoromethyl)- 1H- pyrazol-l-yl]ethanone, acibenzolar, aldimorph, amisulbrom, azaconazole, azoxystrobin, benalaxyl, benomyl, benthiavalicarb, benthiavalicarb-isopropyl, binomial, biphenyl, bitertanol, blasticidin-S, Bordeaux mixture (Tribasic copper sulfate), boscalid/nicobifen, bromuconazole, bupirimate, buthiobate, carboxin, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, chlozolinate, clotrimazole, copper oxychloride, copper salts such as copper sulfate and copper hydroxide, cyazofamid, cyflunamid, cymoxanil, cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinocap, discostrobin, dithianon, dodemorph, dodine, econazole, etaconazole, edifenphos, epoxiconazole, ethaboxam, ethirimol, ethridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fencaramid, fenfuram, fenhexamide, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferfurazoate, ferimzone, fluazinam, fludioxonil, flumetover, fluopicolide, fluoxastrobin, fluquinconazole, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, fluxapyroxad, folpet, fosetyl-aluminum, fthalide, fuberidazole, furalaxyl, furametpyr, hexaconazole, hymexazole, guazatine, imazalil, imibenconazole, iminoctadine, iodicarb, ipconazole, iprobenfos, iprodione, iprovalicarb, isoconazole, isoprothiolane, isotianil, kasugamycin, kresoxim-methyl, mancozeb, mandipropamid, maneb, mapanipyrin, mefenoxam, mepronil, metalaxyl, metconazole, methasulfocarb, metiram, metominostrobin/fenominostrobin, mepanipyrim, metrafenone, miconazole, myclobutanil, neo-asozin (ferric methanearsonate), nuarimol, octhilinone, ofurace, orysastrobin, oxadixyl, oxolinic acid, oxpoconazole, oxycarboxin, paclobutrazol, penconazole, pencycuron, penflufen, penthiopyrad, perfurazoate, phosphonic acid, phthalide, picobenzamid, picoxystrobin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propamocarb-hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pryazophos, pyrifenox, pyrimethanil, pyrifenox, pyriofenone, pyrolnitrine, pyroquilon, quinconazole, quinoxyfen, quintozene, silthiofam, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, tebufloquin, techrazene, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolyfluanid, triadimefon, triadimenol, triarimol, triazoxide, tridemorph, trimorphamide, tricyclazole, trifloxystrobin, triforine, triticonazole, uniconazole, validamycin, valifenalate, vinclozolin, zineb, ziram, and zoxamide; nematocides such as aldicarb, imicyafos, oxamyl and fenamiphos; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad.
Of note are fungicides and compositions comprising fungicides such as l-[4-[4-[5- (2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-l-piperidinyl]-2-[5-methyl-3- (trifluoromethyl)-lH-pyrazol-l-yl]ethanone, azoxystrobin, copper hydroxide, cymoxanil, cyproconazole, difenoconazole, famoxadone, fenoxanil, ferimzone, flusilazole, flutolanil, fthalide, furametpyr, hexaconazole, isoprothiolane, isotianil, kasugamycin, mancozeb, metominostrobin, orysastrobin, pencycuron, penthiopyrad, picoxystrobin, probenazole, propiconazole, proquinazid, pyroquilon, simeconazole, tiadinil, tricyclazole, trifloxystrobin and validamycin.
In certain instances, combinations of a compound of this invention with other biologically active (particularly invertebrate pest control) compounds or agents (i.e. active ingredients) can result in a greater-than-additive (i.e. synergistic) effect. Reducing the quantity of active ingredients released in the environment while ensuring effective pest control is always desirable. When synergism of invertebrate pest control active ingredients occurs at application rates giving agronomically satisfactory levels of invertebrate pest control, such combinations can be advantageous for reducing crop production cost and decreasing environmental load. A greater-than-additive effect increasing crop plant vigor may also be observed.
Compounds of this invention and compositions thereof can be applied to plants genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis delta-endotoxins). Such an application may provide a broader spectrum of plant protection and be advantageous for resistance management. The effect of the exogenously applied invertebrate pest control compounds of this invention may be synergistic with the expressed toxin proteins.
General references for these agricultural protectants (i.e. insecticides, fungicides, nematocides, acaricides, herbicides and biological agents) include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2003 and The BioPesticide Manual, 2nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2001.
For embodiments where one or more of these various mixing partners are used, the weight ratio of these various mixing partners (in total) to the compound of Formula 1, an N- oxide, or salt thereof, is typically between about 1 :3000 and about 3000: 1. Of note are weight ratios between about 1 :300 and about 300: 1 (for example ratios between about 1 :30 and about 30: 1). One skilled in the art can easily determine through simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity. It will be evident that including these additional components can expand the spectrum of invertebrate pests controlled beyond the spectrum controlled by the compound of Formula 1 alone.
Table A lists specific combinations of a compound of Formula 1 with other invertebrate pest control agents illustrative of the mixtures, compositions and methods of the present invention. The first column of Table A lists the specific invertebrate pest control agents (e.g., "Abamectin" in the first line). The second column of Table A lists the mode of action (if known) or chemical class of the invertebrate pest control agents. The third column of Table A lists embodiment(s) of ranges of weight ratios for rates at which a compound of Formula 1 can be applied relative to an invertebrate pest control agent (e.g., "50:1 to 1 :50" of a compound of Formula 1 relative to abamectin by weight). Thus, for example, the first line of Table A specifically discloses the combination of a compound of Formula 1 with abamectin can be applied in a weight ratio between 50: 1 to 1 :50. The remaining lines of Table A are to be construed similarly. Of further note Table A lists specific combinations of a compound of Formula 1 with other invertebrate pest control agents illustrative of the mixtures, compositions and methods of the present invention and includes additional embodiments of weight ratio ranges for application rates.
Table A
Invertebrate Pest Mode of Action or Chemical Class Typical Control Agent Weight Ratio
Abamectin macrocyclic lactones 50 1 to 1 50
Acetamiprid neonicotinoids 150 1 to 1 200
Amitraz octopamine receptor ligands 200 1 to 1 100
Avermectin macrocyclic lactones 50 1 to 1 50
Azadirachtin ecdysone agonists 100 1 to 1 120
Beta-cyfluthrin sodium channel modulators 150 1 to 1 200
Bifenthrin sodium channel modulators 100: 1 to 1 : 10
Buprofezin chitin synthesis inhibitors 500: 1 to 1 :50
Cartap nereistoxin analogs 100 1 to 1 200
Chlorantraniliprole ryanodine receptor ligands 100 1 to 1 120
Chlorfenapyr mitochondrial electron transport inhibitors 300 1 to 1 200
Chlorpyrifos cholinesterase inhibitors 500 1 to 1 200
Clothianidin neonicotinoids 100 1 to 1 400
Cyantraniliprole ryanodine receptor ligands 100 1 to 1 120
Cyf uthrin sodium channel modulators 150 1 to 1 200
Cyhalothrin sodium channel modulators 150 1 to 1 200
Cypermethrin sodium channel modulators 150 1 to 1 200
Cyromazine chitin synthesis inhibitors 400: 1 to 1 :50
Deltamethrin sodium channel modulators 50: 1 to 1 :400 Invertebrate Pest Mode of Action or Chemical Class Typical Control Agent Weight Ratio
Dieldrin cyclodiene insecticides 200:1 to 1:100
Dinotefuran neonicotinoids 150:1 to 1:200
Diofenolan molting inhibitor 150:1 to 1:200
Emamectin macrocyclic lactones 50:1 to 1:10
Endosulfan cyclodiene insecticides 200:1 to 1:100
Esfenvalerate sodium channel modulators 100:1 to 1:400
Ethiprole GABA-regulated chloride channel 200:1 to 1:100 blockers
Fenothiocarb 150:1 to 1:200
Fenoxycarb juvenile hormone mimics 500:1 to 1:100
Fenvalerate sodium channel modulators 150:1 to 1:200
Fipronil GABA-regulated chloride channel 150:1 to 1:100 blockers
Flonicamid 200:1 to 1:100
Flubendiamide ryanodine receptor ligands 100:1 to 1:120
Flufenoxuron chitin synthesis inhibitors 200:1 to 1:100
Hexaflumuron chitin synthesis inhibitors 300:1 to 1:50
Hydramethylnon mitochondrial electron transport inhibitors 150:1 to 1:250
Imidacloprid neonicotinoids 1000:1 to 1:1000
Indoxacarb sodium channel modulators 200:1 to 1:50
Lambda-cyhalothrin sodium channel modulators 50:1 to 1:250
Lufenuron chitin synthesis inhibitors 500:1 to 1:250
Metaflumizone 200:1 to 1:200
Methomyl cholinesterase inhibitors 500:1 to 1:100
Methoprene juvenile hormone mimics 500:1 to 1:100
Methoxyfenozide ecdysone agonists 50:1 to 1:50
Nitenpyram neonicotinoids 150:1 to 1:200
Nithiazine neonicotinoids 150:1 to 1:200
Novaluron chitin synthesis inhibitors 500:1 to 1:150
Oxamyl cholinesterase inhibitors 200:1 to 1:200
Pymetrozine 200:1 to 1:100
Pyrethrin sodium channel modulators 100:1 to 1:10
Pyridaben mitochondrial electron transport inhibitors 200:1 to 1:100
Pyridalyl 200:1 to 1:100
Pyriproxyfen juvenile hormone mimics 500:1 to 1:100 Invertebrate Pest Mode of Action or Chemical Class Typical Control Agent Weight Ratio
Ryanodine ryanodine receptor ligands 100: 1 to 1 : 120
Spinetoram macrocyclic lactones 150: 1 to 1 : 100
Spinosad macrocyclic lactones 500: 1 to 1 : 10
Spirodiclofen lipid biosynthesis inhibitors 200 1 to 1 200
Spiromesifen lipid biosynthesis inhibitors 200 1 to 1 200
Tebufenozide ecdysone agonists 500 1 to 1 250
Thiacloprid neonicotinoids 100 1 to 1 200
Thiamethoxam neonicotinoids 1250 1 to 1 1000
Thiodicarb cholinesterase inhibitors 500 1 to 1 400
Thiosultap-sodium 150 1 to 1 100
Tralomethrin sodium channel modulators 150 1 to 1 200
Triazamate cholinesterase inhibitors 250 1 to 1 100
Triflumuron chitin synthesis inhibitors 200 1 to 1 100
Bacillus thuringiensis biological agents 50 1 to 1 10
Bacillus thuringiensis biological agents 50 1 to 1 10 delta-endotoxin
NPV (e.g., Gemstar) biological agents 50: 1 to 1 : 10
Of note is the composition of the present invention wherein the at least one additional biologically active compound or agent is selected from the Invertebrate Pest Control Agents listed in Table A above.
The weight ratios of a compound, including a compound of Formula 1, an N-oxide, or salt thereof, to the additional invertebrate pest control agent typically are between 1000:1 and 1 : 1000, with one embodiment being between 500: 1 and 1 :500, another embodiment being between 250:1 and 1 :200 and another embodiment being between 100:1 and 1 :50.
Listed below in Tables Bl to B19 are embodiments of specific compositions comprising a compound of Formula 1 (compound numbers (Cmpd. No.) refer to compounds in Index Table A) and an additional invertebrate pest control agent.
Table Bl
Mixture Cmpd. and Invertebrate Pest Control Mixture Cmpd. and Invertebrate Pest No. No. Agent No. No. Control Agent
Bl-1 1 and Abamectin Bl-38 1 and Indoxacarb
Bl-2 1 and Acetamiprid Bl-39 1 and Lambda- cyhalothrin
Bl-3 1 and Amitraz Bl-40 1 and Lufenuron
Bl-4 1 and Avermectin Bl-41 1 and Metaflumizone
Bl-5 1 and Azadirachtin Bl-42 1 and Methomyl
Bl-6 1 and Bensultap Bl-43 1 and Methoprene Mixture Cmpd. and Invertebrate Pest Control Mixture Cmpd. and Invertebrate Pest
No. No. Agent No. No. Control Agent
Bl-7 1 and Beta-cyfluthrin Bl -44 1 and Methoxyfenozide
Bl-8 1 and Bifenthrin Bl-45 1 and Nitenpyram
Bl-9 1 and Buprofezin Bl-46 1 and Nithiazine
Bl -10 1 and Cartap Bl -47 1 and Novaluron
Bl-11 1 and Chlorantraniliprol e Bl-48 1 and Oxamyl
Bl-12 1 and Chlorfenapyr Bl -49 1 and Phosmet
Bl-13 1 and Chlorpyrifos Bl -50 1 and Pymetrozine
Bl-14 1 and Clothianidin Bl-51 1 and Pyrethrin
Bl-15 1 and Cyantraniliprole Bl-52 1 and Pyridaben
B l-16 1 and Cyfluthrin Bl-53 1 and Pyridalyl
Bl -17 1 and Cyhalothrin Bl -54 1 and Pyriproxyfen
Bl-18 1 and Cypermethrin Bl-55 1 and Ryanodine
Bl-19 1 and Cyromazine Bl -56 1 and Spinetoram
Bl-20 1 and Deltamethrin Bl -57 1 and Spinosad
Bl-21 1 and Dieldrin Bl -58 1 and Spirodiclofen
Bl-22 1 and Dinotefuran Bl -59 1 and Spiromesifen
Bl-23 1 and Diofenolan Bl-60 1 and Spirotetramat
Bl-24 1 and Emamectin Bl -61 1 and Sulfoxaflor
Bl-25 1 and Endosulfan Bl -62 1 and Tebufenozide
Bl-26 1 and Esfenvalerate Bl -63 1 and Tefluthrin
Bl-27 1 and Ethiprole Bl -64 1 and Thiacloprid
Bl-28 1 and Fenothiocarb Bl -65 1 and Thiamethoxam
B l-29 1 and Fenoxycarb Bl -66 1 and Thiodicarb
Bl -30 1 and Fenvalerate Bl -67 1 and Thiosultap-sodium
Bl-31 1 and Fipronil Bl-68 1 and Tolfenpyrad
Bl-32 1 and Flonicamid Bl -69 1 and Tralomethrin
Bl-33 1 and Flubendiamide Bl-70 1 and Triazamate
Bl-34 1 and Flufenoxuron Bl-71 1 and Triflumuron
Bl-35 and Hexaflumuron Bl-72 and Bacillus thuringiensis
1 1
Bacil his thuringiensis
Bl -36 and Hydramethylnon Bl -73 and
1 1 delta-endotoxin
Bl-37 1 and Imidacloprid Bl-74 1 and NPV (e.g., Gemstar)
Table B2
Table B2 is identical to Table B 1 , except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 2. For example, the first mixture in Table B2 is designated B2-1 and is a mixture of compound 2 and the additional invertebrate pest control agent abamectin.
Table B3
Table B3 is identical to Table B 1 , except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 3. For example, the first mixture in Table B3 is designated B3-1 and is a mixture of compound 3 and the additional invertebrate pest control agent abamectin.
Table B4
Table B4 is identical to Table B 1 , except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 4. For example, the first mixture in Table B4 is designated B4-1 and is a mixture of compound 4 and the additional invertebrate pest control agent abamectin.
Table B5
Table B5 is identical to Table B 1 , except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 5. For example, the first mixture in Table B5 is designated B5-1 and is a mixture of compound 5 and the additional invertebrate pest control agent abamectin.
Table B6
Table B6 is identical to Table B 1 , except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 6. For example, the first mixture in Table B6 is designated B6-1 and is a mixture of compound 6 and the additional invertebrate pest control agent abamectin.
Table B7
Table B7 is identical to Table B 1 , except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 7. For example, the first mixture in Table B7 is designated B7-1 and is a mixture of compound 7 and the additional invertebrate pest control agent abamectin.
Table B8
Table B8 is identical to Table Bl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 8. For example, the first mixture in Table B8 is designated B8-1 and is a mixture of compound 8 and the additional invertebrate pest control agent abamectin.
Table B9
Table B9 is identical to Table B 1 , except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 9. For example, the first mixture in Table B9 is designated B9-1 and is a mixture of compound 9 and the additional invertebrate pest control agent abamectin.
Table BIO
Table BIO is identical to Table Bl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 10. For example, the first mixture in Table BIO is designated BlO-1 and is a mixture of compound 10 and the additional invertebrate pest control agent abamectin.
Table Bl l
Table Bl 1 is identical to Table Bl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 11. For example, the first mixture in Table Bl 1 is designated Bl 1-1 and is a mixture of compound 11 and the additional invertebrate pest control agent abamectin.
Table B 12
Table B12 is identical to Table Bl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 12. For example, the first mixture in Table B12 is designated B12-1 and is a mixture of compound 12 and the additional invertebrate pest control agent abamectin.
Table B 13
Table B13 is identical to Table Bl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 13. For example, the first mixture in Table B13 is designated B13-1 and is a mixture of compound 13 and the additional invertebrate pest control agent abamectin.
Table B 14
Table B14 is identical to Table Bl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 14. For example, the first mixture in Table B14 is designated B14-1 and is a mixture of compound 14 and the additional invertebrate pest control agent abamectin.
Table B 15
Table B15 is identical to Table Bl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 15. For example, the first mixture in Table B15 is designated B15-1 and is a mixture of compound 15 and the additional invertebrate pest control agent abamectin.
Table B 16
Table B16 is identical to Table Bl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 16. For example, the first mixture in Table B16 is designated B16-1 and is a mixture of compound 16 and the additional invertebrate pest control agent abamectin.
Table B 17
Table B17 is identical to Table Bl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 17. For example, the first mixture in Table B17 is designated B17-1 and is a mixture of compound 17 and the additional invertebrate pest control agent abamectin.
Table B18
Table B18 is identical to Table Bl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 18. For example, the first mixture in Table B18 is designated B18-1 and is a mixture of compound 18 and the additional invertebrate pest control agent abamectin.
Table B 19
Table B19 is identical to Table Bl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 19. For example, the first mixture in Table B18 is designated B19-1 and is a mixture of compound 19 and the additional invertebrate pest control agent abamectin. The specific mixtures listed in Tables Bl to B19 typically combine a compound of
Formula 1 with the other invertebrate pest agent in the ratios specified in Table A.
Listed below in Tables CI to C19 are specific mixtures comprising a compound of Formula 1 (compound numbers (Cmpd. No.) refer to compounds in Index Table A) and an additional invertebrate pest control agent. Tables CI to C19 further list specific weight ratios typical of the mixtures of Tables CI to CI 9. For example, the first weight ratio entry of the first line of Table CI specifically discloses the mixture of Compound 1 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.
Table CI
Mixture Cmpd. Invertebrate Pest
and Typical Mixture Ratios (by weight)
No. No. Control Agent
Cl-1 1 and Abamectin 100:1 10:1 5:1 2: 1 1: 1 1:2 1:5 1: 10 1:100
Cl-2 1 and Acetamiprid 100:1 10:1 5:1 2: 1 1: 1 1:2 1:5 1: 10 1:100
Cl-3 1 and Amitraz 100: 1 10:1 5:1 2:1 1: 1 1:2 1:5 1: 10 1:100
Cl-4 1 and Avermectin 100:1 10:1 5:1 2: 1 1: 1 1:2 1:5 1: 10 1:100
Cl-5 1 and Azadirachtin 100:1 10:1 5:1 2: 1 1: 1 1:2 1:5 1: 10 1:100
Cl-6 1 and Bensultap 100:1 10:1 5:1 2: 1 1: 1 1:2 1:5 1: 10 1:100 Cl-7 1 and Beta-cyfluthrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 110 1:100
Cl-8 1 and Bifenthrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-9 1 and Buprofezin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-10 1 and Cartap 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-11 1 and Chlorantraniliprole 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-12 1 and Chlorfenapyr 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-13 1 and Chlorpyrifos 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-14 1 and Clothianidin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-15 1 and Cyantraniliprole 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-16 1 and Cyfluthrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-17 1 and Cyhalothrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-18 1 and Cypermethrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-19 1 and Cyromazine 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-20 1 and Deltamethrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-21 1 and Dieldrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
CI -22 1 and Dinotefuran 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-23 1 and Diofenolan 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
CI -24 1 and Emamectin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-25 1 and Endosulfan 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-26 1 and Esfenvalerate 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-27 1 and Ethiprole 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-28 1 and Fenothiocarb 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
CI -29 1 and Fenoxycarb 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-30 1 and Fenvalerate 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-31 1 and Fipronil 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-32 1 and Flonicamid 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-33 1 and Flubendiamide 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-34 1 and Flufenoxuron 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-35 1 and Hexaflumuron 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-36 1 and Hydramethylnon 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-37 1 and Imidacloprid 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-38 1 and Indoxacarb 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Lambda-
Cl-39 1 and 100:1 10:1 5:1 2:1 1:2 1:5 1 10 1:100 cyhalothrin
CI -40 1 and Lufenuron 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
Cl-41 1 and Metaflumizone 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100
CI -42 1 and Methomyl 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1 10 1:100 CI -43 1 and Methoprene 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
CI -44 1 and Methoxyfenozide 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
CI -45 1 and Nitenpyram 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
CI -46 1 and Nithiazine 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
CI -47 1 and Novaluron 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-48 1 and Oxamyl 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
CI -49 1 and Phosmet 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-50 1 and Pymetrozine 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-51 1 and Pyrethrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-52 1 and Pyridaben 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-53 1 and Pyridalyl 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-54 1 and Pyriproxyfen 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-55 1 and Ryanodine 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-56 1 and Spinetoram 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-57 1 and Spinosad 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-58 1 and Spirodiclofen 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-59 1 and Spiromesifen 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-60 1 and Spirotetramat 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-61 1 and Sulfoxaflor 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
CI -62 1 and Tebufenozide 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-63 1 and Tefluthrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
CI -64 1 and Thiacloprid 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-65 1 and Thiamethoxam 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-66 1 and Thiodicarb 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-67 1 and Thiosultap-sodium 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-68 1 and Tolfenpyrad 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
CI -69 1 and Tralomethrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-70 1 and Triazamate 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-71 1 and Triflumuron 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Bacillus
Cl-72 1 and 100:1 10:1 5:1 2:1 1:2 1:5 1:10 1:100 thuringiensis
Bacillus
Cl-73 1 and thuringiensis 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 delta- endotoxin
NPV (e.g.,
Cl-74 1 and 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Gemstar) Table C2
Table C2 is identical to Table CI , except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 2. For example, the first weight ratio entry of the first line of Table C2 specifically discloses the mixture of Compound 1 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.
Table C3
Table C3 is identical to Table CI , except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 3. For example, the first weight ratio entry of the first line of Table C3 specifically discloses the mixture of Compound 3 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 3 to 1 part abamectin.
Table C4
Table C4 is identical to Table CI , except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 4. For example, the first weight ratio entry of the first line of Table C4 specifically discloses the mixture of Compound 4 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 4 to 1 part abamectin.
Table C5
Table C5 is identical to Table CI , except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 5. For example, the first weight ratio entry of the first line of Table C5 specifically discloses the mixture of Compound 5 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 5 to 1 part abamectin.
Table C6
Table C6 is identical to Table CI , except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 6. For example, the first weight ratio entry of the first line of Table C6 specifically discloses the mixture of Compound 6 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 6 to 1 part abamectin.
Table C7
Table C7 is identical to Table CI , except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 7. For example, the first weight ratio entry of the first line of Table C7 specifically discloses the mixture of Compound 7 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 7 to 1 part abamectin. Table C8
Table C8 is identical to Table CI , except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 8. For example, the first weight ratio entry of the first line of Table C8 specifically discloses the mixture of Compound 8 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 8 to 1 part abamectin.
Table C9
Table C9 is identical to Table CI , except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 9. For example, the first weight ratio entry of the first line of Table C9 specifically discloses the mixture of Compound 9 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 9 to 1 part abamectin.
Table CIO
Table CIO is identical to Table CI, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 10. For example, the first weight ratio entry of the first line of Table CIO specifically discloses the mixture of Compound 10 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 10 to 1 part abamectin.
Table CI 1
Table C 11 is identical to Table C 1 , except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 11. For example, the first weight ratio entry of the first line of Table C 11 specifically discloses the mixture of Compound 11 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 11 to 1 part abamectin.
Table C 12
Table C12 is identical to Table CI, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 12. For example, the first weight ratio entry of the first line of Table C12 specifically discloses the mixture of Compound 12 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 12 to 1 part abamectin.
Table C 13
Table C13 is identical to Table CI, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 13. For example, the first weight ratio entry of the first line of Table C13 specifically discloses the mixture of Compound 13 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 13 to 1 part abamectin. Table C 14
Table C14 is identical to Table CI, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 14. For example, the first weight ratio entry of the first line of Table C14 specifically discloses the mixture of Compound 14 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 14 to 1 part abamectin.
Table C 15
Table C15 is identical to Table CI, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 15. For example, the first weight ratio entry of the first line of Table C15 specifically discloses the mixture of Compound 15 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 15 to 1 part abamectin.
Table C 16
Table C16 is identical to Table CI, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 16. For example, the first weight ratio entry of the first line of Table C16 specifically discloses the mixture of Compound 16 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 16 to 1 part abamectin.
Table C 17
Table C17 is identical to Table CI, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 17. For example, the first weight ratio entry of the first line of Table C17 specifically discloses the mixture of Compound 17 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 17 to 1 part abamectin.
Table C18
Table C18 is identical to Table CI, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 18. For example, the first weight ratio entry of the first line of Table C 18 specifically discloses the mixture of Compound 18 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 18 to 1 part abamectin.
Table C 19
Table C19 is identical to Table CI, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 19. For example, the first weight ratio entry of the first line of Table C19 specifically discloses the mixture of Compound 19 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 19 to 1 part abamectin. Listed below in Tables Dl to D19 are embodiments of specific compositions comprising a compound of Formula 1 (compound numbers (Cmpd. No.) refer to compounds in Index Table A) and an additional fungicide.
Table Dl
Mixture Cmpd. and Mixture No. Cmpd. and
Fungicide Fungicide
No. No. No.
Dl-1 1 and Probenazole Dl-17 1 and Difenoconazole
Dl-2 1 and Tiadinil Dl-18 1 and Cyproconazole
Dl-3 1 and Isotianil Dl-19 1 and Propiconazole
Dl-4 1 and Pyroquilon Dl-20 1 and Fenoxanil
Dl-5 1 and Metominostrobin Dl-21 1 and Ferimzone
Dl-6 1 and Flutolanil Dl-22 1 and Fthalide
Dl-7 1 and Validamycin Dl-23 1 and Kasugamycin
Dl-8 1 and Furametpyr Dl-24 1 and Picoxystrobin
Dl-9 1 and Pencycuron Dl-25 1 and Penthiopyrad
Dl-10 1 and Simeconazole Dl-26 1 and Famoxadone
Dl-11 1 and Orysastrobin Dl-27 1 and Cymoxanil
Dl-12 1 and Trifloxystrobin Dl-28 1 and Proquinazid
Dl-13 1 and Isoprothiolane Dl-29 1 and Flusilazole
Dl-14 1 and Azoxystrobin Dl-30 1 and Mancozeb
Dl-15 1 and Tricyclazole Dl-31 1 and Copper hydroxide
Dl-16 1 and Hexaconazole Dl-32 1 and (a)
(a) l-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-l-piperidinyl]-2-[5-methyl-3- (trifluoromethyl)- l /-pyrazol- 1 -yljethanone
Table D2
Table D2 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 2. For example, the first mixture in Table D2 is designated D2-1 and is a mixture of compound 2 and the additional fungicide probenazole.
Table D3
Table D3 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 3. For example, the first mixture in Table D3 is designated D3-1 and is a mixture of compound 3 and the additional fungicide probenazole.
Table D4
Table D4 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 4. For example, the first mixture in Table D4 is designated D4-1 and is a mixture of compound 4 and the additional fungicide probenazole.
Table D5
Table D5 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 5. For example, the first mixture in Table D5 is designated D5-1 and is a mixture of compound 5 and the additional fungicide probenazole.
Table D6
Table D6 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 6. For example, the first mixture in Table D6 is designated D6-1 and is a mixture of compound 6 and the additional fungicide probenazole.
Table D7
Table D7 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 7. For example, the first mixture in Table D7 is designated D7-1 and is a mixture of compound 7 and the additional fungicide probenazole.
Table D8
Table D8 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 8. For example, the first mixture in Table D8 is designated D8-1 and is a mixture of compound 8 and the additional fungicide probenazole.
Table D9
Table D9 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 9. For example, the first mixture in Table D9 is designated D9-1 and is a mixture of compound 9 and the additional fungicide probenazole.
Table DIP
Table D10 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 10. For example, the first mixture in Table D10 is designated DlO-1 and is a mixture of compound 10 and the additional fungicide probenazole.
Table Dl l
Table Dl 1 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 11. For example, the first mixture in Table Dl 1 is designated Dl 1-1 and is a mixture of compound 11 and the additional fungicide probenazole.
Table D 12
Table D12 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 12. For example, the first mixture in Table D12 is designated D12-1 and is a mixture of compound 12 and the additional fungicide probenazole.
Table D13
Table D13 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 13. For example, the first mixture in Table D13 is designated D13-1 and is a mixture of compound 13 and the additional fungicide probenazole.
Table D 14
Table D14 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 14. For example, the first mixture in Table D14 is designated D14-1 and is a mixture of compound 14 and the additional fungicide probenazole.
Table D15
Table D15 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 15. For example, the first mixture in Table D15 is designated D15-1 and is a mixture of compound 15 and the additional fungicide probenazole.
Table D16
Table D16 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 16. For example, the first mixture in Table D16 is designated D16-1 and is a mixture of compound 16 and the additional fungicide probenazole.
Table D17
Table D17 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 17. For example, the first mixture in Table D17 is designated D17-1 and is a mixture of compound 17 and the additional fungicide probenazole.
Table Dl 8
Table D18 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 18. For example, the first mixture in Table D18 is designated D18-1 and is a mixture of compound 18 and the additional fungicide probenazole.
Table D19
Table D19 is identical to Table Dl, except that each reference to compound 1 in the column headed "Cmpd. No." is replaced by a reference to compound 19. For example, the first mixture in Table D19 is designated D19-1 and is a mixture of compound 19 and the additional fungicide probenazole.
Invertebrate pests are controlled in agronomic and nonagronomic applications by applying one or more compounds of this invention, typically in the form of a composition, in a biologically effective 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.
Thus the present invention comprises a method for controlling an invertebrate pest in agronomic and/or nonagronomic applications, comprising contacting the invertebrate pest or its environment with a biologically effective amount of one or more of the compounds of the invention, or with a composition comprising at least one such compound or a composition comprising at least one such compound and a biologically effective amount of at least one additional biologically active compound or agent. Examples of suitable compositions comprising a compound of the invention and a biologically effective amount of at least one additional biologically active compound or agent include granular compositions wherein the additional active compound is present on the same granule as the compound of the invention or on granules separate from those of the compound of the invention.
Embodiments of the method of this invention include contacting the environment. Of note is the method wherein the environment is a plant. Also of note is the method wherein the environment is an animal. Also of note is the method wherein the environment is a seed.
To achieve contact with a compound or composition of the invention to protect a field crop from invertebrate pests, the compound or composition is typically applied to the seed of the crop before planting, to the foliage (e.g., leaves, stems, flowers, fruits) of crop plants, or to the soil or other growth medium before or after the crop is planted.
One embodiment of a method of contact is by spraying. Alternatively, a granular composition comprising a compound of the invention can be applied to the plant foliage or the soil. Compounds of this invention can also be effectively delivered through plant uptake by contacting the plant with a composition comprising a compound of this invention applied as a soil drench of a liquid formulation, a granular formulation to the soil, a nursery box treatment or a dip of transplants. Of note is a composition of the present invention in the form of a soil drench liquid formulation. Also of note is a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of the present invention or with a composition comprising a biologically effective amount of a compound of the present invention. Of further note is this method wherein the environment is soil and the composition is applied to the soil as a soil drench formulation. Of further note is that compounds of this invention are also effective by localized application to the locus of infestation. Other methods of contact include application of a compound or a composition 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. One embodiment of a method of contact is a dimensionally stable fertilizer granule, stick or tablet comprising a compound or composition of the invention. The compounds of this invention can also be impregnated into materials for fabricating invertebrate control devices (e.g., insect netting).
Compounds of this invention are also useful in seed treatments for protecting seeds from invertebrate pests. In the context of the present disclosure and claims, treating a seed means contacting the seed with a biologically effective amount of a compound of this invention, which is typically formulated as a composition of the invention. This seed treatment protects the seed from invertebrate soil pests and generally can also protect roots and other plant parts in contact with the soil of the seedling developing from the germinating seed. The seed treatment may also provide protection of foliage by translocation of the compound of this invention or a second active ingredient within the developing plant. Seed treatments 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 glyphosate acetyltransferase, which provides resistance to glyphosate. Seed treatments with compounds of this invention can also increase vigor of plants growing from the seed.
One method of seed treatment is by spraying or dusting the seed with a compound of the invention (i.e. as a formulated composition) before sowing the seeds. Compositions formulated for seed treatment generally comprise a film former or adhesive agent. Therefore typically a seed coating composition of the present invention comprises a biologically effective amount of a compound of Formula 1 and a film former or adhesive agent. Seed can be coated by spraying a flowable suspension concentrate directly into a tumbling bed of seeds and then drying the seeds. Alternatively, other formulation types such as wetted powders, solutions, suspoemulsions, emulsifiable concentrates and emulsions in water can be sprayed on the seed. This process is particularly useful for applying film coatings on seeds. Various coating machines and processes are available to one skilled in the art. Suitable processes include those listed in P. Kosters et al, Seed Treatment: Progress and Prospects, 1994 BCPC Mongraph No. 57, and references listed therein.
Compounds of Formula 1 and their compositions, both alone and in combination with other insecticides and fungicides, are particularly useful in seed treatment for crops including, but not limited to, maize or corn, soybeans, cotton, cereal (e.g., wheat, oats, barley, rye and rice), potatoes, vegetables and oilseed rape.
Other insecticides with which compounds of Formula 1 can be formulated to provide mixtures useful in seed treatment include abamectin, acetamiprid, acrinathrin, amitraz, avermectin, azadirachtin, bensultap, bifenthrin, buprofezin, cadusafos, carbaryl, carbofuran, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flonicamid, flubendiamide, flufenoxuron, fluvalinate, formetanate, fosthiazate, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, metaflumizone, methiodicarb, methomyl, methoprene, methoxyfenozide, nitenpyram, nithiazine, novaluron, oxamyl, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide, tetramethrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate, triflumuron, Bacillus thuringiensis delta-endotoxins, all strains of Bacillus thuringiensis and all strains of Nucleo polyhydrosis viruses.
Fungicides with which compounds of Formula 1 can be formulated to provide mixtures useful in seed treatment include amisulbrom, azoxystrobin, boscalid, carbendazim, carboxin, cymoxanil, cyproconazole, difenoconazole, dimethomorph, fluazinam, fludioxonil, fluquinconazole, fluopicolide, fluoxastrobin, flutriafol, fluxapyroxad, ipconazole, iprodione, metalaxyl, mefenoxam, metconazole, myclobutanil, paclobutrazole, penflufen, picoxystrobin, prothioconazole, pyraclostrobin, sedaxane, silthiofam, tebuconazole, thiabendazole, thiophanate-methyl, thiram, trifloxystrobin and triticonazole.
Compositions comprising compounds of Formula 1 useful for seed treatment can further comprise bacteria such as Bacillus pumilus (e.g., strain GB34) and Bacillus firmus (e.g., isolate 1582), rhizobia inoculants/extenders, isoflavonoids and lipo- chitooligo saccharides .
The treated seed typically comprises a compound of the present invention in an amount from about 0.1 g to 1 kg per 100 kg of seed (i.e. from about 0.0001 to 1% by weight of the seed before treatment). A flowable suspension formulated for seed treatment typically comprises from about 0.5 to about 70% of the active ingredient, from about 0.5 to about 30% of a film- forming adhesive, from about 0.5 to about 20% of a dispersing agent, from 0 to about 5% of a thickener, from 0 to about 5% of a pigment and/or dye, from 0 to about 2% of an antifoaming agent, from 0 to about 1% of a preservative, and from 0 to about 75% of a volatile liquid diluent. The compounds of this invention can be incorporated into a bait composition that is consumed by an invertebrate pest 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 biologically effective amount of a compound of Formula 1 an N-oxide, or salt thereof; (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 0.001-5% 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 lethal by ingestion rather than by direct contact. 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 invertebrate 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 control at least one invertebrate pest selected from the group consisting of ants, termites and cockroaches. A device for controlling an invertebrate pest can comprise the present 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 invertebrate 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 invertebrate pest.
The compounds of this invention can be applied without other adjuvants, but most often application will be of a formulation comprising one or more active ingredients with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. One method of application involves spraying a water dispersion or refined oil solution of a compound of the present invention. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance compound 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 needed for application. Of note is a spray composition comprising a biologically effective amount of a compound or a composition of the present invention and a carrier. One embodiment of such a spray composition comprises a biologically effective amount of a compound or a composition 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 invertebrate 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.
Nonagronomic uses refer to invertebrate pest control in the areas other than fields of crop plants. Nonagronomic uses of the present compounds and compositions include control of invertebrate pests in stored grains, beans and other foodstuffs, and in textiles such as clothing and carpets. Nonagronomic uses of the present compounds and compositions also include invertebrate pest control in ornamental plants, forests, in yards, along roadsides and railroad rights of way, and on turf such as lawns, golf courses and pastures. Nonagronomic uses of the present compounds and compositions also include invertebrate pest control in houses and other buildings which may be occupied by humans and/or companion, farm, ranch, zoo or other animals. Nonagronomic uses of the present compounds and compositions also include the control of pests such as termites that can damage wood or other structural materials used in buildings.
For agronomic applications, the rate of application required for effective control (i.e. "biologically effective amount") will depend on such factors as the species of invertebrate to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredients per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.0001 kg/hectare may be sufficient or as much as 8 kg/hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required. One skilled in the art can easily determine the biologically effective amount necessary for the desired level of invertebrate pest control. Biologically effective amounts for increasing plant vigor are generally similar to biologically effective amounts for invertebrate pest control, and optimal amounts to achieve particular aspects of plant vigor enhancement can determined through simple experimentation.
Representative compounds of this invention prepared by the methods described herein are shown in Index Table A. See Index Table B for 1H NMR data. For mass spectral data (AP+ (M+l)), the numerical value reported is the molecular weight of the parent molecular ion (M) formed by addition of H+ (molecular weight of 1) to the molecule to give a M+l peak observed by mass spectrometry using atmospheric pressure chemical ionization (AP+). The alternate molecular ion peaks (e.g., M+2 or M+4) that occur with compounds containing multiple halogens are not reported.
The following abbreviations are used in the Index Tables which follow: Cmpd means Compound.
INDEX TABLE A
Figure imgf000118_0001
Cmpd Ei m.D. CO AP+ (M+l)
1 phenyl 211-212
2 4-fluorophenyl 349
3 3 -(trifluoromethyl)phenyl 183-185
4 2 -methoxyphenyl 361
5 3 -methoxyphenyl 361
6 2,4-difluorophenyl *
7 3 -(trifluoromethoxy)phenyl 415
8 3-bromophenyl *
9 2-fluorophenyl 349
10 2 - fluoro- 5 - (trifluoromethyl)phenyl *
11 3-methylphenyl *
12 4-fluoro-3-(trifluoromethyl)phenyl 417
13 4- chloro-2 - fluorophenyl 459
14 2-chlorophenyl 365
15 3 - chloro- 5 - (trifluoromethyl)phenyl 433
16 3 ,5 -dichlorophenyl 399
17 3,5-dichloro-4-fluorophenyl 417
18 4 ' - cy ano- 5 ,2 ' -dimethyl [ 1 , Γ -biphenyl] - 3 -yl 460
19 3-chlorophenyl *
* See Index Table B for lU NMR data. INDEX TABLE B
Cmpd IH NMR Data a
6 (acetone-d6) δ 9.41 (d, 1H), 9.07 (s, 1H), 8.89 (s, 2H), 8.36 (t, 1H), 7.96 (d, 1H), 7.56-7.58
(m, 2H), 6.96-7.00 (m, 2H), 5.74 (s, 2H).
8 (acetone-d6) δ 9.47 (d, 1H), 9.07 (s, 1H), 8.90 (s, 2H), 8.36 (t, 1H), 8.19 (s, 1H), 7.93-7.95
(m, 2H), 7.59 (t, 1H), 7.24-7.30 (m, 2H), 5.76 (s, 2H).
10 (acetone-d6) δ 9.43 (d, 1H), 9.07 (s, 1H), 8.90 (s, 2H), 8.39 (t, 1H), 7.98 (d, 1H), 7.95 (dd, 1H), 7.64-7.68 (m, 1H), 7.60 (t, 1H), 7.35 (t, 1H), 5.76 (s, 2H).
11 (dmso-d6) δ 9.33 (d, 1H), 9.11 (s, 1H), 8.82 (s, 2H), 8.27 (t, 1H), 7.87 (d, 1H), 7.47-7.54 (m, 2H), 7.26 (t, 1H), 6.99 (d, 1H), 5.59 (s, 2H), 2.31 (s, 3H).
19 (dmso-d6) δ 9.34 (d, 1H), 9.11 (s, 1H), 8.83 (s, 2H), 8.29 (dt, 1H), 7.77-7.88 (m, 3H), 7.55
(dt, 1H), 7.32-7.36 (m, 1H), 7.23 (d, 1H), 5.60 (s, 2H).
A NMR data are in ppm downfield from tetramethylsilane. CDCI3 solution unless indicated otherwise; "acetone-dg" is CD3C(=0)CD3, "dmso-dg" is CD3 S(=0)CD3. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (m)-multiplet, (dd)-doublet of doublets, (dt)-doublet of triplets, (br s)-broad singlet.
The following Tests demonstrate the control efficacy of compounds of this invention on specific pests. "Control efficacy" represents inhibition of invertebrate pest development (including mortality) that causes significantly reduced feeding. The pest control protection afforded by the compounds is not limited, however, to these species. Compound numbers refer to compounds in Index Table A.
BIOLOGICAL EXAMPLES OF THE INVENTION
TEST A
For evaluating control of diamondback moth (Plutella xylostella) the test unit consisted of a small open container with a 12-14-day-old radish plant inside. This was pre-infested with ~50 neonate larvae that were dispensed into the test unit via corn cob grits using a bazooka inoculator. The larvae moved onto the test plant after being dispensed into the test unit.
Test compounds were formulated using a solution containing 10% acetone, 90% water and 300 ppm X-77® Spreader Lo-Foam Formula non-ionic surfactant containing alkylarylpolyoxyethylene, free fatty acids, glycols and isopropanol (Loveland Industries, Inc. Greeley, Colorado, USA). The formulated compounds were applied in 1 mL of liquid through a SUJ2 atomizer nozzle with 1/8 JJ custom body (Spraying Systems Co., Wheaton, Illinois, USA) positioned 1.27 cm (0.5 inches) above the top of each test unit. Test compounds were sprayed at 250, 50 and/or 10 ppm, and replicated three times. After spraying of the formulated test compound, each test unit was allowed to dry for 1 h and then a black, screened cap was placed on top. The test units were held for 6 days in a growth chamber at 25 °C and 70% relative humidity. Plant feeding damage was then visually assessed based on foliage consumed.
Of the compounds of Formula 1 tested at 250 ppm, the following provided very good to excellent levels of control efficacy (40% or less feeding damage and/or 100% mortality): 1, 3, 4, 7, 8, 13 and 15.
Of the compounds of Formula 1 tested at 50 ppm, the following provided very good to excellent levels of control efficacy (40% or less feeding damage and/or 100% mortality): 1, 3, 4, 5, 8 and 19.
Of the compounds of Formula 1 tested at 10 ppm, the following provided very good to excellent levels of control efficacy (40% or less feeding damage and/or 100% mortality): 7, 15, 16 and 17.
TEST B
For evaluating control of green peach aphid (Myzus persicae) through contact and/or systemic means, the test unit consisted of a small open container with a 12- 15 -day-old radish plant inside. This was pre-infested by placing on a leaf of the test plant 30-40 aphids on a piece of leaf excised from a culture plant (cut-leaf method). The aphids moved onto the test plant as the leaf piece desiccated. After pre-infestation, the soil of the test unit was covered with a layer of sand.
Test compounds were formulated and sprayed at 250, 50 and/or 10 ppm as described for Test A. The applications were replicated three times. After spraying of the formulated test compound, each test unit was allowed to dry for 1 h and then a black, screened cap was placed on top. The test units were held for 6 days in a growth chamber at 19-21 °C and 50- 70% relative humidity. Each test unit was then visually assessed for insect mortality.
Of the compounds of Formula 1 tested at 250 ppm, the following resulted in at least 80% mortality: 1 and 3.
Of the compounds of Formula 1 tested at 50 ppm, the following resulted in at least 80% mortality: 1, 3, 15, 16 and 19.
Of the compounds of Formula 1 tested at 10 ppm, the following resulted in at least 80% mortality: 15.
TEST C
For evaluating control of cotton melon aphid (Aphis gossypii) through contact and/or systemic means, the test unit consisted of a small open container with a 6-7-day-old cotton plant inside. This was pre-infested with 30-40 insects on a piece of leaf according to the cut- leaf method described for Test B, and the soil of the test unit was covered with a layer of sand. Test compounds were formulated and sprayed at 250 and/or 50 ppm as described for Test B. The applications were replicated three times. After spraying, the test units were maintained in a growth chamber and then visually rated as described for Test C.
Of the compounds of Formula 1 tested at 250 ppm, the following resulted in at least 80% mortality: 1 and 3.
Of the compounds of Formula 1 tested at 50 ppm, the following resulted in at least 80% mortality: 3, 7 and 12.
TEST D
For evaluating control of corn planthopper (Peregrinus maidis) through contact and/or systemic means, the test unit consisted of a small open container with a 3-4-day-old maize plant (spike) inside. White sand was added to the top of the soil prior to application. Test compounds were formulated and sprayed at 250, 50, 10 and/or 2 ppm, and replicated three times as described for Test A. After spraying, the test units were allowed to dry for 1 h before they were post-infested with -15-20 nymphs (18 to 21 day old) by sprinkling them onto the sand with a salt shaker. A black, screened cap was placed on the top of each test unit, and the test units were held for 6 days in a growth chamber at 22-24 °C and 50-70% relative humidity. Each test unit was then visually assessed for insect mortality.
Of the compounds of Formula 1 tested at 250 ppm the following provided very good to excellent levels of control efficacy (80% or more mortality): 1, 2, 3 and 10.
Of the compounds of Formula 1 tested at 50 ppm the following provided very good to excellent levels of control efficacy (80%> or more mortality): 1, 2, 3, 4, 5, 9, 10, 11, 12, 15, 16, 17, 18 and 19.
Of the compounds of Formula 1 tested at 10 ppm the following provided very good to excellent levels of control efficacy (80%> or more mortality): 1, 2, 3, 5, 10, 11, 12, 15, 16, 17 and 19.
Of the compounds of Formula 1 tested at 2 ppm the following provided very good to excellent levels of control efficacy (80% or more mortality): 2, 3 and 15.
TEST E
For evaluating control of potato leafhopper (Empoasca fabae) through contact and/or systemic means, the test unit consisted of a small open container with a 5-6-day-old Soleil bean plant (primary leaves emerged) inside. White sand was added to the top of the soil and one of the primary leaves was excised prior to application.
Test compounds were formulated and sprayed at 250, 50, 10 and/or 2 ppm, and the tests were replicated three times as described for Test A. After spraying, the test units were allowed to dry for 1 h before they were post-infested with 5 potato leafhoppers (18-21 -day- old adults). A black, screened cap was placed on the top of each test unit, and the test units were held for 6 days in a growth chamber at 24 °C and 70% relative humidity. Each test unit was then visually assessed for insect mortality.
Of the compounds of Formula 1 tested at 250 ppm the following provided very good to excellent levels of control efficacy (80% or more mortality): 1 and 3.
Of the compounds of Formula 1 tested at 50 ppm the following provided very good to excellent levels of control efficacy (80%> or more mortality): 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 15, 18 and 19.
Of the compounds of Formula 1 tested at 10 ppm the following provided very good to excellent levels of control efficacy (80%> or more mortality): 1, 2, 3, 5, 6, 7, 9, 11, 12, 15 and 19.
Of the compounds of Formula 1 tested at 2 ppm the following provided very good to excellent levels of control efficacy (80% or more mortality): 1, 7 and 15.
TEST F
For evaluating control of Western Flower Thrips {Frankliniella occidentalis) through contact and/or systemic means, the test unit consisted of a small open container with a 5-7- day-old Soleil bean plant inside.
Test compounds were formulated and sprayed at 250 ppm, and the tests were replicated three times as described for Test A. After spraying, the test units were allowed to dry for 1 hour, and then 22-27 adult thrips were added to the unit. A black, screened cap was placed on the top of each test unit, and the test units were held for 7 days at 25 °C and 45-55% relative humidity.
Of the compounds of Formula 1 tested at 250 ppm, the following provided very good to excellent levels of control efficacy (30% or less plant damage and/or 100% mortality): 1 and 4.
TEST G
For evaluating control of rice green leafhopper (Nephotettix virescens) through contact and/or systemic means, the test unit consisted of a plastic pot containing a 13-cm-tall rice plant covered with steel wire mesh (50 mesh) supported by a wire frame. A small amount of sand was added to form a good seal between the bottom of the wire mesh, the soil surface and the top edge of the plastic pot.
Test compounds were formulated and sprayed at 50, 10 and/or 2 ppm, and the tests were replicated three times in a manner similar to the one described for Test A. After spraying, the test units were allowed to dry for 2 h before they were post-infested with 10 green leafhoppers (3rd instar nymphs, 7-9 days post-hatch). After 5 days, each test unit was visually assessed for insect mortality.
Of the compounds of Formula 1 tested at 50 ppm the following provided very good to excellent levels of control efficacy (80% or more mortality): 2, 3, 7, 10, 11 and 12. Of the compounds of Formula 1 tested at 10 ppm the following provided very good to excellent levels of control efficacy (80% or more mortality): 2, 3, 7, 10 and 11.
Of the compounds of Formula 1 tested at 2 ppm the following provided very good to excellent levels of control efficacy (80% or more mortality): 3 and 7.
TEST H
For evaluating control of rice brown planthopper (Nilaparvata lugens) through contact and/or systemic means, the test unit consisted of a plastic pot containing a 13-cm-tall rice plant covered with steel wire mesh (50 mesh) supported by a wire frame. A small amount of sand was added to form a good seal between the bottom of the wire mesh, the soil surface and the top edge of the plastic pot.
Test compounds were formulated and sprayed at 10, 2 and/or 0.4 ppm, and the tests were replicated three times in a manner similar to the one described for Test A. After spraying, the test units were allowed to dry for 2 h before they were post-infested with 10 brown planthoppers (3rd instar nymphs, 7-9 days post-hatch). After 5 days, each test unit was visually assessed for insect mortality.
Of the compounds of Formula 1 tested at 10 ppm the following provided very good to excellent levels of control efficacy (80%> or more mortality): 2, 3, 7, 9, 10, 11, 12 and 15.
Of the compounds of Formula 1 tested at 2 ppm the following provided very good to excellent levels of control efficacy (80% or more mortality): 2, 3, 7 and 10.
Of the compounds of Formula 1 tested at 0.4 ppm the following provided very good to excellent levels of control efficacy (80% or more mortality): 7.
To evaluate the effect of application of a compound of the invention on the vigor of rice crops grown under outdoor conditions, Tests I through O were conducted, "a.i." refers to the amount of active ingredient applied.
TEST I
Rice plants (indica cultivar 'MTU1010') were transplanted into flooded 5 m x 3 m test plots of clay loam soil in the delta region of the West Godavri district, Andhra Pradesh, India, during the rainy season, and grown using local agronomic practices. After 47 days, aqueous mixtures of Compound 3 were applied to the foliage of the rice plants at 12.5, 25 or 50 g a.i./ha in a spray volume of 387 L/ha using a backpack sprayer. Plots of unsprayed rice plants were used as controls. Each treatment and control was replicated three times, and the plots were arranged in a randomized complete block design. At the time of application of Compound 3, the pest level of rice brown planthopper {Nilaparvata lugens) was high, i.e. much above the level considered economically significant.
The crop vigor of the rice plants in each plot was visually rated based on general external appearance (e.g., plant height) 20 days after application on a 0 to 200% scale, wherein the plants in untreated control plots were considered to represent 100%, and the results for the three replicates for each treatment were averaged. More than 100% means the plants in a treated plot were more vigorous than those in the untreated control plot, while less than 100% means the plants in the treated pot were less vigorous. The rice plants treated with 12.5, 25 and 50 g a.i./ha of Compound 3 demonstrated 140%), 143% and 143% crop vigor, respectively, compared to 100%) of untreated controls.
TEST J
Rice plants (indica cultivar 'MTU1010') were transplanted into flooded 5 m x 3 m test plots of clay loam soil in the delta region of the West Godavri district, Andhra Pradesh, India, during the rainy season, and grown using local agronomic practices. After 52 days, aqueous mixtures of Compound 3 were applied to the foliage of the rice plants at 12.5, 25 or 50 g a.i./ha in a spray volume of 387 L/ha using a backpack sprayer. Plots of unsprayed rice plants were used as controls. Each treatment and control was replicated three times, and the plots were arranged in a randomized complete block design. At the time of application of Compound 3, the pest level of rice brown planthopper {Nilaparvata lugens) was high, i.e. much above the level considered economically significant. 20 days after the first treatment, the foliar applications of aqueous mixtures of Compound 3 were repeated at the same application rates in a spray volume of 467 L/ha.
The crop vigor of the rice plants in earch plot was visually rated 48 days after first application on a 0 to 200% scale as described for Test I. The rice plants treated with 12.5, 25 and 50 g a.i./ha of Compound 3 demonstrated 148%), 148% and 148%) crop vigor, respectively, compared to 100% of untreated controls.
TEST
Rice plants (indica cultivar 'JAY A') were transplanted into flooded 6 m x 5 m test plots of clay loam soil under shade cloth in the State of Gujarat, India during the hot season before monsoon arrival, and grown using local agronomic practices. Accordingly, after 44 days from transplanting, all rice plants in this test were sprayed with an aqueous mixture containing 30 g a.i./ha of cypermethrin and 100 g a.i./ha of picoxystrobin. After 53 days from transplanting, aqueous mixtures of Compound 3 were applied to the foliage of the rice plants at 6.25, 12.5, 25 or 50 g a.i./ha in a spray volume of 500 L/ha using a backpack sprayer. Plots of unsprayed rice plants were used as controls. Each treatment and control was replicated three times, and the plots were arranged in a randomized complete block design. At the time of application of Compound 3, the pest level of rice brown planthopper {Nilaparvata lugens) was moderate, but still above the level considered economically significant.
The crop vigor of the rice plants in each plot was visually rated 32 days after application on a 0 to 200% scale as described for Test I. The rice plants treated with 6.25, 12.5, 25 and 50 g a.i./ha of Compound 3 demonstrated 115%, 113%, 122% and 115% crop vigor, respectively, compared to 100% of untreated controls.
At 45 days after application, the height and panicle length of the rice plants were measured. Plant height was determined by measuring length from vertically extended longest leaf tip to soil surface. Panicle length was measured similarly. The average height of rice plants treated with 6.25, 12.5, 25 and 50 g a.i./ha of Compound 3 was 0.94, 0.92, 0.92 and 0.99 m, respectively, compared to 0.78 m for untreated control plants. The average panicle length of rice plants treated with 6.25, 12.5, 25 and 50 g a.i./ha of Compound 3 was 23.8, 23.7, 24.9 and 24.6 cm, respectively, compared to 22.4 cm for untreated control plants. While the only treatments with Compound 3 at 25 and 50 g a.i./ha significantly increased panicle length, all the treatments substantially increased plant height.
TEST L
Rice plants (indica cultivar 'IR 64') were transplanted into flooded 6 m x 5 m test plots of clay loam soil in the Dhamtari district, State of Chhattisgarh, India, in the early spring season, and grown using local agronomic practices. After 79 days, in the hot season before monsoon arrival, aqueous mixtures containing 30 g a.i./ha of indoxacarb in form of STEWARD® Insecticide, 20 g a.i./ha of chlorantraniliprole, and 6.25, 12.5, 25 or 50 g a.i./ha of Compound 3 were applied to the foliage of the rice plants at in a spray volume of 500 L/ha using a backpack sprayer. Plots of control rice plants were sprayed with an aqueous mixture containing 30 g a.i./ha of indoxacarb in form of STEWARD® Insecticide and 20 g a.i./ha of chlorantraniliprole (i.e. no Compound 3). Each treatment and control was replicated three times, and the plots were arranged in a randomized complete block design. At the time of application of Compound 3, the pest level of rice brown planthopper {Nilaparvata lugens) was high, i.e. above the level considered economically significant.
The crop vigor of the rice plants in each plot was visually rated 21 days after application on a 0 to 200% scale as described for Test I. At all application rates the treated rice plants showed the same level of crop vigor (i.e. 100%) as untreated control plants. Even though the pest level was high, at the time of treatment the plants had already reached full height and produced panicles, so the treatment with Compound 3 was too late to noticeably increase crop vigor rated by general external appearance (e.g., plant height, number of panicles). Nevertheless, the treatments substantially benefited crop vigor as measured by harvest yield. Harvest yields from the crops treated with 6.25, 12.5, 25 and 50 g a.i./ha of Compound 3 were 4630, 4830, 4730 and 4930 kg/ha, respectively, compared to 2630 kg/ha from the untreated controls. Therefore even the late treatments substantially increased crop yield by preventing planthopper damage that would otherwise stop the process of grain filling, resulting in empty panicles. TEST M
Rice plants (indica cultivar) were direct seeded into flooded 6 m χ 5 m test plots of clay loam soil in An Giang Province of Vietnam shortly before the monsoon, and grown using local agronomic practices. After 42 days, at the beginning of the wet season, aqueous mixtures containing 30 g a.i./ha of indoxacarb in form of STEWARD® Insecticide, 20 g a.i./ha of chlorantraniliprole, and 6.25, 12.5, 25 or 50 g a.i./ha of Compound 3 were applied to the foliage of the rice plants at in a spray volume of 400 L/ha using a motorized sprayer. Plots of control rice plants were sprayed with an aqueous mixture containing 30 g a.i./ha of indoxacarb in form of STEWARD® Insecticide and 20 g a.i./ha of chlorantraniliprole (i.e. no Compound 3). Each treatment and control was replicated three times, and the plots were arranged in a randomized complete block design. At the time of application of Compound 3, the pest level of rice brown planthopper {Nilaparvata lugens) was very low.
The crop vigor of the rice plants in each plot was visually rated 18 days after application on a 0 to 200% scale as described for Test I. At all application rates the treated rice plants showed the same level of crop vigor (i.e. 100%) as untreated control plants. Because the pest level was very low and growing conditions were ideal, applications of Compound 3 did not noticeably increase plant vigor.
TEST N
Rice plants (indica cultivar 'Swarna') were transplanted into flooded 4 m x 3 m test plots of clay loam soil in the Bargarh district, Orissa, India, during the rainy season, and grown using local agronomic practices. After 70 days, aqueous mixtures of Compound 3 were applied to the foliage of the rice plants at 12.5, 25 or 50 g a.i./ha in a spray volume of 400 L/ha using a backpack sprayer. Plots of unsprayed rice plants were used as controls. Each treatment and control was replicated three times, and the plots were arranged in a randomized complete block design. At the time of application of Compound 3, the pest level of rice brown planthopper {Nilaparvata lugens) was high, i.e. much above the level considered economically significant. 14 days after the first treatment, the foliar applications of aqueous mixtures of Compound 3 were repeated at the same application rates in a spray volume of 400 L/ha.
Harvest yields from the crops treated with 12.5, 25 and 50 g a.i./ha of Compound 3 were 3190, 3660 and 4220 kg/ha, respectively, compared to 620 kg/ha from the untreated controls.
TEST O
Rice plants (indica cultivar 'IR-64') were transplanted into flooded 5 m x 5 m test plots of clay loam soil the Bargarh district, Orissa, India, at the end of the winter season, and grown using local agronomic practices. After 79 days, aqueous mixtures containing 30 g a.i./ha of indoxacarb in form of STEWARD® Insecticide, 20 g a.i./ha of chlorantraniliprole, and 6.25, 12.5, 25 or 50 g a.i./ha of Compound 3 were applied to the foliage of the rice plants at in a spray volume of 500 L/ha using a backpack sprayer. Plots of control rice plants were sprayed with an aqueous mixture containing 30 g a.i./ha of indoxacarb in form of STEWARD® Insecticide and 20 g a.i./ha of chlorantraniliprole (i.e. no Compound 3). Each treatment and control was replicated three times, and the plots were arranged in a randomized complete block design. At the time of application of Compound 3, the pest level of rice brown planthopper {Nilaparvata lugens) was high, i.e. much above the level considered economically significant.
Harvest yields from the crops treated with 12.5, 25 and 50 g a.i./ha of Compound 3 were 2470, 3430, 3470 and 4600 kg/ha, respectively, compared to 1370 kg/ha from the untreated controls.
TEST P
In this test, the effect of a compound of the invention on the vigor of maize plants grown in a greenhouse in absence of pest pressure was measured.
Single maize seeds (Prairie Hybrid 2431 organic field corn) were planted 2.0 to 2.5 cm deep in 10 cm x 10 cm x 8 cm plastic pots containing either Redi-Earth sphagnum peat moss-based potting media (Sun Gro Horticulture Canada Ltd., Vancouver, British Columbia) or a 50/50 mixture of Matapeake soil and sand. Seeded pots were initially watered to a 5 cm depth and placed in a growth chamber maintained at 25 °C withn a 16 h light / 8 h dark photoperiod. The pots were watered whenever the soil surface dried.
After 8 days from initial watering, the potted plants were treated by applying as a surface drench 40 mL of an aqueous treatment mixture containing either 0.2 or 2.5 mg of Compound 3. To the pots of untreated control plants, 40 mL of tap water was similarly applied. Treatments and untreated controls were replicated 10 times.
Treated and untreated plants were then arranged in a complete randomized block design in a greenhouse maintained at 25.6-27.8 °C during the day and 23.0-25.0 °C at night. Supplemental lighting was added when outside light levels dropped below 200 watts mr2 during a 16-h growing period, except that no supplemental lighting was activated when outside light energy had already accumulated to more than 5000 w h mr2 during the growing period. Greenhouse shading closed when outside light levels rose above 600 watts mr2 for for more than 20 minutes.
No modifications to relative humidity were made. Tap water irrigation was provided twice daily as needed to maintain soil moisture. Every second or third day the plants were fertilized with irrigation water containing 100 ppm N-P-K from Peters® soluble 20-20-20 general purpose fertilizer (The Scotts Company, Marysville, Ohio, U.S.A.). The applied nutrient levels were considered less that ideal for optimal growth of maize plants.
Plant height was determined at 0, 7, 14, 21 and 28 days after treatment by measuring the length from the vertically extended longest leaf tip to the soil surface. The heights averaged across the 10 replicates are listed in Test Tables 1 and 2 for plants grown in Redi- Earth soil and Matapeake Soil/Sand, respectively.
TEST TABLE 1
Effect of Treatments with Compound 3 on Heights of Maize Plants Grown on Redi-Earth
Soil
Figure imgf000128_0001
TEST TABLE 2
Effect of Treatments with Compound 3 on Heights of Maize Plants Grown in Matapeake
Soil/Sand
Figure imgf000128_0002
The results in Test Tables 1 and 2 show that little growth enhancing effect was noticeable from applications of Compound 3 to maize plants grown in a pest-free environment under growing conditions that were close to ideal except for being nutrient constrained.

Claims

BA9495 WO 2012/092115 PCT/US2011/066798 128 CLAIMS What is claimed is:
1. A compound of Formula 1 ,
Figure imgf000129_0001
wherein
R1 is phenyl or pyridinyl, each optionally substituted with Q and up to 3 substituents independently selected from R2;
each R2 is independently halogen, cyano, SF5, C1 -C4 alkyl, C 1 -C4 haloalkyl, C 1 -C4 10 alkoxy, C 1 -C4 haloalkoxy, C1 -C4 alkylthio or C 1 -C4 haloalkylthio; and
Q is phenyl or pyridinyl, each optionally substituted with up to 5 substituents
independently selected from the group consisting of halogen, cyano, C1-C4 alkyl, C 1 -C4 haloalkyl, C1 -C4 alkoxy and C 1 -C4 haloalkoxy.
2. A compound of Claim 1 wherein
15 R1 is phenyl optionally substituted with Q and up to 3 substituents independently selected from R2; and
Q is phenyl or pyridinyl, each optionally substituted with up to 3 substituents
independently selected from the group consisting of halogen, cyano, C1-C4 alkyl, C 1 -C4 haloalkyl, C1 -C4 alkoxy and C 1 -C4 haloalkoxy.
20 3. A compound of Claim 2 wherein
R1 is phenyl optionally substituted with up to 3 substituents independently selected from the group consisting of halogen, C 1 -C4 alkyl, C 1 -C4 haloalkyl, C1-C4 alkoxy and C 1 -C4 haloalkoxy.
4. A compound of Claim 3 that is selected from the group consisting of:
2-hydroxy-4-oxo-3 -phenyl- 1 -(5-pyrimidinylmethyl)-4H-pyrido[ 1 ,2- ajpyrimidinium inner salt;
3 -(4-fluorophenyl)-2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H-pyrido [ 1 ,2- ajpyrimidinium inner salt;
2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-3 - [3 -(trifluoromethyl)phenyl] -4H- pyrido[l,2-a]pyrimidinium inner salt;
2-hydroxy-3-(2-methoxyphenyl)-4-oxo- 1 -(5-pyrimidinylmethyl)-4H-pyrido[ 1 ,2- ajpyrimidinium inner salt;
2- hydroxy-3 -(3 -methoxyphenyl)-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H-pyrido [ 1 ,2- ajpyrimidinium inner salt;
3- (2,4-difluorophenyl)-2-hydroxy-4-oxo-l-(5-pyrimidinylmethyl)-4H- pyrido[l,2-a]pyrimidinium inner salt;
2- hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-3 - [3 -(trifluoromethoxy)phenyl] -4H- pyrido[l,2-a]pyrimidinium inner salt;
3 -(2-bromophenyl)-2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H-pyrido [1,2- ajpyrimidinium inner salt;
3 -(2-fluorophenyl)-2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H-pyrido [ 1 ,2- ajpyrimidinium inner salt;
3- [2-fluoro-5-(trifluoromethyl)phenyl]-2-hydroxy-4-oxo- 1 -(5- pyrimidinylmethyl)-4H-pyrido[l,2-a]pyrimidinium inner salt;
2- hydroxy-3 -(3 -methylphenyl)-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H-pyrido [1,2- ajpyrimidinium inner salt;
3- [4-fluoro-3-(trifluoromethyl)phenyl]-2-hydroxy-4-oxo- 1 -(5- pyrimidinylmethyl)-4H-pyrido[l,2-a]pyrimidinium inner salt (i.e. compound 12 of Index Table A);
3 -(4-chloro-2-fluorophenyl)-2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H- pyrido[l,2-a]pyrimidinium inner salt;
3 -(2-chlorophenyl)-2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H-pyrido [1,2- ajpyrimidinium inner salt;
3-[3-chloro-5-(trifiuoromethyl)phenyl]-2-hydroxy-4-oxo- 1 -(5- pyrimidinylmethyl)-4H-pyrido[l,2-a]pyrimidinium inner salt;
3 -(3 ,5 -dichlorophenyl)-2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H- pyrido[l,2-a]pyrimidinium inner salt;
3 -(3 ,5 -dichloro-4-fluorophenyl)-2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H- pyrido[l,2-a]pyrimidinium inner salt;
3-(4'-cyano-5,2'-dimethyl[l, -biphenyl]-3-yl)-2-hydroxy-4-oxo-l-(5- pyrimidinylmethyl)-4H-pyrido[l,2-a]pyrimidinium inner salt; and
3 -(3 -chlorophenyl)-2-hydroxy-4-oxo- 1 -(5 -pyrimidinylmethyl)-4H-pyrido [1,2- ajpyrimidinium inner salt.
5. A composition comprising a compound of Claim 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
6. The composition of Claim 5 further comprising at least one additional biologically active compound or agent.
7. The composition of Claim 6 wherein the at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acephate, acequinocyl, acetamiprid, acrinathrin, amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, bensultap, bifenthrin, bifenazate, bistrifluron, borate, buprofezin, cadusafos, carbaryl, carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr,
chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin, cyantraniliprole, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid, flubendiamide, flucythrinate, flufenerim, flufenoxuron, fluvalmate, tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide, hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidal soaps, isofenphos, lufenuron, malathion, metaflumizone, metaldehyde, methamidophos, methidathion, methiocarb, methomyl, methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, propargite, protrifenbute, pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulprofos, sulfoxaflor, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, tetramethrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate, trichlorfon, triflumuron, Bacillus thuringiensis delta-endotoxins, entomopathogenic bacteria, entomopathogenic viruses and entomopathogenic fungi.
8. A composition for protecting an animal from an invertebrate parasitic pest comprising a parasiticidally effective amount of a compound of Claim 1 and at least one carrier.
9. A method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Claim 1.
10. A method for increasing vigor of a crop plant comprising contacting the crop plant, the seed from which the crop plant is grown or the locus of the crop plant with a biologically effective amount of a compound of Claim 1.
11. A treated seed comprising a compound of Claim 1 in an amount of from about 0.0001 to 1 % by weight of the seed before treatment.
12. The compound N-[(5-pyrimidinyl)methyl]-2-pyridinamine.
PCT/US2011/066798 2010-12-29 2011-12-22 Mesoionic pyrido [1,2 -a] pyrimidine pesticides WO2012092115A1 (en)

Priority Applications (19)

Application Number Priority Date Filing Date Title
RU2013135410/04A RU2585616C2 (en) 2010-12-29 2011-12-22 MESOIONIC PYRIDO [1,2-a] PYRIMIDINE PESTICIDES
MA36116A MA34830B1 (en) 2010-12-29 2011-12-22 PESTICIDES BASED ON MESOIONIC PYRIDO [1,2-A] PYRAMIDINES
BR112013009935A BR112013009935B8 (en) 2010-12-29 2011-12-22 COMPOUNDS
MX2013007494A MX358389B (en) 2010-12-29 2011-12-22 Mesoionic pyrido [1,2 -a] pyrimidine pesticides.
JP2013547567A JP5911510B2 (en) 2010-12-29 2011-12-22 Mesoionic pyrido [1,2-a] pyrimidine pest control agent
UAA201308111A UA110953C2 (en) 2010-12-29 2011-12-22 Mesoionic Pyrides [1,2-a] Pyrimidine Pesticides
CN201180062994.4A CN103459387B (en) 2010-12-29 2011-12-22 Mesoionic pyrido [1,2-A] pyrimidine sterilant
ES11808109.0T ES2536305T3 (en) 2010-12-29 2011-12-22 Mesoionic pyrido [1,2-a] pyrimidine pesticides
EP11808109.0A EP2658856B1 (en) 2010-12-29 2011-12-22 Mesoionic pyrido [1,2-a] pyrimidine pesticides
AU2011352379A AU2011352379B2 (en) 2010-12-29 2011-12-22 Mesoionic pyrido [1,2 -a] pyrimidine pesticides
KR1020137019825A KR101897840B1 (en) 2010-12-29 2011-12-22 Mesoionic pyrido [1,2-a] pyrimidine pesticides
SG2013024237A SG189206A1 (en) 2010-12-29 2011-12-22 Mesoionic pyrido [1,2 -a] pyrimidine pesticides
US13/876,636 US8895738B2 (en) 2010-12-29 2011-12-22 Mesoionic pyrido [1, 2-A] pyrimidine pesticides
CA2817902A CA2817902A1 (en) 2010-12-29 2011-12-22 Mesoionic pyrido [1,2-a] pyrimidine pesticides
ZA2013/02430A ZA201302430B (en) 2010-12-29 2013-04-04 Mesoionic pyrido [1,2-a] pyrimidine pesticides
TNP2013000152A TN2013000152A1 (en) 2011-12-22 2013-04-04 Mesoionic pesticides
IL225859A IL225859A (en) 2010-12-29 2013-04-21 N-[(5-pyrimidinyl)methyl]-2-pyridinamine and n-(5-pyrimidinylmethylene)-2-pyridinamine
PH12013501402A PH12013501402A1 (en) 2010-12-29 2013-06-27 Mesoionic Pyrido [1,2 -A] Pyrimidine Pesticides
US14/520,593 US20150038329A1 (en) 2010-12-29 2014-10-22 Mesoionic pesticides

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201061427855P 2010-12-29 2010-12-29
US61/427,855 2010-12-29
US201161550675P 2011-10-24 2011-10-24
US61/550,675 2011-10-24

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US13/876,636 A-371-Of-International US8895738B2 (en) 2010-12-29 2011-12-22 Mesoionic pyrido [1, 2-A] pyrimidine pesticides
US14/520,593 Continuation US20150038329A1 (en) 2010-12-29 2014-10-22 Mesoionic pesticides

Publications (1)

Publication Number Publication Date
WO2012092115A1 true WO2012092115A1 (en) 2012-07-05

Family

ID=45476679

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2011/066798 WO2012092115A1 (en) 2010-12-29 2011-12-22 Mesoionic pyrido [1,2 -a] pyrimidine pesticides

Country Status (22)

Country Link
US (2) US8895738B2 (en)
EP (1) EP2658856B1 (en)
JP (1) JP5911510B2 (en)
KR (1) KR101897840B1 (en)
CN (2) CN103459387B (en)
AR (1) AR084646A1 (en)
AU (1) AU2011352379B2 (en)
BR (1) BR112013009935B8 (en)
CA (1) CA2817902A1 (en)
CO (1) CO6761321A2 (en)
ES (1) ES2536305T3 (en)
HU (1) HUE025531T2 (en)
IL (1) IL225859A (en)
MA (1) MA34830B1 (en)
MX (1) MX358389B (en)
PH (1) PH12013501402A1 (en)
RU (1) RU2585616C2 (en)
SG (1) SG189206A1 (en)
TW (1) TWI528899B (en)
UY (1) UY33842A (en)
WO (1) WO2012092115A1 (en)
ZA (1) ZA201302430B (en)

Cited By (202)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2658379A1 (en) * 2010-12-27 2013-11-06 Sumitomo Chemical Company Limited Arthropod pest control composition and method for controlling arthropod pests
WO2013191114A1 (en) * 2012-06-21 2013-12-27 住友化学株式会社 Arthropod pest control composition and arthropod pest control method
EP2684879A1 (en) 2012-07-09 2014-01-15 Basf Se Substituted mesoionic compounds for combating animal pests
WO2014053401A2 (en) 2012-10-01 2014-04-10 Basf Se Method of improving plant health
WO2014053407A1 (en) 2012-10-01 2014-04-10 Basf Se N-thio-anthranilamide compounds and their use as pesticides
WO2014053405A1 (en) 2012-10-01 2014-04-10 Basf Se Pesticidally active mixtures comprising anthranilamide compounds
WO2014053403A1 (en) 2012-10-01 2014-04-10 Basf Se Method of controlling insecticide resistant insects
WO2014053406A1 (en) 2012-10-01 2014-04-10 Basf Se Method of controlling ryanodine-modulator insecticide resistant insects
WO2014053404A1 (en) 2012-10-01 2014-04-10 Basf Se Pesticidally active mixtures comprising anthranilamide compounds
WO2014053395A1 (en) 2012-10-01 2014-04-10 Basf Se Use of n-thio-anthranilamide compounds on cultivated plants
US8697707B2 (en) 2009-08-05 2014-04-15 E I Du Pont De Nemours And Company Mixtures of mesoionic pesticides
WO2014067838A1 (en) 2012-10-31 2014-05-08 Syngenta Participations Ag Insecticidal compounds
US8722690B2 (en) 2009-08-05 2014-05-13 E I Du Pont De Nemours And Company Mesoionic pesticides
WO2014079820A1 (en) 2012-11-22 2014-05-30 Basf Se Use of anthranilamide compounds for reducing insect-vectored viral infections
WO2014090700A1 (en) 2012-12-14 2014-06-19 Basf Se Malononitrile compounds for controlling animal pests
WO2014102244A1 (en) 2012-12-27 2014-07-03 Basf Se 2-(pyridin-3-yl)-5-hetaryl-thiazole compounds carrying an imine or imine-derived substituent for combating invertebrate pests
WO2014154488A1 (en) 2013-03-28 2014-10-02 Syngenta Participations Ag Methods of controlling neonicotinoid resistant pests
WO2014167084A1 (en) * 2013-04-11 2014-10-16 Basf Se Substituted pyrimidinium compounds and derivatives for combating animal pests
WO2014170300A1 (en) 2013-04-19 2014-10-23 Basf Se N-substituted acyl-imino-pyridine compounds and derivatives for combating animal pests
WO2014202751A1 (en) 2013-06-21 2014-12-24 Basf Se Methods for controlling pests in soybean
WO2015000715A1 (en) 2013-07-02 2015-01-08 Syngenta Participations Ag Pesticidally active bi- or tricyclic heterocycles with sulfur containing substituents
WO2015007682A1 (en) 2013-07-15 2015-01-22 Basf Se Pesticide compounds
WO2015040116A1 (en) 2013-09-19 2015-03-26 Basf Se N-acylimino heterocyclic compounds
WO2015055757A1 (en) 2013-10-18 2015-04-23 Basf Se Use of pesticidal active carboxamide derivative in soil and seed application and treatment methods
WO2015055497A1 (en) 2013-10-16 2015-04-23 Basf Se Substituted pesticidal pyrazole compounds
EP2873668A1 (en) 2013-11-13 2015-05-20 Syngenta Participations AG. Pesticidally active bicyclic heterocycles with sulphur containing substituents
WO2015091945A1 (en) 2013-12-20 2015-06-25 Syngenta Participations Ag Pesticidally active substituted 5,5-bicyclic heterocycles with sulphur containing substituents
WO2015091645A1 (en) 2013-12-18 2015-06-25 Basf Se Azole compounds carrying an imine-derived substituent
WO2015091649A1 (en) 2013-12-18 2015-06-25 Basf Se N-substituted imino heterocyclic compounds
WO2015097237A1 (en) 2013-12-23 2015-07-02 Syngenta Participations Ag Benzoxaborole fungicides
WO2015104422A1 (en) 2014-01-13 2015-07-16 Basf Se Dihydrothiophene compounds for controlling invertebrate pests
US9108965B2 (en) 2011-12-15 2015-08-18 E I Du Pont De Nemours And Company Malonic acid di-salts and a method for preparing malonyl dihalides
WO2015177063A1 (en) 2014-05-19 2015-11-26 Syngenta Participations Ag Insecticidally active amide derivatives with sulfur-substituted phenyl or pyridine groups
US9204649B2 (en) 2011-02-01 2015-12-08 Bayer Intellectual Property Gmbh Heteroarylpiperidine and- piperazine derivates as fungicides
WO2016091731A1 (en) 2014-12-11 2016-06-16 Syngenta Participations Ag Pesticidally active tetracyclic derivatives with sulfur containing substituents
WO2016120182A1 (en) 2015-01-30 2016-08-04 Syngenta Participations Ag Pesticidally active amide heterocyclic derivatives with sulphur containing substituents
US20160287618A1 (en) * 2013-11-15 2016-10-06 Nestec S.A. Compositions for use in the prevention or treatment of urt infections in infants or young children at risk
WO2016166252A1 (en) 2015-04-17 2016-10-20 Basf Agrochemical Products B.V. Method for controlling non-crop pests
WO2016169886A1 (en) 2015-04-24 2016-10-27 Syngenta Crop Protection Ag Pesticidally active polycyclic derivatives with sulfur substituted five-membered ring heterocyles
WO2016169882A1 (en) 2015-04-24 2016-10-27 Syngenta Participations Ag Pesticidally active polycyclic derivatives with sulfur substituted five membered ring heterocyles
WO2017001311A1 (en) 2015-07-01 2017-01-05 Syngenta Participations Ag Pesticidally active tetracyclic derivatives with sulfur containing substituents
KR20170021886A (en) 2014-07-04 2017-02-28 스미또모 가가꾸 가부시끼가이샤 Pest control composition and use for same
WO2017050751A1 (en) 2015-09-25 2017-03-30 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulphur containing substituents
WO2017050922A1 (en) 2015-09-23 2017-03-30 Syngenta Participations Ag Isoxazoline-substituted benzamides and analogues as insecticides
WO2017050685A1 (en) 2015-09-25 2017-03-30 Syngenta Participations Ag Pesticidally active polycyclic derivatives with 5-membered sulfur containing heterocyclic ring systems
WO2017055147A1 (en) 2015-09-28 2017-04-06 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulphur containing substituents
WO2017063973A1 (en) 2015-10-14 2017-04-20 Syngenta Participations Ag Fungicidal compositions
WO2017067839A1 (en) 2015-10-23 2017-04-27 Syngenta Participations Ag Microbiocidal phenylamidine derivatives
WO2017067837A1 (en) 2015-10-23 2017-04-27 Syngenta Participations Ag Microbiocidal phenylamidine derivatives
WO2017072247A1 (en) 2015-10-28 2017-05-04 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017076982A1 (en) 2015-11-04 2017-05-11 Syngenta Participations Ag Microbiocidal anilide derivatives
WO2017089190A1 (en) 2015-11-23 2017-06-01 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulphur and cyclopropyl containing substituents
WO2017093214A1 (en) 2015-12-03 2017-06-08 Bayer Cropscience Aktiengesellschaft Mesoionic halogenated 3-(acetyl)-1-[(1,3-thiazol-5-yl)methyl]-1h-imidazo[1,2-a]pyridin-4-ium-2-olate derivatives and related compounds as insecticides
WO2017102006A1 (en) 2015-12-17 2017-06-22 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017108569A1 (en) 2015-12-22 2017-06-29 Syngenta Participations Ag Pesticidally active pyrazole derivatives
CN106973923A (en) * 2017-05-13 2017-07-25 北京科发伟业农药技术中心 A kind of Pesticidal combination of the pyrimidine containing trifluoro-benzene
WO2017134066A1 (en) 2016-02-05 2017-08-10 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulphur containing substituents
JP2017141250A (en) * 2012-06-21 2017-08-17 住友化学株式会社 Harmful arthropod control composition and harmful arthropod control method
WO2017140771A1 (en) 2016-02-18 2017-08-24 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2017157962A1 (en) 2016-03-15 2017-09-21 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017162868A1 (en) 2016-03-24 2017-09-28 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017174158A1 (en) 2016-04-08 2017-10-12 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017174449A1 (en) 2016-04-07 2017-10-12 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulphur containing substituents
WO2017178549A1 (en) 2016-04-12 2017-10-19 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017178408A1 (en) 2016-04-15 2017-10-19 Syngenta Participations Ag Microbiocidal silicon containing aryl derivatives
WO2017189339A1 (en) 2016-04-26 2017-11-02 E I Du Pont De Nemours And Company Process for the preparation of n-[(5-pyrimidinyl)methyl]-2-pyridinamines
WO2017207757A1 (en) 2016-06-03 2017-12-07 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017220485A1 (en) 2016-06-21 2017-12-28 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
EP3269245A1 (en) * 2014-06-25 2018-01-17 Basf Agro B.V. Arnhem (NL) Pesticidal compositions
WO2018015449A1 (en) 2016-07-22 2018-01-25 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018015447A1 (en) 2016-07-22 2018-01-25 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018015458A1 (en) 2016-07-22 2018-01-25 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018029242A1 (en) 2016-08-11 2018-02-15 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018041729A2 (en) 2016-09-01 2018-03-08 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulphur containing substituents
WO2018055133A1 (en) 2016-09-23 2018-03-29 Syngenta Participations Ag Microbiocidal tetrazolone derivatives
WO2018055135A1 (en) 2016-09-23 2018-03-29 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018060039A1 (en) 2016-09-28 2018-04-05 Syngenta Participations Ag Fungicidal compositions
WO2018065414A1 (en) 2016-10-06 2018-04-12 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018077565A1 (en) 2016-10-27 2018-05-03 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulphur and hydroxylamine substituents
WO2018091389A1 (en) 2016-11-17 2018-05-24 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulphur containing substituents
WO2018095795A1 (en) 2016-11-23 2018-05-31 Syngenta Participations Ag Pesticidally active polycyclic derivatives with sulfur containing substituents
WO2018099812A1 (en) 2016-12-01 2018-06-07 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
EP3336086A1 (en) 2016-12-19 2018-06-20 Syngenta Participations Ag Pesticidally active azetidine sulfone amide isoxazoline derivatives
EP3336087A1 (en) 2016-12-19 2018-06-20 Syngenta Participations Ag Pesticidally active azetidine sulfone amide isoxazoline derivatives
WO2018108730A1 (en) 2016-12-16 2018-06-21 Bayer Aktiengesellschaft Mesoionic imidazopyridines for use as insecticides
WO2018108726A1 (en) 2016-12-15 2018-06-21 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2018149851A1 (en) 2017-02-16 2018-08-23 Syngenta Participations Ag Fungicidal compositions
WO2018153778A1 (en) 2017-02-21 2018-08-30 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2018158365A1 (en) 2017-03-03 2018-09-07 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018162643A1 (en) 2017-03-10 2018-09-13 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018172471A1 (en) 2017-03-22 2018-09-27 Syngenta Participations Ag Pesticidally active cyclopropyl methyl amide derivatives
WO2018172477A1 (en) 2017-03-23 2018-09-27 Syngenta Participations Ag Insecticidal compounds
WO2018172480A1 (en) 2017-03-23 2018-09-27 Syngenta Participations Ag Insecticidal compounds
WO2018177894A1 (en) 2017-03-31 2018-10-04 Syngenta Participations Ag Fungicidal compositions
WO2018177880A1 (en) 2017-03-31 2018-10-04 Syngenta Participations Ag Fungicidal compositions
WO2018185187A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2018184987A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184985A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184984A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018185191A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2018185211A1 (en) 2017-04-06 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184988A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018185185A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2018185013A1 (en) 2017-04-03 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184982A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184986A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018189077A1 (en) 2017-04-12 2018-10-18 Bayer Aktiengesellschaft Mesoionic imidazopyridines for use as insecticides
CN108699031A (en) * 2015-12-14 2018-10-23 Fmc公司 Two ring azoles insecticides of heterocyclic substituted
WO2018197315A1 (en) 2017-04-25 2018-11-01 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2018202540A1 (en) 2017-05-02 2018-11-08 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2018206419A1 (en) 2017-05-12 2018-11-15 Syngenta Participations Ag Microbiocidal heterobicyclic derivatives
WO2018206348A1 (en) 2017-05-08 2018-11-15 Syngenta Participations Ag Imidazopyrimidine derivatives with sulfur containing phenyl and pyridyl substituents
WO2018215304A1 (en) 2017-05-22 2018-11-29 Syngenta Participations Ag Tetracyclic pyridazine sulphur containing compounds and their use as pesticides
WO2018219773A1 (en) 2017-06-02 2018-12-06 Syngenta Participations Ag Fungicidal compositions
WO2018219825A1 (en) 2017-06-02 2018-12-06 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018229202A1 (en) 2017-06-16 2018-12-20 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
WO2018228896A1 (en) 2017-06-14 2018-12-20 Syngenta Participations Ag Fungicidal compositions
WO2018234240A1 (en) 2017-06-19 2018-12-27 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2019002151A1 (en) 2017-06-28 2019-01-03 Syngenta Participations Ag Fungicidal compositions
WO2019008115A1 (en) 2017-07-07 2019-01-10 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2019008072A1 (en) 2017-07-05 2019-01-10 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2019012011A1 (en) 2017-07-12 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011923A1 (en) 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011926A1 (en) 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019012003A1 (en) 2017-07-13 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019012001A1 (en) 2017-07-12 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011929A1 (en) 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011928A1 (en) 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019030359A1 (en) 2017-08-11 2019-02-14 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2019030358A1 (en) 2017-08-11 2019-02-14 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2019030355A1 (en) 2017-08-11 2019-02-14 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2019030357A1 (en) 2017-08-11 2019-02-14 Syngenta Participations Ag Pesticidally active thiophene derivatives
WO2019034796A1 (en) 2017-12-01 2019-02-21 Syngenta Participations Ag Novel pyrimidine derivatives
WO2019042932A1 (en) * 2017-08-31 2019-03-07 Basf Se Method of controlling rice pests in rice
WO2019052930A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Fungicidal compositions
WO2019053024A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053019A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053010A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053015A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053027A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053182A1 (en) 2017-09-18 2019-03-21 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2019053016A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053026A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019068819A1 (en) 2017-10-06 2019-04-11 Syngenta Participations Ag Pesticidally active pyrrole derivatives
WO2019068812A1 (en) 2017-10-05 2019-04-11 Syngenta Participations Ag Microbiocidal picolinamide derivatives
WO2019068820A1 (en) 2017-10-06 2019-04-11 Syngenta Participations Ag Pesticidally active pyrrole derivatives
WO2019068809A1 (en) 2017-10-05 2019-04-11 Syngenta Participations Ag Microbiocidal picolinamide derivatives
WO2019076778A1 (en) 2017-10-16 2019-04-25 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur and sulfonimidamides containing substituents
WO2019086474A1 (en) 2017-10-31 2019-05-09 Syngenta Participations Ag Pesticidally active mesoionics heterocyclic compounds
WO2019097054A1 (en) 2017-11-20 2019-05-23 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019096709A1 (en) 2017-11-15 2019-05-23 Syngenta Participations Ag Microbiocidal picolinamide derivatives
WO2019105933A1 (en) 2017-11-29 2019-06-06 Syngenta Participations Ag Microbiocidal thiazole derivatives
WO2019115404A1 (en) 2017-12-13 2019-06-20 Syngenta Participations Ag Pesticidally active mesoionic heterocyclic compounds
WO2019121149A1 (en) 2017-12-19 2019-06-27 Syngenta Participations Ag Microbiocidal picolinamide derivatives
WO2019134840A1 (en) * 2018-01-05 2019-07-11 Basf Se Control of pests of soybean plants with mesoionic compounds
WO2019138018A1 (en) 2018-01-15 2019-07-18 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2019173173A1 (en) 2018-03-05 2019-09-12 E. I. Du Pont De Nemours And Company Process and intermidiates for the preparation of certain mesoionic pesticides
WO2019219689A1 (en) 2018-05-18 2019-11-21 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfoximine containing substituents
WO2019229088A1 (en) 2018-05-30 2019-12-05 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2019229089A1 (en) 2018-05-31 2019-12-05 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2019234158A1 (en) 2018-06-06 2019-12-12 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfoximine containing substituents
WO2019234160A1 (en) 2018-06-06 2019-12-12 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
US10512267B2 (en) 2013-07-08 2019-12-24 BASF Agro, B.V. Compositions comprising a triazole compound and a biopesticide
WO2019243253A1 (en) 2018-06-19 2019-12-26 Syngenta Crop Protection Ag Pesticidally active isoxazoline derivatives containing an amide group and an azetidine sulfone group
WO2019243256A1 (en) 2018-06-19 2019-12-26 Syngenta Crop Protection Ag Pesticidally active isoxazoline derivatives containing an amide group and an azetidine sulfone group
WO2019243262A1 (en) 2018-06-19 2019-12-26 Syngenta Crop Protection Ag Pesticidally active azetidine sulfones amide isoxazoline derivatives
WO2019243263A1 (en) 2018-06-19 2019-12-26 Syngenta Participations Ag Insecticidal compounds
US10519122B2 (en) 2013-01-09 2019-12-31 BASF Agro B.V. Process for the preparation of substituted oxiranes and triazoles
WO2020002563A1 (en) 2018-06-29 2020-01-02 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020002331A1 (en) 2018-06-29 2020-01-02 Syngenta Crop Protection Ag Microbiocidal oxadiazole derivatives
WO2020007658A1 (en) 2018-07-02 2020-01-09 Syngenta Crop Protection Ag 3-(2-thienyl)-5-(trifluoromethyl)-1,2,4-oxadiazole derivatives as agrochemical fungicides
WO2020011808A1 (en) 2018-07-13 2020-01-16 Syngenta Crop Protection Ag Pesticidally-active bicyclic heteroaromatic compounds
WO2020016180A1 (en) 2018-07-16 2020-01-23 Syngenta Crop Protection Ag Microbiocidal oxadiazole derivatives
WO2020025658A1 (en) 2018-08-03 2020-02-06 Syngenta Crop Protection Ag Pesticidally-active bicyclic heteroaromatic compounds
WO2020030503A1 (en) 2018-08-07 2020-02-13 Syngenta Crop Protection Ag Pesticidally-active bicyclic heteroaromatic compounds
WO2020035565A1 (en) 2018-08-17 2020-02-20 Syngenta Crop Protection Ag Pesticidally-active mesoionic bicyclic heteroaromatic compounds
WO2020058207A1 (en) 2018-09-19 2020-03-26 Syngenta Crop Protection Ag Microbiocidal quinoline carboxamide derivatives
WO2020064564A1 (en) 2018-09-26 2020-04-02 Syngenta Participations Ag Insecticidal compounds
WO2020070049A1 (en) 2018-10-02 2020-04-09 Syngenta Participations Ag Pesticidally active benzene- and azine-amide compounds
WO2020070131A1 (en) 2018-10-06 2020-04-09 Syngenta Participations Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2020070132A1 (en) 2018-10-06 2020-04-09 Syngenta Participations Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2020084075A1 (en) 2018-10-24 2020-04-30 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfoximine containing substituents
WO2020120697A1 (en) 2018-12-14 2020-06-18 Syngenta Crop Protection Ag Pesticidally-active cyanamide heterocyclic compounds
WO2020120694A1 (en) 2018-12-14 2020-06-18 Syngenta Participations Ag Pesticidally-active bicyclic heteroaromatic compounds
WO2020127345A1 (en) 2018-12-21 2020-06-25 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2020141135A1 (en) 2018-12-31 2020-07-09 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2020141136A1 (en) 2018-12-31 2020-07-09 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
EP3683213A1 (en) 2015-03-27 2020-07-22 Syngenta Participations Ag Microbiocidal heterobicyclic derivatives
EP3696175A1 (en) 2019-02-18 2020-08-19 Syngenta Crop Protection AG Pesticidally active azole-amide compounds
WO2020164993A1 (en) 2019-02-13 2020-08-20 Syngenta Crop Protection Ag Pesticidally active pyrazole derivatives
WO2020164994A1 (en) 2019-02-13 2020-08-20 Syngenta Crop Protection Ag Pesticidally active pyrazole derivatives
US10759767B2 (en) 2012-12-20 2020-09-01 BASF Agro B.V. Compositions comprising a triazole compound
WO2020174094A1 (en) 2019-02-28 2020-09-03 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2020174096A1 (en) 2019-02-28 2020-09-03 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2020182577A1 (en) 2019-03-08 2020-09-17 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2020239517A1 (en) 2019-05-29 2020-12-03 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
WO2021009311A1 (en) 2019-07-17 2021-01-21 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
EP3769623A1 (en) 2019-07-22 2021-01-27 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
WO2022180096A1 (en) 2021-02-26 2022-09-01 Syngenta Crop Protection Ag Pesticidal compositions
WO2023086802A1 (en) 2021-11-10 2023-05-19 Corteva Agriscience Llc Processes for the preparation of certain mesoionic pesticides
RU2805872C1 (en) * 2023-04-26 2023-10-24 Общество с ограниченной ответственностью "Рустарк" Insecticidal preparation and method of its use
WO2024040111A1 (en) 2022-08-18 2024-02-22 Corteva Agriscience Llc Process for the preparation and isolation of intermediates of certain mesoionic pesticides

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI401023B (en) 2008-02-06 2013-07-11 Du Pont Mesoionic pesticides
CN104082333A (en) * 2014-07-03 2014-10-08 广西农喜作物科学有限公司 Insecticidal composition containing clothianidin
CN105532680B (en) * 2016-01-27 2018-06-01 江西省农业科学院植物保护研究所 A kind of highly efficiency compositional composition pesticide of pyrimidine containing trifluoro-benzene and cycloxaprid
CA3038631A1 (en) 2016-09-28 2018-04-05 Nippon Kayaku Kabushiki Kaisha Novel mesoionic insecticidal compound
BR112019023474B1 (en) * 2017-05-09 2023-12-19 Fmc Corporation COMPOUND, COMPOSITION AND METHOD FOR CONTROLING AN INVERTEBRATE PEST
CN107156151A (en) * 2017-06-16 2017-09-15 江苏天容集团股份有限公司 Pesticidal combination containing trifluoro-benzene pyrimidine and dimehypo
CN107232214A (en) * 2017-06-22 2017-10-10 江苏天容集团股份有限公司 Pesticidal combination containing trifluoro-benzene pyrimidine and cartap
CN107156152A (en) * 2017-06-22 2017-09-15 江苏天容集团股份有限公司 Pesticidal combination containing trifluoro-benzene pyrimidine and bensultap
CN109553615B (en) * 2017-09-26 2020-09-22 沈阳中化农药化工研发有限公司 Pyrimidine salt compound and application thereof
CN110452238B (en) * 2018-04-18 2020-08-11 东莞市东阳光农药研发有限公司 Pyrimidinium compounds and uses thereof
CN108373468B (en) * 2018-05-18 2019-12-17 武汉工程大学 Preparation method of N-2-pyridine-5-pyrimidine methylamine
CN109006842A (en) * 2018-08-13 2018-12-18 广东顾地丰生物科技有限公司 A kind of highly efficiency compositional composition pesticide of pyrimidine containing trifluoro-benzene and paichongding
CN111620867A (en) * 2019-02-28 2020-09-04 东莞市东阳光农药研发有限公司 Mesoionic insecticides
CN110151762A (en) * 2019-05-19 2019-08-23 青海大学 A kind of new application of thiacloprid
CN112442026B (en) * 2019-08-27 2023-08-08 东莞市东阳光农药研发有限公司 Mesoionic derivative and preparation method and application thereof
CN110495463B (en) * 2019-09-10 2021-08-24 泰安市农业科学研究院 Synergistic pesticide composition containing trifluoro-benzene pyrimidine and application thereof
CN112851665B (en) * 2019-11-28 2023-08-08 东莞市东阳光农药研发有限公司 Novel mesoionic compounds and their use in agriculture
CN111183999A (en) * 2020-03-06 2020-05-22 江苏丘陵地区镇江农业科学研究所 Composition containing trifluoro-benzene pyrimidine and azoxystrobin, seed treating agent and application
CN111296463A (en) * 2020-03-17 2020-06-19 浙江中山化工集团股份有限公司 Compound pesticide containing trifluoro-benzene pyrimidine and chlorfenapyr
CN111592539B (en) * 2020-06-03 2022-11-15 江西农业大学 Preparation method of trifluoro-benzene pyrimidine
CN113951268A (en) * 2020-07-21 2022-01-21 江苏功成生物科技有限公司 Sanitary insecticidal composition containing trifluoro-benzene pyrimidine and application thereof
CN115211434A (en) * 2021-04-19 2022-10-21 江苏扬农化工股份有限公司 Fly killing composition containing lufenuron and trifluoropyrimidine and application thereof
CN113956081B (en) * 2021-11-10 2023-02-28 江苏科技大学 Method for biotransformation of silkworm excrement waste by fly maggot and product application thereof

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2891855A (en) 1954-08-16 1959-06-23 Geigy Ag J R Compositions and methods for influencing the growth of plants
US3060084A (en) 1961-06-09 1962-10-23 Du Pont Improved homogeneous, readily dispersed, pesticidal concentrate
US3235361A (en) 1962-10-29 1966-02-15 Du Pont Method for the control of undesirable vegetation
US3299566A (en) 1964-06-01 1967-01-24 Olin Mathieson Water soluble film containing agricultural chemicals
US3309192A (en) 1964-12-02 1967-03-14 Du Pont Method of controlling seedling weed grasses
US3920442A (en) 1972-09-18 1975-11-18 Du Pont Water-dispersible pesticide aggregates
US4144050A (en) 1969-02-05 1979-03-13 Hoechst Aktiengesellschaft Micro granules for pesticides and process for their manufacture
US4172714A (en) 1976-12-20 1979-10-30 E. I. Du Pont De Nemours And Company Dry compactible, swellable herbicidal compositions and pellets produced therefrom
GB2095558A (en) 1981-03-30 1982-10-06 Avon Packers Ltd Formulation of agricultural chemicals
DE3246493A1 (en) 1982-12-16 1984-06-20 Bayer Ag, 5090 Leverkusen METHOD FOR PRODUCING WATER-DISPERSIBLE GRANULES
WO1991013546A1 (en) 1990-03-12 1991-09-19 E.I. Du Pont De Nemours And Company Water-dispersible or water-soluble pesticide granules from heat-activated binders
US5180587A (en) 1988-06-28 1993-01-19 E. I. Du Pont De Nemours And Company Tablet formulations of pesticides
US5208030A (en) 1989-08-30 1993-05-04 Imperial Chemical Industries Plc Active ingredient dosage device
US5232701A (en) 1990-10-11 1993-08-03 Sumitomo Chemical Company, Limited Boron carbonate and solid acid pesticidal composition
WO2003024222A1 (en) 2001-09-21 2003-03-27 E. I. Du Pont De Nemours And Company Anthranilamide arthropodicide treatment
WO2009099929A1 (en) 2008-02-06 2009-08-13 E. I. Du Pont De Nemours And Company Mesoionic pesticides
WO2011017342A2 (en) * 2009-08-05 2011-02-10 E. I. Du Pont De Nemours And Company Mesoionic pesticides
WO2011017351A2 (en) * 2009-08-05 2011-02-10 E. I. Du Pont De Nemours And Company Mixtures of mesoionic pesticides
WO2011017347A2 (en) * 2009-08-05 2011-02-10 E. I. Du Pont De Nemours And Company Mesoionic pesticides

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2010279574A1 (en) * 2009-08-05 2012-02-09 E. I. Du Pont De Nemours And Company Mesoionic pesticides
WO2012106495A1 (en) 2011-02-03 2012-08-09 E. I. Du Pont De Nemours And Company Mesoionic pesticides
TWI572587B (en) * 2011-12-15 2017-03-01 杜邦股份有限公司 Malonic acid di-salts and a method for preparing malonyl dihalides

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2891855A (en) 1954-08-16 1959-06-23 Geigy Ag J R Compositions and methods for influencing the growth of plants
US3060084A (en) 1961-06-09 1962-10-23 Du Pont Improved homogeneous, readily dispersed, pesticidal concentrate
US3235361A (en) 1962-10-29 1966-02-15 Du Pont Method for the control of undesirable vegetation
US3299566A (en) 1964-06-01 1967-01-24 Olin Mathieson Water soluble film containing agricultural chemicals
US3309192A (en) 1964-12-02 1967-03-14 Du Pont Method of controlling seedling weed grasses
US4144050A (en) 1969-02-05 1979-03-13 Hoechst Aktiengesellschaft Micro granules for pesticides and process for their manufacture
US3920442A (en) 1972-09-18 1975-11-18 Du Pont Water-dispersible pesticide aggregates
US4172714A (en) 1976-12-20 1979-10-30 E. I. Du Pont De Nemours And Company Dry compactible, swellable herbicidal compositions and pellets produced therefrom
GB2095558A (en) 1981-03-30 1982-10-06 Avon Packers Ltd Formulation of agricultural chemicals
DE3246493A1 (en) 1982-12-16 1984-06-20 Bayer Ag, 5090 Leverkusen METHOD FOR PRODUCING WATER-DISPERSIBLE GRANULES
US5180587A (en) 1988-06-28 1993-01-19 E. I. Du Pont De Nemours And Company Tablet formulations of pesticides
US5208030A (en) 1989-08-30 1993-05-04 Imperial Chemical Industries Plc Active ingredient dosage device
WO1991013546A1 (en) 1990-03-12 1991-09-19 E.I. Du Pont De Nemours And Company Water-dispersible or water-soluble pesticide granules from heat-activated binders
US5232701A (en) 1990-10-11 1993-08-03 Sumitomo Chemical Company, Limited Boron carbonate and solid acid pesticidal composition
WO2003024222A1 (en) 2001-09-21 2003-03-27 E. I. Du Pont De Nemours And Company Anthranilamide arthropodicide treatment
WO2009099929A1 (en) 2008-02-06 2009-08-13 E. I. Du Pont De Nemours And Company Mesoionic pesticides
WO2011017342A2 (en) * 2009-08-05 2011-02-10 E. I. Du Pont De Nemours And Company Mesoionic pesticides
WO2011017351A2 (en) * 2009-08-05 2011-02-10 E. I. Du Pont De Nemours And Company Mixtures of mesoionic pesticides
WO2011017347A2 (en) * 2009-08-05 2011-02-10 E. I. Du Pont De Nemours And Company Mesoionic pesticides

Non-Patent Citations (32)

* Cited by examiner, † Cited by third party
Title
"Developments infonnulation technology", 2000, PJB PUBLICATIONS
"McCutcheon's Emulsifiers and Detergents", MCCUTCHEON'S DIVISION, THE MANUFACTURING CONFECTIONER PUBLISHING CO.
"McCutcheon's Volume 2: Functional Materials", vol. 2, MCCUTCHEON'S DIVISION, THE MANUFACTURING CONFECTIONER PUBLISHING CO.
"Perry's Chemical Engineer's Handbook", 1963, MCGRAW-HILL, pages: 8 - 57
A. S. DAVIDSON; B. MILWIDSKY: "Synthetic Detergents", 1987, JOHN WILEY AND SONS
ARCHIV DER PHARMAZIE, vol. 324, 1991, pages 863 - 866
BROWNING: "Agglomeration", CHEMICAL ENGINEERING, 4 December 1967 (1967-12-04), pages 147 - 48
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, vol. 72, no. 3, 1999, pages 503 - 509
E. NEGISHI: "Handbook of Organopalladium Chemistry for Organic Synthesis", 2002, WILEY-INTERSCIENCE
GREENE, T. W.; WUTS, P. G. M.: "Protective Groups in Organic Synthesis", 1991, WILEY
HANCE ET AL.: "Weed Control Handbook", 1989, BLACKWELL SCIENTIFIC PUBLICATIONS
HELVETICA CHIMICA ACTA, vol. 74, no. 2, 1991, pages 309 - 314
J. A>N. CHERN. SOC., vol. 124, 2002, pages 6872 - 6878
J. HET. CHEM., vol. 17, 1980, pages 337
J. MED. CHEM, vol. 25, no. 6, 1982, pages 745 - 747
J. ORG. CHEM, vol. 67, 2002, pages 541 - 555
J. ORG. CHEM., vol. 37, no. 9, 1972, pages 1422 - 1425
KAPPE, T. ET AL., MONATSCHEFTEFUR CHEMIE, vol. 102, 1971, pages 412 - 424
KLINGMAN: "Weed Control as a Science", 1961, JOHN WILEY AND SONS, INC., pages: 81 - 96
KOCH, A. ET AL., TETRAHEDRON, vol. 60, 2004, pages 10011 - 10018
MARSDEN: "Solvents Guide", 1950, INTERSCIENCE
ORG. LETT., vol. 4, 2002, pages 269 - 272
ORG. LETT., vol. 7, 2005, pages 4693 - 4695
P. KOSTERS ET AL.: "Seed Treatment: Progress and Prospects", 1994, BCPC MONGRAPH NO. 57
SCIENCE OF SYNTHESIS, vol. 21, 2005, pages 17 - 25
SISELY; WOOD: "Encyclopedia of Surface Active Agents", 1964, CHEMICAL PUBL. CO., INC.
T. S. WOODS: "Pesticide Chemistry and Bioscience, The Food-Environment Challenge", 1999, THE ROYAL SOCIETY OF CHEMISTRY, article "The Formulator's Toolbox - Product Forms for Modem Agriculture", pages: 120 - 133
TETRAHEDRON, vol. 61, 2005, pages 10827 - 10852
URBAN, M. G.; ARNOLD,W., HELVETICA CHIMICA ACTA, vol. 53, 1970, pages 905 - 922
WATKINS ET AL.: "Handbook of Insecticide Dust Diluents and Carriers", DORLAND BOOKS
XIE, MA ET AL., ORG. LETT., vol. 7, 2005, pages 4693 - 4695
ZEITSCHRIFT FLIR NATURFORSCHUNG, TEIL B: ANORGANISCHE CHEMIE, ORGANISCHE CHEMIE, vol. 37B, no. 2, 1982, pages 222 - 233

Cited By (228)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8697707B2 (en) 2009-08-05 2014-04-15 E I Du Pont De Nemours And Company Mixtures of mesoionic pesticides
US8722690B2 (en) 2009-08-05 2014-05-13 E I Du Pont De Nemours And Company Mesoionic pesticides
EP2658379A1 (en) * 2010-12-27 2013-11-06 Sumitomo Chemical Company Limited Arthropod pest control composition and method for controlling arthropod pests
EP2658379A4 (en) * 2010-12-27 2014-05-28 Sumitomo Chemical Co Arthropod pest control composition and method for controlling arthropod pests
US9204649B2 (en) 2011-02-01 2015-12-08 Bayer Intellectual Property Gmbh Heteroarylpiperidine and- piperazine derivates as fungicides
US9108965B2 (en) 2011-12-15 2015-08-18 E I Du Pont De Nemours And Company Malonic acid di-salts and a method for preparing malonyl dihalides
WO2013191114A1 (en) * 2012-06-21 2013-12-27 住友化学株式会社 Arthropod pest control composition and arthropod pest control method
JP2014024829A (en) * 2012-06-21 2014-02-06 Sumitomo Chemical Co Ltd Noxious arthropod control composition and control method of noxious arthropod
JP2017141250A (en) * 2012-06-21 2017-08-17 住友化学株式会社 Harmful arthropod control composition and harmful arthropod control method
KR20150023374A (en) 2012-06-21 2015-03-05 스미또모 가가꾸 가부시끼가이샤 Arthropod pest control composition and arthropod pest control method
EP2684879A1 (en) 2012-07-09 2014-01-15 Basf Se Substituted mesoionic compounds for combating animal pests
WO2014053401A2 (en) 2012-10-01 2014-04-10 Basf Se Method of improving plant health
WO2014053395A1 (en) 2012-10-01 2014-04-10 Basf Se Use of n-thio-anthranilamide compounds on cultivated plants
WO2014053404A1 (en) 2012-10-01 2014-04-10 Basf Se Pesticidally active mixtures comprising anthranilamide compounds
WO2014053406A1 (en) 2012-10-01 2014-04-10 Basf Se Method of controlling ryanodine-modulator insecticide resistant insects
WO2014053403A1 (en) 2012-10-01 2014-04-10 Basf Se Method of controlling insecticide resistant insects
WO2014053405A1 (en) 2012-10-01 2014-04-10 Basf Se Pesticidally active mixtures comprising anthranilamide compounds
WO2014053407A1 (en) 2012-10-01 2014-04-10 Basf Se N-thio-anthranilamide compounds and their use as pesticides
WO2014067838A1 (en) 2012-10-31 2014-05-08 Syngenta Participations Ag Insecticidal compounds
WO2014079820A1 (en) 2012-11-22 2014-05-30 Basf Se Use of anthranilamide compounds for reducing insect-vectored viral infections
WO2014090700A1 (en) 2012-12-14 2014-06-19 Basf Se Malononitrile compounds for controlling animal pests
US10117430B2 (en) 2012-12-14 2018-11-06 Basf Se Malononitrile compounds for controlling animal pests
US10759767B2 (en) 2012-12-20 2020-09-01 BASF Agro B.V. Compositions comprising a triazole compound
WO2014102244A1 (en) 2012-12-27 2014-07-03 Basf Se 2-(pyridin-3-yl)-5-hetaryl-thiazole compounds carrying an imine or imine-derived substituent for combating invertebrate pests
US10981883B2 (en) 2013-01-09 2021-04-20 BASF Agro B.V. Process for the preparation of substituted oxiranes and triazoles
US10519122B2 (en) 2013-01-09 2019-12-31 BASF Agro B.V. Process for the preparation of substituted oxiranes and triazoles
WO2014154488A1 (en) 2013-03-28 2014-10-02 Syngenta Participations Ag Methods of controlling neonicotinoid resistant pests
CN105121441A (en) * 2013-04-11 2015-12-02 巴斯夫欧洲公司 Substituted pyrimidinium compounds and derivatives for combating animal pests
JP2016521264A (en) * 2013-04-11 2016-07-21 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Substituted pyrimidinium compounds and derivatives for controlling animal pests
US9730451B2 (en) 2013-04-11 2017-08-15 Basf Se Substituted pyrimidinium compounds and derivatives for combating animal pests
US11019820B2 (en) 2013-04-11 2021-06-01 Basf Se Substituted pyrimidinium compounds and derivatives for combating animal pests
WO2014167084A1 (en) * 2013-04-11 2014-10-16 Basf Se Substituted pyrimidinium compounds and derivatives for combating animal pests
CN105121441B (en) * 2013-04-11 2018-04-20 巴斯夫欧洲公司 For preventing and kill off the substituted pyrimidines compound and derivative of animal pest
AU2014253086B2 (en) * 2013-04-11 2018-01-18 Basf Se Substituted pyrimidinium compounds and derivatives for combating animal pests
WO2014170300A1 (en) 2013-04-19 2014-10-23 Basf Se N-substituted acyl-imino-pyridine compounds and derivatives for combating animal pests
WO2014202751A1 (en) 2013-06-21 2014-12-24 Basf Se Methods for controlling pests in soybean
EP3778598A2 (en) 2013-07-02 2021-02-17 Syngenta Participations Ag Pesticidally active bi- or tricyclic heterocycles with sulfur containing substituents
WO2015000715A1 (en) 2013-07-02 2015-01-08 Syngenta Participations Ag Pesticidally active bi- or tricyclic heterocycles with sulfur containing substituents
US10512267B2 (en) 2013-07-08 2019-12-24 BASF Agro, B.V. Compositions comprising a triazole compound and a biopesticide
WO2015007682A1 (en) 2013-07-15 2015-01-22 Basf Se Pesticide compounds
WO2015040116A1 (en) 2013-09-19 2015-03-26 Basf Se N-acylimino heterocyclic compounds
WO2015055497A1 (en) 2013-10-16 2015-04-23 Basf Se Substituted pesticidal pyrazole compounds
WO2015055757A1 (en) 2013-10-18 2015-04-23 Basf Se Use of pesticidal active carboxamide derivative in soil and seed application and treatment methods
EP3456201A1 (en) 2013-10-18 2019-03-20 BASF Agrochemical Products B.V. Use of pesticidal active carboxamide derivative in soil and seed application and treatment meth-ods
WO2015071180A1 (en) 2013-11-13 2015-05-21 Syngenta Participations Ag Pesticidally active bicyclic heterocycles with sulphur containing substituents
EP2873668A1 (en) 2013-11-13 2015-05-20 Syngenta Participations AG. Pesticidally active bicyclic heterocycles with sulphur containing substituents
US20160287618A1 (en) * 2013-11-15 2016-10-06 Nestec S.A. Compositions for use in the prevention or treatment of urt infections in infants or young children at risk
WO2015091649A1 (en) 2013-12-18 2015-06-25 Basf Se N-substituted imino heterocyclic compounds
WO2015091645A1 (en) 2013-12-18 2015-06-25 Basf Se Azole compounds carrying an imine-derived substituent
WO2015091945A1 (en) 2013-12-20 2015-06-25 Syngenta Participations Ag Pesticidally active substituted 5,5-bicyclic heterocycles with sulphur containing substituents
WO2015097237A1 (en) 2013-12-23 2015-07-02 Syngenta Participations Ag Benzoxaborole fungicides
WO2015104422A1 (en) 2014-01-13 2015-07-16 Basf Se Dihydrothiophene compounds for controlling invertebrate pests
WO2015177063A1 (en) 2014-05-19 2015-11-26 Syngenta Participations Ag Insecticidally active amide derivatives with sulfur-substituted phenyl or pyridine groups
US10212934B2 (en) 2014-06-25 2019-02-26 BASF Agro B.V. Pesticidal compositions
EP3269245A1 (en) * 2014-06-25 2018-01-17 Basf Agro B.V. Arnhem (NL) Pesticidal compositions
KR20170021886A (en) 2014-07-04 2017-02-28 스미또모 가가꾸 가부시끼가이샤 Pest control composition and use for same
WO2016091731A1 (en) 2014-12-11 2016-06-16 Syngenta Participations Ag Pesticidally active tetracyclic derivatives with sulfur containing substituents
WO2016120182A1 (en) 2015-01-30 2016-08-04 Syngenta Participations Ag Pesticidally active amide heterocyclic derivatives with sulphur containing substituents
EP3848364A1 (en) 2015-03-27 2021-07-14 Syngenta Participations Ag Microbiocidal heterobicyclic derivatives and intermediates for their preparation
EP3683213A1 (en) 2015-03-27 2020-07-22 Syngenta Participations Ag Microbiocidal heterobicyclic derivatives
WO2016166252A1 (en) 2015-04-17 2016-10-20 Basf Agrochemical Products B.V. Method for controlling non-crop pests
US11234436B2 (en) 2015-04-17 2022-02-01 Basf Agrochemical Products B.V. Method for controlling non-crop pests
EP3656770A2 (en) 2015-04-24 2020-05-27 Syngenta Participations AG Pesticidally active polycyclic derivatives with sulfur substituted five-membered ring heterocycles
WO2016169886A1 (en) 2015-04-24 2016-10-27 Syngenta Crop Protection Ag Pesticidally active polycyclic derivatives with sulfur substituted five-membered ring heterocyles
WO2016169882A1 (en) 2015-04-24 2016-10-27 Syngenta Participations Ag Pesticidally active polycyclic derivatives with sulfur substituted five membered ring heterocyles
WO2017001311A1 (en) 2015-07-01 2017-01-05 Syngenta Participations Ag Pesticidally active tetracyclic derivatives with sulfur containing substituents
WO2017050922A1 (en) 2015-09-23 2017-03-30 Syngenta Participations Ag Isoxazoline-substituted benzamides and analogues as insecticides
WO2017050685A1 (en) 2015-09-25 2017-03-30 Syngenta Participations Ag Pesticidally active polycyclic derivatives with 5-membered sulfur containing heterocyclic ring systems
WO2017050751A1 (en) 2015-09-25 2017-03-30 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulphur containing substituents
WO2017055147A1 (en) 2015-09-28 2017-04-06 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulphur containing substituents
WO2017063973A1 (en) 2015-10-14 2017-04-20 Syngenta Participations Ag Fungicidal compositions
WO2017067839A1 (en) 2015-10-23 2017-04-27 Syngenta Participations Ag Microbiocidal phenylamidine derivatives
WO2017067837A1 (en) 2015-10-23 2017-04-27 Syngenta Participations Ag Microbiocidal phenylamidine derivatives
WO2017072247A1 (en) 2015-10-28 2017-05-04 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017076982A1 (en) 2015-11-04 2017-05-11 Syngenta Participations Ag Microbiocidal anilide derivatives
WO2017089190A1 (en) 2015-11-23 2017-06-01 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulphur and cyclopropyl containing substituents
WO2017093214A1 (en) 2015-12-03 2017-06-08 Bayer Cropscience Aktiengesellschaft Mesoionic halogenated 3-(acetyl)-1-[(1,3-thiazol-5-yl)methyl]-1h-imidazo[1,2-a]pyridin-4-ium-2-olate derivatives and related compounds as insecticides
CN108699031A (en) * 2015-12-14 2018-10-23 Fmc公司 Two ring azoles insecticides of heterocyclic substituted
CN108699031B (en) * 2015-12-14 2021-06-15 Fmc公司 Heterocyclic substituted bicyclic azole insecticides
WO2017102006A1 (en) 2015-12-17 2017-06-22 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017108569A1 (en) 2015-12-22 2017-06-29 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2017134066A1 (en) 2016-02-05 2017-08-10 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulphur containing substituents
WO2017140771A1 (en) 2016-02-18 2017-08-24 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2017157962A1 (en) 2016-03-15 2017-09-21 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017162868A1 (en) 2016-03-24 2017-09-28 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017174449A1 (en) 2016-04-07 2017-10-12 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulphur containing substituents
WO2017174158A1 (en) 2016-04-08 2017-10-12 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017178549A1 (en) 2016-04-12 2017-10-19 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017178408A1 (en) 2016-04-15 2017-10-19 Syngenta Participations Ag Microbiocidal silicon containing aryl derivatives
WO2017189339A1 (en) 2016-04-26 2017-11-02 E I Du Pont De Nemours And Company Process for the preparation of n-[(5-pyrimidinyl)methyl]-2-pyridinamines
WO2017207757A1 (en) 2016-06-03 2017-12-07 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017220485A1 (en) 2016-06-21 2017-12-28 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018015458A1 (en) 2016-07-22 2018-01-25 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018015447A1 (en) 2016-07-22 2018-01-25 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018015449A1 (en) 2016-07-22 2018-01-25 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018029242A1 (en) 2016-08-11 2018-02-15 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018041729A2 (en) 2016-09-01 2018-03-08 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulphur containing substituents
WO2018055135A1 (en) 2016-09-23 2018-03-29 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018055133A1 (en) 2016-09-23 2018-03-29 Syngenta Participations Ag Microbiocidal tetrazolone derivatives
WO2018060039A1 (en) 2016-09-28 2018-04-05 Syngenta Participations Ag Fungicidal compositions
WO2018065414A1 (en) 2016-10-06 2018-04-12 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018077565A1 (en) 2016-10-27 2018-05-03 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulphur and hydroxylamine substituents
WO2018091389A1 (en) 2016-11-17 2018-05-24 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulphur containing substituents
WO2018095795A1 (en) 2016-11-23 2018-05-31 Syngenta Participations Ag Pesticidally active polycyclic derivatives with sulfur containing substituents
WO2018099812A1 (en) 2016-12-01 2018-06-07 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2018108726A1 (en) 2016-12-15 2018-06-21 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2018108730A1 (en) 2016-12-16 2018-06-21 Bayer Aktiengesellschaft Mesoionic imidazopyridines for use as insecticides
WO2018114791A1 (en) 2016-12-19 2018-06-28 Syngenta Participations Ag Pesticidally active azetidine sulfones amide isoxazoline derivatives
EP3336086A1 (en) 2016-12-19 2018-06-20 Syngenta Participations Ag Pesticidally active azetidine sulfone amide isoxazoline derivatives
EP3336087A1 (en) 2016-12-19 2018-06-20 Syngenta Participations Ag Pesticidally active azetidine sulfone amide isoxazoline derivatives
WO2018114790A1 (en) 2016-12-19 2018-06-28 Syngenta Participations Ag Pesticidally active azetidine sulfones amide isoxazoline derivatives
WO2018149851A1 (en) 2017-02-16 2018-08-23 Syngenta Participations Ag Fungicidal compositions
WO2018153778A1 (en) 2017-02-21 2018-08-30 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2018158365A1 (en) 2017-03-03 2018-09-07 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018162643A1 (en) 2017-03-10 2018-09-13 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018172471A1 (en) 2017-03-22 2018-09-27 Syngenta Participations Ag Pesticidally active cyclopropyl methyl amide derivatives
WO2018172477A1 (en) 2017-03-23 2018-09-27 Syngenta Participations Ag Insecticidal compounds
WO2018172480A1 (en) 2017-03-23 2018-09-27 Syngenta Participations Ag Insecticidal compounds
WO2018177880A1 (en) 2017-03-31 2018-10-04 Syngenta Participations Ag Fungicidal compositions
WO2018177894A1 (en) 2017-03-31 2018-10-04 Syngenta Participations Ag Fungicidal compositions
WO2018185013A1 (en) 2017-04-03 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018185185A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2018185191A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2018185187A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2018184985A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184982A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184988A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184984A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184987A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184986A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018185211A1 (en) 2017-04-06 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018189077A1 (en) 2017-04-12 2018-10-18 Bayer Aktiengesellschaft Mesoionic imidazopyridines for use as insecticides
WO2018197315A1 (en) 2017-04-25 2018-11-01 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2018202540A1 (en) 2017-05-02 2018-11-08 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2018206348A1 (en) 2017-05-08 2018-11-15 Syngenta Participations Ag Imidazopyrimidine derivatives with sulfur containing phenyl and pyridyl substituents
WO2018206419A1 (en) 2017-05-12 2018-11-15 Syngenta Participations Ag Microbiocidal heterobicyclic derivatives
CN106973923A (en) * 2017-05-13 2017-07-25 北京科发伟业农药技术中心 A kind of Pesticidal combination of the pyrimidine containing trifluoro-benzene
WO2018215304A1 (en) 2017-05-22 2018-11-29 Syngenta Participations Ag Tetracyclic pyridazine sulphur containing compounds and their use as pesticides
WO2018219825A1 (en) 2017-06-02 2018-12-06 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018219773A1 (en) 2017-06-02 2018-12-06 Syngenta Participations Ag Fungicidal compositions
WO2018228896A1 (en) 2017-06-14 2018-12-20 Syngenta Participations Ag Fungicidal compositions
WO2018229202A1 (en) 2017-06-16 2018-12-20 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
WO2018234240A1 (en) 2017-06-19 2018-12-27 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2019002151A1 (en) 2017-06-28 2019-01-03 Syngenta Participations Ag Fungicidal compositions
WO2019008072A1 (en) 2017-07-05 2019-01-10 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2019008115A1 (en) 2017-07-07 2019-01-10 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2019011926A1 (en) 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011928A1 (en) 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011923A1 (en) 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011929A1 (en) 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019012011A1 (en) 2017-07-12 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019012001A1 (en) 2017-07-12 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019012003A1 (en) 2017-07-13 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019030358A1 (en) 2017-08-11 2019-02-14 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2019030359A1 (en) 2017-08-11 2019-02-14 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2019030355A1 (en) 2017-08-11 2019-02-14 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2019030357A1 (en) 2017-08-11 2019-02-14 Syngenta Participations Ag Pesticidally active thiophene derivatives
WO2019043183A1 (en) * 2017-08-31 2019-03-07 Basf Se Method of controlling rice pests in rice
CN111031798A (en) * 2017-08-31 2020-04-17 巴斯夫欧洲公司 Method for controlling rice pests in rice
KR20200041892A (en) * 2017-08-31 2020-04-22 바스프 에스이 How to control rice pests from rice
WO2019042932A1 (en) * 2017-08-31 2019-03-07 Basf Se Method of controlling rice pests in rice
KR102659381B1 (en) 2017-08-31 2024-04-19 바스프 에스이 How to Control Rice Pests in Rice
WO2019053027A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053026A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019052930A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Fungicidal compositions
WO2019053024A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053019A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053010A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053015A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053016A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053182A1 (en) 2017-09-18 2019-03-21 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2019068809A1 (en) 2017-10-05 2019-04-11 Syngenta Participations Ag Microbiocidal picolinamide derivatives
WO2019068812A1 (en) 2017-10-05 2019-04-11 Syngenta Participations Ag Microbiocidal picolinamide derivatives
WO2019068820A1 (en) 2017-10-06 2019-04-11 Syngenta Participations Ag Pesticidally active pyrrole derivatives
WO2019068819A1 (en) 2017-10-06 2019-04-11 Syngenta Participations Ag Pesticidally active pyrrole derivatives
WO2019076778A1 (en) 2017-10-16 2019-04-25 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur and sulfonimidamides containing substituents
WO2019086474A1 (en) 2017-10-31 2019-05-09 Syngenta Participations Ag Pesticidally active mesoionics heterocyclic compounds
WO2019096709A1 (en) 2017-11-15 2019-05-23 Syngenta Participations Ag Microbiocidal picolinamide derivatives
WO2019097054A1 (en) 2017-11-20 2019-05-23 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019105933A1 (en) 2017-11-29 2019-06-06 Syngenta Participations Ag Microbiocidal thiazole derivatives
WO2019034796A1 (en) 2017-12-01 2019-02-21 Syngenta Participations Ag Novel pyrimidine derivatives
WO2019115404A1 (en) 2017-12-13 2019-06-20 Syngenta Participations Ag Pesticidally active mesoionic heterocyclic compounds
WO2019121149A1 (en) 2017-12-19 2019-06-27 Syngenta Participations Ag Microbiocidal picolinamide derivatives
WO2019134840A1 (en) * 2018-01-05 2019-07-11 Basf Se Control of pests of soybean plants with mesoionic compounds
WO2019138018A1 (en) 2018-01-15 2019-07-18 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2019173173A1 (en) 2018-03-05 2019-09-12 E. I. Du Pont De Nemours And Company Process and intermidiates for the preparation of certain mesoionic pesticides
WO2019219689A1 (en) 2018-05-18 2019-11-21 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfoximine containing substituents
WO2019229088A1 (en) 2018-05-30 2019-12-05 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2019229089A1 (en) 2018-05-31 2019-12-05 Syngenta Participations Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2019234160A1 (en) 2018-06-06 2019-12-12 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
EP4342297A2 (en) 2018-06-06 2024-03-27 Syngenta Crop Protection AG Pesticidally active heterocyclic derivatives with sulfoximine containing substituents
WO2019234158A1 (en) 2018-06-06 2019-12-12 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfoximine containing substituents
WO2019243263A1 (en) 2018-06-19 2019-12-26 Syngenta Participations Ag Insecticidal compounds
WO2019243262A1 (en) 2018-06-19 2019-12-26 Syngenta Crop Protection Ag Pesticidally active azetidine sulfones amide isoxazoline derivatives
WO2019243256A1 (en) 2018-06-19 2019-12-26 Syngenta Crop Protection Ag Pesticidally active isoxazoline derivatives containing an amide group and an azetidine sulfone group
WO2019243253A1 (en) 2018-06-19 2019-12-26 Syngenta Crop Protection Ag Pesticidally active isoxazoline derivatives containing an amide group and an azetidine sulfone group
WO2020002331A1 (en) 2018-06-29 2020-01-02 Syngenta Crop Protection Ag Microbiocidal oxadiazole derivatives
WO2020002563A1 (en) 2018-06-29 2020-01-02 Syngenta Participations Ag Pesticidally active azole-amide compounds
WO2020007658A1 (en) 2018-07-02 2020-01-09 Syngenta Crop Protection Ag 3-(2-thienyl)-5-(trifluoromethyl)-1,2,4-oxadiazole derivatives as agrochemical fungicides
WO2020011808A1 (en) 2018-07-13 2020-01-16 Syngenta Crop Protection Ag Pesticidally-active bicyclic heteroaromatic compounds
WO2020016180A1 (en) 2018-07-16 2020-01-23 Syngenta Crop Protection Ag Microbiocidal oxadiazole derivatives
WO2020025658A1 (en) 2018-08-03 2020-02-06 Syngenta Crop Protection Ag Pesticidally-active bicyclic heteroaromatic compounds
WO2020030503A1 (en) 2018-08-07 2020-02-13 Syngenta Crop Protection Ag Pesticidally-active bicyclic heteroaromatic compounds
WO2020035565A1 (en) 2018-08-17 2020-02-20 Syngenta Crop Protection Ag Pesticidally-active mesoionic bicyclic heteroaromatic compounds
WO2020058207A1 (en) 2018-09-19 2020-03-26 Syngenta Crop Protection Ag Microbiocidal quinoline carboxamide derivatives
WO2020064564A1 (en) 2018-09-26 2020-04-02 Syngenta Participations Ag Insecticidal compounds
WO2020070049A1 (en) 2018-10-02 2020-04-09 Syngenta Participations Ag Pesticidally active benzene- and azine-amide compounds
WO2020070132A1 (en) 2018-10-06 2020-04-09 Syngenta Participations Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2020070131A1 (en) 2018-10-06 2020-04-09 Syngenta Participations Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2020084075A1 (en) 2018-10-24 2020-04-30 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfoximine containing substituents
WO2020120694A1 (en) 2018-12-14 2020-06-18 Syngenta Participations Ag Pesticidally-active bicyclic heteroaromatic compounds
WO2020120697A1 (en) 2018-12-14 2020-06-18 Syngenta Crop Protection Ag Pesticidally-active cyanamide heterocyclic compounds
WO2020127345A1 (en) 2018-12-21 2020-06-25 Syngenta Participations Ag Pesticidally active pyrazole derivatives
WO2020141136A1 (en) 2018-12-31 2020-07-09 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2020141135A1 (en) 2018-12-31 2020-07-09 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2020164994A1 (en) 2019-02-13 2020-08-20 Syngenta Crop Protection Ag Pesticidally active pyrazole derivatives
WO2020164993A1 (en) 2019-02-13 2020-08-20 Syngenta Crop Protection Ag Pesticidally active pyrazole derivatives
EP3696175A1 (en) 2019-02-18 2020-08-19 Syngenta Crop Protection AG Pesticidally active azole-amide compounds
WO2020174096A1 (en) 2019-02-28 2020-09-03 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2020174094A1 (en) 2019-02-28 2020-09-03 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2020182577A1 (en) 2019-03-08 2020-09-17 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2020239517A1 (en) 2019-05-29 2020-12-03 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
WO2021009311A1 (en) 2019-07-17 2021-01-21 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
EP3769623A1 (en) 2019-07-22 2021-01-27 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
WO2022180096A1 (en) 2021-02-26 2022-09-01 Syngenta Crop Protection Ag Pesticidal compositions
WO2023086802A1 (en) 2021-11-10 2023-05-19 Corteva Agriscience Llc Processes for the preparation of certain mesoionic pesticides
WO2024040111A1 (en) 2022-08-18 2024-02-22 Corteva Agriscience Llc Process for the preparation and isolation of intermediates of certain mesoionic pesticides
RU2805872C1 (en) * 2023-04-26 2023-10-24 Общество с ограниченной ответственностью "Рустарк" Insecticidal preparation and method of its use

Also Published As

Publication number Publication date
MX358389B (en) 2018-08-17
ZA201302430B (en) 2014-06-25
EP2658856B1 (en) 2015-02-25
BR112013009935B1 (en) 2017-08-01
EP2658856A1 (en) 2013-11-06
MA34830B1 (en) 2014-01-02
KR101897840B1 (en) 2018-09-12
AU2011352379A1 (en) 2013-04-11
US20150038329A1 (en) 2015-02-05
SG189206A1 (en) 2013-06-28
IL225859A0 (en) 2013-07-31
US8895738B2 (en) 2014-11-25
PH12013501402A1 (en) 2013-08-28
RU2013135410A (en) 2015-02-10
CN103459387B (en) 2015-08-26
MX2013007494A (en) 2013-08-01
AR084646A1 (en) 2013-05-29
CA2817902A1 (en) 2012-07-05
JP5911510B2 (en) 2016-04-27
BR112013009935B8 (en) 2022-11-08
US20130190171A1 (en) 2013-07-25
TW201225842A (en) 2012-07-01
RU2585616C2 (en) 2016-05-27
BR112013009935A2 (en) 2016-07-05
KR20140014122A (en) 2014-02-05
CN105198874A (en) 2015-12-30
IL225859A (en) 2016-08-31
BR112013009935C8 (en) 2017-09-19
JP2014503550A (en) 2014-02-13
TWI528899B (en) 2016-04-11
UY33842A (en) 2012-07-31
AU2011352379B2 (en) 2016-07-14
HUE025531T2 (en) 2016-05-30
ES2536305T3 (en) 2015-05-22
CN103459387A (en) 2013-12-18
CO6761321A2 (en) 2013-09-30
AU2011352379A2 (en) 2013-05-02

Similar Documents

Publication Publication Date Title
AU2011352379B2 (en) Mesoionic pyrido [1,2 -a] pyrimidine pesticides
TWI652014B (en) Heterocyclic substituted bicycloazole insecticide
WO2012106495A1 (en) Mesoionic pesticides
EP3268359A1 (en) Heterocycle-substituted bicyclic azole pesticides
EP3390385B1 (en) Heterocycle-substituted bicyclic azole pesticides
EP3621964B1 (en) Mesoionic insecticides
EP2770831B1 (en) 1,3-diaryl-substituted heterocyclic pesticides
EP3887354B1 (en) Meta-diamide compounds for controlling invertebrate pests
EP2850074A1 (en) 1,3-diaryl-substituted heterocyclic pesticides
EP3280713A1 (en) Bicyclic pyrazole pesticides
US20220135562A1 (en) Heterocycle-substituted bicyclic azole pesticides
EP4093738A1 (en) Mesoionic insecticides

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11808109

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 13876636

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2011808109

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2011352379

Country of ref document: AU

Date of ref document: 20111222

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2817902

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2013001866

Country of ref document: CL

WWE Wipo information: entry into national phase

Ref document number: A201308111

Country of ref document: UA

Ref document number: MX/A/2013/007494

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 12013501402

Country of ref document: PH

ENP Entry into the national phase

Ref document number: 2013547567

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20137019825

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 13177712

Country of ref document: CO

ENP Entry into the national phase

Ref document number: 2013135410

Country of ref document: RU

Kind code of ref document: A

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112013009935

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112013009935

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20130424