WO2012106495A1 - Pesticides méso-ioniques - Google Patents

Pesticides méso-ioniques Download PDF

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Publication number
WO2012106495A1
WO2012106495A1 PCT/US2012/023583 US2012023583W WO2012106495A1 WO 2012106495 A1 WO2012106495 A1 WO 2012106495A1 US 2012023583 W US2012023583 W US 2012023583W WO 2012106495 A1 WO2012106495 A1 WO 2012106495A1
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Prior art keywords
och3
compound
ocf3
methyl
scf3
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PCT/US2012/023583
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English (en)
Inventor
Caleb William Holyoke Jr
My-Hanh Thi Tong
Wenming Zhang
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E. I. Du Pont De Nemours And Company
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Publication of WO2012106495A1 publication Critical patent/WO2012106495A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

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.
  • PCT Patent Publication WO 09/099929 discloses certain mesoionic pyrimidinium compounds of Formula i as insecticides
  • 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:
  • each R 1 is independently halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4
  • cycloalkyl C3-C4 halocycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio or C1-C4 haloalkylthio;
  • each R 2 is independently halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4
  • cycloalkyl C3-C4 halocycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 haloalkylthio, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, Ci ⁇ C 4 alkylsulfonyl or C1-C4 haloalkylsulfonyl;
  • n 0, 1 or 2;
  • n 1, 2 or 3.
  • 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.
  • compositions comprising, “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.
  • 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 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 (e.g., berries and cherries) and other specialty crops (e.g., canola, sunflower and olives).
  • wheat 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 e.g., sweet potatoes, grapes, cotton, tree fruits (e
  • 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.
  • horticultural crops e.g., greenhouse, nursery or ornamental plants not grown in a field
  • turf e.g., sod farm, pasture, golf course, lawn, sports field, etc.
  • wood products e.g., 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
  • 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.
  • 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.
  • Cycloalkyl includes cyclopropyl and cyclobutyl.
  • 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.
  • 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 CF 3 , CH 2 C1, CH 2 CF 3 and CC1 2 CF 3 .
  • haloalkoxy "haloalkylthio”
  • haloalkylsulfmyl and “haloalkylsulfonyl” are defined analogously to the term “haloalkyl”.
  • haloalkoxy examples include CF 3 0, CC1 3 CH 2 0, HCF 2 CH 2 CH 2 0 and CF 3 CH 2 0.
  • haloalkylthio examples include CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S.
  • 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.
  • 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.
  • 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".
  • 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 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.
  • Q represents
  • 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 a sterically demanding alkyl group (e.g., isopropyl) in the ortho-position of the phenyl ring with respect to the pyrimidinium ring may exist as two rotamers due to restricted rotation about the phenyl ring-pyrimidinium ring bond.
  • 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 each R 1 is independently halogen,
  • Embodiment la A compound of Embodiment 1 wherein each R 1 is independently F, CI, CH 3 or OCH3.
  • Embodiment 2 A compound of Formula 1 or any one of Embodiments 1-1 a wherein each R 2 is independently halogen or C1-C4 haloalkyl.
  • Embodiment 2a A compound of Embodiment 2 wherein each R 2 is independently CI or CF 3 .
  • Embodiment 2b A compound of Embodiment 2 or 2a wherein one R 2 is at the 3- position.
  • Embodiment 2c A compound of Embodiment 2 or 2a wherein one R 2 is at the 5- position.
  • Embodiment 2d A compound of any one of Embodiments 2-2c wherein one R 2 is at the
  • Embodiment 3 A compound of Formula 1 or any one of Embodiments l-2a wherein n is 0 or 1.
  • Embodiment 4 A compound of Formula 1 or any one of Embodiments 1-3 wherein m is 1 or 2.
  • Embodiments of this invention 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 1-4 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
  • each R 1 is independently halogen, C1-C4 alkyl or C1-C4 alkoxy
  • each R 2 is independently halogen or C1-C4 haloalkyl.
  • Embodiment B A compound of Embodiment A wherein
  • each R 1 is independently F, CI, CH 3 or OCH 3 ;
  • each R 2 is independently CI or CF 3 .
  • Embodiment C A compound of Embodiment B wherein
  • n 0 or 1 ;
  • n 1 or 2.
  • Specific embodiments include compounds of Formula 1 selected from the group consisting of: l-[(2-chloro-5-thiazolyl)methyl]-3-[3-(3,5-dichloro-2-pyridinyl)phenyl]-2- hydroxy-9-methyl-4-oxo-4H-pyrido[l,2-a]pyrimidinium inner salt;
  • 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.
  • 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.
  • Embodiments of the invention also include any of the preceding embodiments, alone or in combination, wherein the invertebrate pest is an arthropod.
  • Embodiments of the invention also include any of the preceding embodiments, alone or in combination, 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, alone or in combination, wherein the arthropod is an insect.
  • Embodiments of the invention also include any of the preceding embodiments, alone or in combination, wherein the insect is in the order Hemiptera.
  • Embodiments of the invention also include any of the preceding embodiments, alone or in combination, wherein the insect is a planthopper. Embodiments of the invention also include any of the preceding embodiments, alone or in combination, wherein the insect is a planthopper in the family Delphacidae. Embodiments of the invention also include any of the preceding embodiments, alone or in combination, wherein the insect is a leafhopper. Embodiments of the invention also include any of the preceding embodiments, alone or in combination, wherein the insect is a leafhopper in the family Cicadellidae. Embodiments of the invention also include any of the preceding embodiments, alone or in combination, wherein the invertebrate pest is a gastropod. Embodiments of the invention also include any of the preceding embodiments, alone or in combination, 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, alone or in combination, wherein the invertebrate pest is a nematode.
  • Embodiments of the invention also include any of the preceding embodiments, alone or in combination, wherein the nematode is selected from phytophagous nematodes.
  • Embodiments of the invention also include any of the preceding embodiments, alone or in combination, wherein the invertebrate pest is a helminth.
  • Embodiments of the invention also include any of the preceding embodiments, alone or in combination, wherein the helminth is selected from the group consisting of roundworms, heartworms, flukes, acanthocephalans and tapeworms.
  • 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 C1-C5 alkyl or an optionally substituted phenyl group as shown in Scheme 2 (examples of substituted phenyl groups include 4-nitrophenyl, 2,4,6-trichlorophenyl, pentachlorophenyl or pentafluorophenyl). 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 described in Tables 1-34, 1-35 and 1-36) catalyzed by palladium (J. Org. Chem
  • R is C -C5 alkyl or 3b (R is C -C5 alkyl or optionally substituted optionally substituted phenyl) phenyl)
  • Esters of Formula 4 can be prepared from the corresponding acids by methods well known in the art.
  • the corresponding acids of Formula 4 wherein R is H are readily prepared by methods known in the art (examples are listed in Table 1-1).
  • 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.
  • B R is alkyl
  • Compounds of Formula 1 can also be prepared by treatment of compound 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 m 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 compound 2 with compounds of Formula 3d or 3e, or by condensation of compound 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 one or more equivalents of an acid acceptor (see, for example, Zeitschrift f r Naturutz, 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.
  • Compound la can be prepared by condensation of compound 2 with carbon suboxide (3f) (see, for example, J. Org. Chem. 1972, 37(9), 1422-1425) as shown in Scheme 5.
  • the reaction is typically performed in an inert solvent such as ether and can include the use of a catalyst such as AICI3.
  • Compounds of Formula 1 can be prepared from compounds of Formula lb and compounds of Formula 5 wherein M is a boronic acid, boronic acid ester or trifluoroborate salt, or M is trialkylstannyl or zinc, as shown in Scheme 6.
  • compounds of Formula 13c 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 pyridine ring to provide the 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 C -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 compound la 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 compound la by halogenation using, for example, liquid bromine or N-halosuccinimides of Formula 10 as shown in Scheme 8.
  • 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 9 (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 9, and these bases and solvents are well known in the art.
  • Compounds of Formula 11 can be prepared from 2-amino-3-methylpyridine by methods analogous to those shown in Schemes 1 through 5.
  • compound 2 is an important intermediate useful in the preparation of compounds of Formula 1.
  • Compound 2 is an embodiment of the present invention.
  • a further embodiment of the present invention is the use of compound 2 in the preparation of compounds of Formula 1.
  • compound 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 compound 2 is shown in Scheme 10.
  • 2-amino-3-methylpyridine (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 the 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 compound 2.
  • Another alternative method for the preparation of compound 2 is by the reaction of an appropriate amine with the halogen-substituted compound analogous to compound 2a (i.e. compound 2a wherein the amino group is replaced with halogen) in the presence of a copper or palladium catalyst.
  • R x is C(0)OH; is H; n is 0
  • 5-CN ⁇ is C(0)OH; Ry is H; (R 1 ⁇ is 6-iluoro
  • 5-CN ⁇ is C(0)OH; Ry is H; (R l ) n is 4-chloro
  • 5-CN ⁇ is C(0)OH; Ry is H; (R ⁇ ) n is 4-methoxy
  • 5-CN ⁇ is C(0)OH; Ry is H; (R 1 ⁇ is 5-iodo
  • 5-CN ⁇ is C(0)OH; Ry is H; (R ⁇ ) n is 5-cyclobutyl
  • 5-CN ⁇ is C(0)OH; Ry is H; (R ⁇ ) n is 5-isopropoxy
  • R x is C(0)OH
  • 5-CN k is C(0)OH; Ry is H; (R 1 ⁇ is 5,6-difluoro
  • Table 1-2 is identical to Table I- 1 , 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
  • 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- 1 , except that R x is C(0)OH and R is C(0)OH.
  • Table 1-9 is identical to Table I-l, except that R x is C(0)OH and R is C(0)OMe.
  • Table I- 10 is identical to Table I-l, except that R x is C(0)OH and Ry is C(0)OEt.
  • Table I-l 1 is identical to Table I-l, except that R x is C(0)OH and Ry is C(0)OC(CH 3 ) 3 .
  • Table 1-12 is identical to Table I-l, except that R x is C(0)OH and Ry is C(0)OPh.
  • Table 1-13 is identical to Table I-l, except that R x is C(0)OH and Ry is C(0)0(2,4,6- trichloropheny 1) .
  • Table 1-14 is identical to Table I-l, except that R x is C(0)OH and Ry is C(0)0(4- nitrophenyl).
  • Table 1-15 is identical to Table I-l, 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 I- 17 is identical to Table I- 1 , 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
  • Table 1-19 is identical to Table I-l, except that R x is C(0)OPh and R 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 R 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- 1 , 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 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
  • 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 1-34 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 n is 0, (R 2 ) m is 3-fluoro, 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 is identical to Table 1-34, except that R is CH(CN)C0 2 Me. TABLE 1-41
  • Table 1-41 is identical to Table 1-34, except that R is CH(CN)C0 2 Et.
  • 1,3-Diethyl 2-(3-bromophenyl)propanedioate (5.74 g), 4,4,4',4',5,5,5',5'-octamethyl- 2,2'-bi-l,3,2-dioxaborolane (5.4 g), dichloro[l, -bis(diphenylphosphino)ferrocene]- palladium(II), 810 mg) and potassium acetate (8.0 g) were added to anhydrous dioxane (80 mL), and the reaction mixture was heated to reflux and stirred for 3 hours. The reaction was then cooled room temperature, poured into water (100 mL), and extracted with hexanes (2 x 100 mL).
  • Step B Preparation of 1,3-diethyl 2-[3-[3-chloro-5-(trifluoromethyl)-2- pyridinyl]phenyl]propanedioate
  • 1,3-Diethyl 2-[3-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenyl]propanedioate (5.34 g), 2,3-dichloro-5-(trifluoromethyl)pyridine (4.3 g) and potassium carbonate (3.5 g) were added to tetrahydrofuran (50 mL) and water (15 mL), and the reaction mixture was then degassed by bubbling nitrogen gas through the reaction mixture for 10 minutes.
  • Bis(triphenylphosphine)palladium(II) dichloride 350 mg was added, and the reaction mixture was heated to reflux and stirred for 3 hours.
  • the resulting reaction mixture was heated to 45-48 °C, and the reaction mixture was maintained at this temperature for 6.5 hours.
  • the reaction mixture was then cooled to room temperature, diluted with water (750 mL), and extracted with ethyl acetate (750 mL).
  • Step D Preparation of N- [(2-chloro-5 -thiazolyl)methyl] -3 -methyl-2-pyridinamine
  • N-(3-methyl-2-pyridinyl)formamide 100 g
  • potassium carbonate 109.6 g
  • tetrabutylammonium bromide 4.73 g
  • isopropyl alcohol 7500 mL
  • 2-chloro-5- (chloromethyl)thiazole distilled, 123.9 g
  • the reaction mixture was then heated to 73-75 °C and maintained at that temperature for 5.5 hours.
  • the mixture was then cooled to 50 °C, and 10%> aqueous NaOH (880 g) was added via an addition funnel over a period of 20 minutes.
  • the resulting turbid reaction mass was stirred at 57-60 °C for approximately 3.5 hours.
  • Water approximately 800 mL was added over a period of 5 minutes to the reaction mixture; the reaction mixture was then cooled to 10 °C and stirred at 10 °C for 10 minutes.
  • the slurry was filtered, and the resulting solids were washed with chilled water (2 x 200 mL), air dried, and further dried under reduced pressure at 40 °C overnight to provide a white solid (134 g).
  • Step E Preparation of l-[(2-chloro-5-thiazolyl)methyl]-3-[3-[3-chloro-5-
  • a solution of aqueous sodium hydroxide (20 mL of a 20%> solution by weight) was heated to 50 °C and then poured into 1,3-diethyl 2-[3-[3-chloro-5-(trifluoromethyl)-2- pyridinyl]phenyl]propanedioate (1.5 g).
  • the reaction mixture was heated at 50 °C for 1 hour, cooled in a water ice-acetone bath, cautiously acidified to pH 2, and extracted with ethyl acetate (100 mL).
  • the organic layer was dried (MgSC ⁇ ), filtered, and concentrated under reduced pressure.

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Abstract

La présente invention concerne des composés de formule 1, dans laquelle chaque R1 est indépendamment halogène, cyano, alkyle en C1-C4, halogénoalkyle en C1-C4, cycloalkyle en C3-C4, halogénocycloalkyle en C3-C4, alcoxy en C1-C4, halogénoalcoxy en C1-C4, alkylthio en C1-C4 ou halogénoalkylthio en C1-C4 ; chaque R2 est indépendamment halogène, cyano, alkyle en C1-C4, halogénoalkyle en C1-C4, cycloalkyle en C3-C4, halogénocycloalkyle en C3-C4, alcoxy en C1-C4, halogénoalcoxy en C1-C4, alkylthio en C1-C4, halogénoalkylthio en C1-C4, alkylsulfinyle en C1-C4, halogénoalkylsulfinyle en C1-C4, alkylsulfonyle en C1-C4 ou halogénoalkylsulfonyle en C1-C4 ; (1) où n est 0, 1 ou 2 ; et m est 1, 2 ou 3. La présente invention concerne en outre des compositions contenant les composés de Formule 1 et des procédés pour lutter contre un organisme nuisible invertébré comprenant la mise en contact de l'organisme nuisible invertébré ou son environnement avec une quantité biologiquement efficace d'un composé ou d'une composition de l'invention.
PCT/US2012/023583 2011-02-03 2012-02-02 Pesticides méso-ioniques WO2012106495A1 (fr)

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WO2013090547A1 (fr) * 2011-12-15 2013-06-20 E. I. Du Pont De Nemours And Company Di-sels d'acide malonique et procédé de fabrication de dihalogénures de malonyle
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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
US8895738B2 (en) 2010-12-29 2014-11-25 E I Du Pont De Nemours And Company Mesoionic pyrido [1, 2-A] pyrimidine pesticides
US9018220B2 (en) 2008-02-06 2015-04-28 E I Du Pont De Nemours And Company Mesoionic pesticides
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JPWO2016121970A1 (ja) * 2015-01-30 2017-11-09 住友化学株式会社 ビピリジン化合物及びその有害節足動物防除用途
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