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WO2023023572A1 - Molécules ayant certaines utilités pesticides, et intermédiaires, compositions et procédés associés à celles-ci - Google Patents

Molécules ayant certaines utilités pesticides, et intermédiaires, compositions et procédés associés à celles-ci Download PDF

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WO2023023572A1
WO2023023572A1 PCT/US2022/075104 US2022075104W WO2023023572A1 WO 2023023572 A1 WO2023023572 A1 WO 2023023572A1 US 2022075104 W US2022075104 W US 2022075104W WO 2023023572 A1 WO2023023572 A1 WO 2023023572A1
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Prior art keywords
alkyl
phenyl
haloalkyl
triazol
cycloalkyl
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Inventor
Erich W. Baum
Gary Crouse
David A. Demeter
Natalie C. GIAMPIETRO
Lindsey G. HORTY
Jeffrey Petkus
Thomas C. Sparks
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Corteva Agriscience LLC
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Corteva Agriscience LLC
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    • 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
    • C07D417/14—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 three or more hetero rings
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/02—Acaricides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
    • C07D253/06—1,2,4-Triazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • This disclosure relates to the field of molecules having pesticidal utility against pests in Phyla Arthropoda, Mollusca, and Nematoda, processes to produce such molecules, intermediates used in such processes, and processes of using such pesticidal compositions against such pests.
  • These pesticidal compositions may be used, for example, as acaricides, insecticides, miticides, molluscicides, and nematicides.
  • Vector-borne diseases are responsible for about 17% of the global parasitic and infectious diseases. Malaria alone causes over 800,000 deaths a year, 85% of which occur in children under five years of age. Each year there are about 50 to about 100 million cases of dengue fever. A further 250,000 to 500,000 cases of dengue hemorrhagic fever occur each year (Matthews., Integrated Vector Management: Controlling Vectors of Malaria and Other Insect Vector Borne Diseases, Ch. 1, p. 1, 2011). Vector control plays a critical role in the prevention and control of infectious diseases. However, insecticide resistance, including resistance to multiple insecticides, has arisen in all insect species that are major vectors of human diseases (Rivero et al.).
  • arthropod species have developed resistance to at least one pesticide (Whalon et al., Analysis of Global Pesticide Resistance in Arthropods, Global Pesticide Resistance in Arthropods, Ch. 1, p. 5-33, 2008). Furthermore, the cases of insect resistance continue to exceed by far the number of cases of herbicide and fungicide resistance (Sparks et al., IRAC: Mode of action classification and insecticide resistance management, Pesticide Biochemistry and Physiology (2014) available online 4 December 2014).
  • Plant parasitic nematodes are among the most widespread pests, and are frequently one of the most insidious and costly. It has been estimated that losses attributable to nematodes are from about 9% in developed countries to about 15% in undeveloped countries. However, in the United States of America a survey of 35 States on various crops indicated nematode-derived losses of up to 25% (Nicol et al., Current Nematode Threats to World Agriculture, Genomic and Molecular Genetics of Plant - Nematode Interactions, p. 21-43, 2011).
  • gastropods are pests of less economic importance than other arthropods or nematodes, but in certain places, they may reduce yields substantially, severely affecting the quality of harvested products, as well as, transmitting human, animal, and plant diseases. While only a few dozen species of gastropods are serious regional pests, a handful of species are important pests on a worldwide scale. In particular, gastropods affect a wide variety of agricultural and horticultural crops, such as, arable, scenic, and fiber crops; vegetables; bush and tree fruits; herbs; and ornamentals (Speiser, B., Molluscicides, Encyclopedia of Pest Management, Ch. 219, p. 506-508, 2002).
  • Termites cause damage to all types of private and public structures, as well as to agricultural and forestry resources. In 2005, it was estimated that termites cause over USS50 billion in damage worldwide each year (Korb, J., Termites, Current Biology, Vol. 17, No. 23, 2007).
  • alkenyl means an acyclic, unsaturated (at least one carbon-carbon double bond), branched or unbranched, substituent consisting of carbon and hydrogen, for example, vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, and decenyl.
  • alkoxy means an alkyl further consisting of a carbon-oxygen single bond, for example, methoxy, ethoxy, propoxy, isopropoxy, 1 -butoxy, 2-butoxy, isobutoxy, tert-butoxy, pentoxy, 2-methylbutoxy, 1,1- dimethylpropoxy, hexoxy, heptoxy, octoxy, nonoxy, and decoxy.
  • alkyl means an acyclic, saturated, branched or unbranched, substituent consisting of carbon and hydrogen, for example, methyl, ethyl, propyl, isopropyl, 1 -butyl, 2 -butyl, isobutyl, tert-butyl, pentyl, 2-methylbutyl, 1,1 -dimethylpropyl, hexyl, heptyl, octyl, nonyl, and decyl.
  • alkynyl means an acyclic, unsaturated (at least one carbon-carbon triple bond, and any double bonds), branched or unbranched, substituent consisting of carbon and hydrogen, for example, ethynyl, propargyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, and decynyl.
  • aryl means a cyclic, aromatic substituent consisting of hydrogen and carbon, for example, phenyl, naphthyl, and biphenyl.
  • cycloalkenyl means a monocyclic or polycyclic, unsaturated (at least one carbon-carbon double bond) substituent consisting of carbon and hydrogen, for example, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, norbomenyl, bicyclo[2.2.2]octenyl, tetrahydronaphthyl, hexahydronaphthyl, and octahydronaphthyl.
  • cycloalkyl means a monocyclic or polycyclic, saturated substituent consisting of carbon and hydrogen, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, norbomyl, bicyclo[2.2.2]octyl, and decahydronaphthyl.
  • cycloalkoxy means a cycloalkyl further consisting of a carbon-oxy gen single bond, for example, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclodecyloxy, norbomyloxy, andbicyclo[2.2.2]octyloxy.
  • halo means fluoro, chloro, bromo, and iodo.
  • haloalkyl means an alkyl further consisting of, from one to the maximum possible number of, identical or different, halos, for example, fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoromethyl, 2- fluoroethyl, 2,2,2-trifluoroethyl, chloromethyl, trichloromethyl, and 1,1,2,2-tetrafluoroethyl.
  • heterocyclyl means a cyclic substituent that may be fully saturated, partially unsaturated, or fully unsaturated, where the cyclic structure contains at least one carbon and at least one heteroatom, where said heteroatom is nitrogen, sulfitr, or oxygen. Examples are:
  • aromatic heterocyclyl substituents include, but are not limited to, benzofuranyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzothienyl, benzothiazolyl, cinnolinyl, furanyl, indazolyl, indolyl, imidazolyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, 1,3,4-oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl, 1,2,3,4-tetrazolyl, thiazolinyl, thiazolyl, thi
  • (2) fully saturated heterocyclyl substituents include, but are not limited to, piperazinyl, piperidinyl, morpholinyl, pyrrolidinyl, tetrahydrofuranyl, and tetrahydropyranyl;
  • (3) partially or fully unsaturated heterocyclyl substituents include, but are not limited to, 4,5-dihydro- isoxazolyl, 4,5-dihydro-oxazolyl, 4, 5-dihydro- 1 //-pyrazolyl. 2,3-dihydro-[l,3,4]-oxadiazolyl, and 1,2,3,4-tetrahydro-quinolinyl; and
  • heterocyclyls include the following: thietanyl thietanyl-oxide and thietanyl-dioxide.
  • ambient pressure refers to pressures from about 80 kilopascals (kPa) to about 105 kPa.
  • the term “ambient temperature” or “room temperature” refers to temperatures ranging from about 20 °C to about 24 °C.
  • locus means a habitat, breeding ground, plant, seed, soil, material, or environment, m which a pest is growing, may grow, or may traverse.
  • a locus may be where crops, trees, fruits, cereals, fodder species, vines, turf, and/or ornamental plants, are growing; where domesticated animals are residing; the interior or exterior surfaces of buildings (such as places where grains are stored); the materials of construction used in buildings (such as impregnated wood); and the soil around buildings.
  • substituted furanyl, substituted phenyl, substituted pyridazinyl, substituted pyridyl, substituted pyrimidinyl, or substituted thienyl wherein said substituted furanyl, substituted phenyl, substituted pyridazinyl, substituted pyridyl, substituted pyrimidinyl, and substituted thienyl have one or more substituents independently selected from H, F, Cl, Br, I, CN, OH, SH, NO2, oxo, thioxo, NR x R y , Ci-Cg alkyl, Ci-Cg haloalkyl, Cs-Cg cycloalkyl, Ci-Cx halocycloalkyl, C’.-Cx cycloalkoxy, C 3 -C 8 halocycloalkoxy, Ci-C 8 alkoxy, Ci-C 8 haloalkoxy, CL-Cs alkenyl,
  • each alkyl, haloalkyl, cycloalkyl, halocycloalkyl, alkoxy, haloalkoxy, alkenyl, cycloalkenyl, haloalkenyl, alkynyl, phenyl, phenoxy, and (Het-1) substituent may be optionally substituted with one or more substituents independently selected from H, F, Cl, Br, I, CN, OH, SH, NO2, oxo, thioxo, NR*R y , Ci-C 8 alkyl, Ci-Cg haloalkyl, C 3 -Cg cycloalkyl, Ci-Cg halocycloalkyl, C 3 -C 8 cycloalkoxy, C 3 -C 8 halocycloalkoxy, Ci-Cs alkoxy, Ci-Cg haloalkoxy,
  • Het is a 5- or 6-membered, saturated or unsaturated, heterocyclic ring, containing one or more heteroatoms independently selected from nitrogen, sulfur, or oxygen, and where said heterocyclic ring may also be substituted with one or more substituents independently selected from H, F, Cl, Br, I, CN, OH, SH, NO 2 , oxo, thioxo, NR x R y , Ci-C 8 alkyl, Ci-Cg haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 3 -Cg cycloalkoxy, C 3 -C 8 halocycloalkoxy, Ci-Cg alkoxy, Ci-Cg haloalkoxy, C 2 -C 8 alkenyl, C 3 -Cg cycloalkenyl, C 2 -Cg haloalkenyl, C 2 -Cg alkynyl,
  • a 6-membered non-aromatic carbocyclic ring optionally substituted with one or more substituents independently selected fromH, Cl, Br, F, I, CN, oxo, Ci-Ce alkyl, Ci-Cs -haloalkyl, Ci-Cs alkoxy, Ci-Cs haloalkoxy, Ci-Ce alkylthio, Ci-Ce haloalkylthio, Cz-Cs alkenyl, C2-C6 haloalkenyl, and C2-C6 haloalkenyl;
  • (D) L is a linker selected from
  • each of R a , R b , R c , R d , R e , and R f is selected from H, F, Cl, Br, I, CN, OH, SH, NO2, oxo, thioxo,
  • each of Q 1 and Q 2 is independently selected from O or S;
  • R 2 and R 4 together may optionally form a 1- to 4-membered saturated or unsaturated, hydrocarbyl link, which may contain one or more heteroatoms selected from nitrogen, sulfur, and oxygen, and together with (Q 2 )(C)(N) forms a 4- to 7-membered cyclic structure, wherein said hydrocarbyl link may optionally be substituted with one or more substituents independently selected from H, F, Cl, Br, I, CN, OH, SH, NO 2 , oxo, thioxo, NR x R y , Ci-C 8 alkyl, Ci-C 8 haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 3 -C 8 cycloalkoxy, C 3 -C 8 halocycloalkoxy, Ci-C 8 alkoxy, Ci-C 8 haloalkoxy, C 2 -C 8 alkenyl, C 3 --
  • (L) (Het-1) is a 5- or 6-membered, saturated or unsaturated, heterocyclic ring, containing one or more heteroatoms independently selected from nitrogen, sulfur or oxygen, wherein said heterocyclic ring may also be substituted with one or more substituents independently selected from H, F, Cl, Br, I, CN, OH, SH, NO 2 , oxo, thioxo, NR x R y , Ci-C 8 alkyl, Ci-C 8 haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 3 -C 8 cycloalkoxy, C 3 -C 8 halocycloalkoxy, Ci-C 8 alkoxy, Ci-C 8 haloalkoxy, C 2 -C 8 alkenyl, C 3 -C 8 cycloalkenyl, C 2 -C 8 haloalkenyl, C 2 -C 8 alkyn
  • each alkyl, cycloalkyl, alkoxy, alkenyl, alkynyl, phenyl, and phenoxy may be optionally substituted with one or more substituents independently selected from H, F, Cl, Br, I, CN, OH, SH, NOz, oxo, thioxo, ⁇ R'R y .
  • Ar 1 is a phenyl or a substituted phenyl having one or more substituents independently selected from Ci-Cs alkyl, Ci-Ce haloalkyl, and Ci-Cg haloalkoxy;
  • Het is a triazolyl, imidazolyl, pyrrolyl, or pyrazolyl;
  • a 6-membered non-aromatic carbocyclic ring optionally substituted with one or more substituents independently selected fromH, Cl, Br, F, I, CN, oxo, Ci-Ce alkyl, Ci-Ce haloalkyl, Ci-Ce alkoxy, Ci-Ce haloalkoxy, Ci-Ce alkylthio, Ci-Ce haloalkylthio, G-G, alkenyl, and G-G, haloalkenyl;
  • each of R 1 , R 4 , and R 5 is independently selected from H, Ci-Ce alkyl, Ci-Ce haloalkyl, Ci-Ce alkoxy, Ci-Ce haloalkoxy, or phenyl;
  • R 2 is selected from H, Ci-Ce alkyl, or (i);
  • R 2 and R 4 together may form a 1- to 4-membered saturated or unsaturated, hydrocarbyl link, which may contain one or more heteroatoms selected from nitrogen, sulfur, and oxygen, and together with (Q 2 )(C)(N) forms a 4- to 7-membered cyclic structure, wherein said hydrocarbyl link, wherein said hydrocarbyl link may optionally be substituted with one or more R 6 , wherein each R 6 is independently selected fromH, F, Cl, Br, I, CN, Ci-Ce alkyl, oxo, thioxo, Ci-Ce haloalkyl, Ci-Ce alkoxy, Ci-Ce haloalkoxy, phenyl, and phenoxy;
  • R 3 is selected from phenyl, (Ci-Ce alkyl)phenyl, or (Ci-Ce alkyl)-O-phenyl, wherein each alkyl and phenyl is optionally substituted with one or more substituents independently selected from F, Cl, Br, I, CN, NO2, oxo, thioxo, Ci-Ce alkyl, Ci-Ce haloalkyl, Ci-Cg alkoxy, Ci-Cg haloalkoxy, phenyl, or phenoxy.
  • Ar 1 is a phenyl. In another embodiment, Ar 1 is a substituted phenyl having one or more substituents independently selected from OCF 3 , OCF 2 CF 3 , and CF 3 . In another embodiment, Het is 1,2,4-triazolyl. In another embodiment, A is azetidinyl, pyrrolidinyl, piperidinyl, piperazinyl, or tetrahydropyridinyl. In another embodiment, A is substituted azetidinyl, substituted pyrrolidinyl, substituted piperidinyl, substituted piperazinyl, or substituted tetrahydropyridinyl.
  • A is piperidinyl, substituted piperidinyl, piperazinyl, substituted piperazinyl, tetrahydropyridinyl, or substituted tetrahydropyridinyl.
  • A is substituted piperidinyl, substituted piperazinyl, or substituted tetrahydropyridinyl having one or more substituents independently selected fromH, Cl, Br, F, I, oxo, Ci-Ce alkyl, Ci-Cg -haloalkyl, Ci-Ce alkoxy, and Ci-Ce haloalkoxy.
  • A is a cyclohexyl, cyclohexenyl, cyclohexadienyl, substituted cyclohexyl, substituted cyclohexenyl, or substituted cyclohexadienyl.
  • A is a substituted cyclohexyl, substituted cyclohexenyl, or substituted cyclohexadienyl having one or more substituents independently selected from H, Cl, Br, F, I, oxo, Ci-Cs alkyl, Ci-Ce haloalkyl, Ci-Ce alkoxy, and Ci-Cg haloalkoxy.
  • L is a bond, -CH2-, or -CH2CH2-.
  • each of R 1 , R 4 and R 5 is independently H or Ci-Ce alkyl.
  • R 1 is H or Ci-Ce alkyl.
  • R 2 is H or Ci-Ce alkyl.
  • R 4 is H or Ci-Ce alkyl.
  • R 5 is H or Ci-Ce alkyl.
  • R 3 is a substituted phenyl having one or more substituents independently selected from F, Cl, Br, I, Ci-Ce alkyl, Ci-Ce haloalkyl, Ci-Ce alkoxy, and Ci-Ce haloalkoxy.
  • the compound has a structure listed in Table 1A or Table IB.
  • the compound has the structure of Formula Three or Formula Four: wherein
  • A is a (1) 4-, 5- or 6- membered nitrogen-containing non-aromatic ring containing between 0 and 1 additional nitrogen atoms optionally substituted with one or more substituents independently selected from H, Cl, Br, F, I, CN, oxo, Ci-Ce alkyl, Ci-Cg -haloalkyl, Ci-Ce alkoxy, Ci-Ce haloalkoxy, Ci-Ce alkylthio, Ci-Ce haloalkylthio, C 2 -Ce alkenyl, and C 2 -Ce haloalkenyl; or
  • a 6-membered non-aromatic carbocyclic ring optionally substituted with one or more substituents independently selected fromH, Cl, Br, F, I, CN, oxo, Ci-Cg alkyl, Ci-Ce -haloalkyl, Ci-Cs alkoxy, Ci-Cs haloalkoxy, Ci-Ce alkylthio, Ci-Ce haloalkylthio, C 2 -Cs alkenyl, and C 2 -Cs haloalkenyl;
  • L is a bond, -CR a R b -, -CR a R b -CR c R d -, or -CR a R b -CR c R d -CR e R f -; wherein each R a , R b , R c , R d , R e , and R f is selected from H, F, Cl, Br, I, OH, CN, NO 2 , Ci-Ce alkyl, Ci-Ce haloalkyl, Ci-Ce alkoxy, Ci-Ce haloalkoxy, and phenyl;
  • R 3 is a substituted phenyl with 1, 2, 3, 4, or 5 substituents R 7 independently selected from F, Cl, Br, I, Ci- G, alkyl, Ci-Ce haloalkyl, Ci-Ce alkoxy, and Ci-Ce haloalkoxy; and
  • R 8 is selected from Ci-Cg alkyl, Ci-Ce haloalkyl, Ci-Ce alkoxy, and Ci-Cc haloalkoxy.
  • A is selected from the following:
  • L is abend, -CH 2 -, -CH 2 CH 2 -, -CHFCH 2 -, or -CH 2 CH(CH 3 )-.
  • R 7 represents one, two, or three substituents independently selected from F, Cl, Ci-Ce alkyl, Ci-Ce haloalkoxy and Ci-Ce alkoxy.
  • R 8 is selected from OCF 3 , OC FiCF .. and CF3.
  • a process comprising applying a compound provided herein, to an area to control a pest, in an amount sufficient to control such pest.
  • the pest is beet armyworm (B AW), cabbage looper (CL), or green peach aphid (GPA).
  • a compound that is a pesticidally acceptable acid addition salt, a salt derivative, a solvate, or an ester derivative, of a compound provided herein in another aspect, provided is a compound provided herein wherein at least one H is 2 H or at least one C is 14 C. In another aspect, provided is a composition comprising a compound provided herein and a seed.
  • a process comprising applying a compound provided herein to a genetically modified plant, or genetically -modified seed, which has been genetically modified to express one or more specialized traits.
  • a process comprising: orally administering; or topically applying; a compound provided herein, to a non-human animal, to control endoparasites, ectoparasites, or both.
  • the compounds are selected from the structures listed in Tables 1 A and IB, wherein said compound is selected from the group consisting of Al, A2, A3, A4, A5, A6, A7, A9, A10, All, A12, A13, A14, A15, A16, A17, A18, A19, A20, A21, A22, A23, A24, A25, A27, A28, A29, Bl, B2, B3, B4, B5, and B6.
  • Thiobiurets disclosed herein are prepared from the corresponding isocyanate, Ar'-Hci-A-L-NCO (1-2). Usually, these isocyanates are not isolated, but are instead generated in situ from a suitable precursor and used directly in the preparation of a thiobiuret.
  • One such suitable precursor is an amine (1-1) which can be converted into an isocyanate by using one of several common reagents such as phosgene, diphosgene, triphosgene, or carbonyldiimidazole (Scheme 1, step a), in a mixed solvent system such as dichloromethane and water or diethyl ether and water, in the presence of a base such as sodium bicarbonate or triethylamine, at temperatures from about - 10 °C to about 50 °C.
  • phosgene diphosgene
  • triphosgene triphosgene
  • carbonyldiimidazole Scheme 1, step a
  • a mixed solvent system such as dichloromethane and water or diethyl ether and water
  • a base such as sodium bicarbonate or triethylamine
  • Formation of an acyl azide (Scheme 1, step b) occurs either by treatment of the acid with ethyl chloroformate and sodium azide in the presence of an amine base such as triethylamine, or with diphenylphosphoryl azide in the presence of an amine base such as triethylamine.
  • the acyl azide is then made to undergo a Curtins rearrangement leading to the corresponding isocyanate (1-2).
  • this rearrangement may occur spontaneously at ambient temperature, or it may require heating from about 40 °C to about 100 °C in a suitable solvent, such as toluene, acetonitrile, or an ethereal solvent such as dioxane or tetrahydrofuran.
  • a suitable solvent such as toluene, acetonitrile, or an ethereal solvent such as dioxane or tetrahydrofuran.
  • Azides of arylacetic acids are known, though due to their reactivity, are often not isolated as pure solids. Accordingly, the acyl azide intermediate is not always fully characterized, but may simply be heated directly without characterization, to generate the isocyanate.
  • An isocyanate, Ar'-Hei-A-L-NCO (1-2), can be treated directly with an V-ary 1 thiourea (2-1) in the presence of about 0.1 to about 2 equivalents of an inorganic base such as cesium carbonate or sodium hydride, resulting in the formation of a thiobiuret (2-2, Scheme 2).
  • an inorganic base such as cesium carbonate or sodium hydride
  • the reaction can be performed at temperatures from about 0 °C to about 100 °C, preferably from about 20 °C to about 80 °C, in an aprotic solvent or solvent mixture chosen from acetonitrile, acetone, toluene, tetrahydrofuran, 1,2-dichloroethane, dichloromethane, or mixtures thereof, but use of acetonitrile is preferred.
  • an aprotic solvent or solvent mixture chosen from acetonitrile, acetone, toluene, tetrahydrofuran, 1,2-dichloroethane, dichloromethane, or mixtures thereof, but use of acetonitrile is preferred.
  • Thiobiurets (2-2) generated in situ can be converted directly without purification into cyclized analogs (Scheme 3), or they can be isolated from the reaction medium prior to cyclization. Cyclization can be achieved by treatment with an oc-halo ester such as methyl bromoacetate to form 2-imino l,3-thiazolin-4-ones (3-1, step a) unsubstituted or mono- or di-substituted with R 5 .
  • a protic solvent such as ethanol or methanol
  • the reaction can be performed at temperatures from about 0 °C to about 100 °C, preferably from about 20 °C to about 80 °C, in an aprotic solvent or solvent mixture chosen from acetonitrile, acetone, toluene, tetrahydrofuran, 1,2-dichloroethane, dichloromethane, or mixtures thereof, but use of acetonitrile is preferred.
  • an aprotic solvent or solvent mixture chosen from acetonitrile, acetone, toluene, tetrahydrofuran, 1,2-dichloroethane, dichloromethane, or mixtures thereof, but use of acetonitrile is preferred.
  • the 4-imino-3-arylthiazolidinone-2-one (3-la) may be reacted with 4-nitrophenyl chloroformate (step b), forming a 4-nitrophenyl carbamate intermediate (3-2a).
  • This reaction is conducted with equimolar quantities of the imine and the chloroformate, in a polar aprotic solvent such as tetrahydrofuran or dioxane, and in the presence of from about 0.1 to about 2 equivalents of an inorganic base such as cesium carbonate or potassium carbonate, preferably at room temperature.
  • the intermediate (3-2a) may be isolated by filtration from inorganic salts and evaporation of solvent, or it can be used directly in step c.
  • step c treatment of 3 -2a with a primary or secondary alkyl amine Ari-Het-A-L-NHR 1 (3-3a), wherein R 1 is H or alkyl, respectively, may generate cyclized thiobiuret (3-1).
  • Step c may also be conducted in the presence of an inorganic base such as cesium carbonate or potassium carbonate, from about 0.1 to about 2 equivalents, preferably about 1 to about 1.2 equivalents; it is also most conveniently undertaken at room temperature, although it may be undertaken at temperatures from about 0 °C to about 100 °C.
  • an inorganic base such as cesium carbonate or potassium carbonate
  • Compounds of Formula One, Two, Three, Four, and/or Five can be prepared by making a three-ring intermediate, Ar'-Hei-A. and then linking it to an appropriate intermediate to form a desired compound.
  • a wide variety of three-ring intermediates can be used to prepare compounds of Formula One, Two, Three, Four, and/or Five, provided that such three-ring intermediates contain a suitable functional group on A and/or L to which the rest of the desired functional group can be attached.
  • Suitable functional groups include an amino, amino via nitro, isocyanate, carboxyl, or a halogen (preferably bromo or iodo).
  • the alcohol (OH) can be oxidized to the corresponding aldehyde 4-3, wherein Ar 1 , Het, and A are as previously disclosed, using pyridine-sulfur trioxide in the presence of dimethylsulfoxide, and a base, such as triethylamine, and in a solvent, such as dichloro methane, at a temperature from about 0 °C to about ambient temperature as in step b of Scheme 4.
  • a in 4-2 contains a -NHC(O)OC(CH 3 )3 group
  • the protecting group (C(O)OC(CH 3 )3) can be removed to provide the corresponding amine 4-4, wherein Ar 1 , Het, and A are as previously disclosed, using either trifluoroacetic acid or 4 molar (M) hydrogen chloride in dioxane in a solvent such as dichloromethane at a temperature from about 0 °C to about ambient temperature as in step c of Scheme 4.
  • the aldehyde 4-3 and amine 4- 4 can be further functionalized to arrive at the compounds of Formula One, Two, Three, Four, and/or Five.
  • a in 5-2 contains both an alkene and an ester such as -C(O)OCH2CH3
  • the alkene can first be reduced using hydrogen gas at about 480 kilopascal (kPa) / 70 pounds per square inch (psi) and a palladium catalyst such as 10% palladium on carbon to provide the alkane, and the ester can be reduced to the corresponding alcohol 5-3, wherein Ar 1 , Het, and A are as previously disclosed, using a reducing agent such as lithium aluminum hydride in a polar aprotic solvent such as tetrahydrofuran at a temperature from about 0 °C to about ambient temperature as in steps b and c of Scheme 5.
  • a reducing agent such as lithium aluminum hydride in a polar aprotic solvent such as tetrahydrofuran at a temperature from about 0 °C to about ambient temperature as in steps b and c of Scheme 5.
  • a in 5-2 contains an ester such as -C(O)OCH2CHa
  • the ester can be reduced to the corresponding alcohol 5-3, wherein Ar 1 , Het, and A are as previously disclosed, using a reducing agent such as lithium aluminum hydride in a polar aprotic solvent such as tetrahydrofuran at a temperature from about 0 °C to about ambient temperature as in step c of Scheme 5.
  • a reducing agent such as lithium aluminum hydride in a polar aprotic solvent such as tetrahydrofuran at a temperature from about 0 °C to about ambient temperature as in step c of Scheme 5.
  • a in 5-2 contains an ester such as -C(O)OCH2CH3
  • the ester can be saponified to the corresponding carboxylic acid 5-4, wherein Ar 1 , Het, and A are as previously disclosed, with a base such a 2 normal (N) sodium hydroxide in a polar solvent such as methanol at about ambient temperature as in step d of Scheme 5.
  • the alcohol 5-3 wherein Ar 1 , Het, and A are as previously disclosed, can be oxidized to the corresponding aldehyde 4-3 with an oxidizing agent such as Dess-Martin periodinane in a solvent such as dichloromethane at ambient temperature as in step e of Scheme 5.
  • the acid 5-4 and aldehyde 5-5 can be further functionalized to arrive at the compounds of Formula One, Two, Three, Four, and/or Five.
  • the alkene can be reduced using hydrogen gas (balloon) and a palladium catalyst such as 10% palladium on carbon in a polar aprotic solvent such as ethyl acetate to provide the saturated ester 6-2 (step b).
  • Saponification of the resultant ester may be achieved by using a strong base such as sodium hydroxide in ethyl acetate to furnish the carboxylic acid (6-3, step c).
  • the acid 6-3 can be further functionalized (e.g., as in Schemes 1, 2, 3, and 3a) to arrive at the compounds of Formula One, Two, Three, Four, and/or Five.
  • Carbinols 7-1 can be treated with phthalimide under Mitsunobu conditions to generate V-phthalimido intermediates 7-2 (step a).
  • Deprotection using hydrazine and methanol or other suitable solvent can furnish the amines 7-3 (step b).
  • Aldehyde 4-3 can be converted to the corresponding cyanohydrin 8-1, wherein Ar 1 , Het, and A are as previously disclosed, by treatment with zinc iodide and trimethylsilyl cyanide in a solvent such as dichloromethane at ambient temperature as in step a of Scheme 8.
  • the cyanohydrin 8-1 can be reacted with borane tetrahydrofuran complex in a solvent such as dichloromethane at a temperature from about 0 °C to about ambient temperature, followed by acid workup, to furnish the amine hydrochloride 8-2, wherein Ar 1 , Het, and A are as previously disclosed, as in step b of Scheme 8.
  • the amine functionality on 8-2 can be protected using di-tert-butyl dicarbonate in the presence of a base such as triethylamine and in a solvent such as dichloromethane at ambient temperature to provide 8-3, wherein Ar 1 , Het, and A are as previously disclosed, as in step c of Scheme 8.
  • Reaction of 8-3 with a fluorinating reagent such as (diethylamino)sulfur trifluoride in the presence of abase such as triethylamine and in a solvent such as dichloromethane at a temperature from about 0 °C to about ambient temperature can afford 8-4, wherein Ar 1 , Het, and A are as previously disclosed, as in step d of Scheme 8.
  • amine hydrochloride 8-6 Deprotection using 4 molar (M) hydrogen chloride in 1,4-dioxane or other suitable solvent at a temperature of about 0 °C to about ambient temperature can furnish the amine hydrochloride 8-6 (step /).
  • the amine hydrochloride 8-6 can be further functionalized (e.g., as in Schemes 1, 2, 3, 3a, and 3a’) to arrive at the compounds of Formula One, Two, Three, Four, and/or Five.
  • the cyanohydrin 8-1 can be reacted with a fluorinating reagent such as (diethylamino)sulfur trifluoride in the presence of a base such as triethylamine and in a solvent such as dichloromethane at temperature from about 0 °C to about ambient temperature can afford 8-5, wherein Ar 1 , Het, and A are as previously disclosed, as in step d of Scheme 8.
  • the cyano moiety on 8-5 can be reduced in the presence of a reducing agent such as borane tetrahydrofuran complex in a solvent such as tetrahydrofuran at a temperature from about 0 °C to about ambient temperature.
  • Incomplete reaction may require a different reducing agent such as lithium aluminum hydride to furnish the amine 8-6, wherein Ar 1 , Het, and A are as previously disclosed, as in step f of Scheme 8.
  • the amine 8-6 can be further functionalized (e.g., as in Schemes 1, 2, 3, 3a, and 3a’) to arrive at the compounds of Formula One, Two, Three, Four, and/or Five.
  • Method A A 25 mL vial under an atmosphere of nitrogen and equipped with a stir bar was charged with 3- bromo-l-(4-(trifluoromethoxy)phenyl)-177-l,2,4-triazole (Cl, 1 g, 3.25 mmol) and piperidin-4-ylmethanol (2.13 g, 18.5 mmol). The reaction mixture was heated to 120 °C. The reaction mixture was poured into ice water (250 mL). The solid was filtered, washed with water, and dried under vacuum (25 mm Hg) at 50 °C overnight.
  • Method B A mixture of 3-bromo-l-(4-(trifluoromethoxy)phenyl)-17f-l,2,4-triazole (Cl, 2 g, 6.49 mmol) and piperidin-4-ylmethanol (1.8 g, 16.22 mmol) in dimethyl sulfoxide (10 mL) was heated at 130 °C for 4 days in a sealed tube. The reaction mixture was cooled to room temperature, poured into ice water (100 mL), stirred for 1 hour.
  • reaction mixture was diluted with ethyl acetate and washed with water.
  • the aqueous layer was extracted with ethyl acetate.
  • the combined organic layers were washed with water (5x), dried over sodium sulfate, filtered, and concentrated.
  • reaction mixture was diluted with ethyl acetate and was washed with water.
  • the aqueous layer was extracted with ethyl acetate (2x).
  • the combined organic layers were washed with water (4x), dried over sodium sulfate, filtered, and concentrated.
  • the solid was dissolved in dichloromethane and washed with saturated sodium bicarbonate. The aqueous layer was extracted with dichloro methane (2x). The combined organic layers were washed with saturated sodium bicarbonate. The organic layers were poured through a phase separator and concentrated. The solid was dried overnight at 50 °C and ⁇ 25 mm Hg.
  • Example 17 Preparation of tert-butyl (l-(4-(l-(4-(trifhioromethoxv)phenvl)-l//-l,2,4-triazol-3-yl)-3,6- dihydropyridin-1(2//)-yl)propari-2-yl)carbamate (C21)
  • the reaction mixture was diluted with ethyl acetate and water.
  • the organic layer was pipetted off and filtered through a sodium sulfate cartridge directly onto a Celite® cartridge, rinsing with ethyl acetate.
  • the cartridge was dried in the vacuum oven. Purification by flash chromatography (0 - 100% ethyl acetate-hexanes) provided the title compound as a yellow oil (21 mg, 31%), which was used in the next step without purification: ESIMS m/z 468 ([M+H] + ).
  • Example 18 Preparation of l-(4-(l-(4-(trifluoromethoxy)phenyl)-l//-l,2,4-triazol-3-yl)-3,6-dihydropyridin- l(2Zf)-yl)propan-2-amine (
  • Example 19 Preparation of 2-(2-(4-(l-(4-(trifluoromethoxy)phenyl)-lZZ-l,2,4-triazol-3-yl)piperazin-l- yl)ethyl)isoindoline-l, 3-dione (C23) l-(l-(4-(Trifluoromethoxy)phenyl)-lH-l,2,4-triazol-3-yl)piperazine (C19, 193 mg, 0.616 mmol), 2-(2- bromoethyl)isoindo line- 1,3 -dione (235 mg, 0.924 mmol), and potassium carbonate (255 mg, 1.848 mmol) in ⁇ ' ⁇ - dimethylformamide (DMF, 1540 ji L) were heated in a Biotage microwave reactor at 120 °C for 1 hour.
  • DMF ⁇ ' ⁇ - dimethylformamide
  • reaction mixture was diluted with water and extracted with dichloromethane.
  • the organic layers were filtered through a phase separator directly onto a Celite® cartridge. Purification by flash chromatography (0 - 100% ethyl acetatehexanes) provided 65 mg of the title compound as a white solid. Recovery was low so the aqueous layer was extracted with ethyl acetate.
  • the reaction mixture was stirred at 120 °C for 16 hours.
  • the reaction mixture was cooled to room temperature, filtered through a pad of Celite®, washed with ethyl acetate (50 mL), and the filtrate was concentrated under reduced pressure.
  • the title compound was synthesized from 3-bromo-l-(4-(trifluoromethoxy)phenyl)-lH-l,2,4-triazole (Cl) and tert-butyl 4-(4,4,5,5-tetramethyl- 1 ,3,2-dioxaborolan-2-y l)-3,6-dihydropy ridine-l(2f/)-carboxy late and was isolated as an off-white solid (6.5 g) that was used without purification: ESIMS m/z 411 ([M+H] + ).
  • the reaction mixture was heated to 140 °C for 30 minutes in a Biotage Initiator microwave synthesizer.
  • the reaction mixture was diluted with ethyl acetate and washed with water.
  • the aqueous layer was extracted with ethyl acetate.
  • the combined organic layer was washed with brine, dried over sodium sulfate, filtered, and concentrated.
  • Example 25 Preparation of ethyl 4-(l-(4-(tritluoromethoxy)phenyl)-l/f-l,2,4-triazol-3-yl)cyclohexane-1- carboxylate (C30)
  • the title compound was prepared from (4-(l-(4-(trifluoromethoxy)phenyl)-lH-l,2,4-triazol-3- yl)cyclohexyl)methanol (C34) and isolated as a pale yellow sticky solid, which was used in the next step without any purification and analysis (3.8 g).
  • the title compound was prepared from 1 -( 1 -(4-(trifluoromethoxy)phenyl)-l H- 1 ,2,4-triazol-3-yl)piperidin- 4-yl)methanol (C2) and was isolated as a pale yellow sticky solid, which was used in the next step without purification and analysis (5.5 g).
  • reaction mixture was quenched with saturated sodium bicarbonate (10 mL) and was extracted with dichloro methane (3 x 20 mL). The organic layers were washed with water (10 mL) followed by brine (5 mL), dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure.
  • the reaction mixture was stirred at room temperature for 12 hours.
  • the mixture was quenched with saturated ammonium chloride solution (80 mL) and extracted with ethyl acetate (2 x 150 mL).
  • the organic layer was washed with water (100 mL) followed by brine (50 mL), dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to provide the title compound as a pale yellow sticky liquid (14.2 g), which was used in the next step without further purification.
  • Example 40 Preparation of l-[(2-isopropyl-5-methyl-phenyl)carbamothioyl]-3-[2-[l-[l-[4- (trifluoromethoxy)phenyl]-l,2,4-triazol-3-yl]-4-piperidyl]ethyl]urea (A2)
  • Method A 4-(2-Isocyanatoethyl)-l-(l-(4-(trifluoromethoxy)phenyl)-l./7-l,2,4-triazol-3-yl)piperidine (C7 used as is; 239 mg, 0.627 mmol) was diluted with acetonitrile (4.0 mL), and the mixture was warmed in a heating block preheated to 80 °C for 60 minutes. The reaction mixture was cooled and l-(2-isopropyl-5- methylphenyl)thiourea (144 mg, 0.689 mmol), and cesium carbonate (245 mg, 0.752 mmol) were added. The reaction mixture was allowed to stir overnight at room temperature.
  • reaction mixture was diluted with water and dichloromethane and passed through a phase separator.
  • the organic filtrate was concentrated. Purification of the resulting residue by reverse phase chromatography (Cis silica gel; 10 - 100% acetonitrile in water) provided the title compound as an orange solid (18 mg, 5%).
  • Method B To a biphasic solution of bis(trichloro methyl) carbonate (0.638 grams (g), 2.15 mmol) and sodium bicaibonate (1.36 g, 16.1 mmol)) in dichloromethane (20 mL) and water (10 mL) was added a suspension of 2-(l-(l-(4-(trifluoromethoxy)phenyl)-lZ7-l,2,4-triazol-3-yl)piperidin-4-yl)ethanamine (C9, 1.91 g, 5.37 mmol) in dichloromethane (40 mL). The reaction mixture was allowed to stir at room temperature for 4 hours.
  • the reaction mixture was diluted with dichloromethane and passed through a phase separator and the filtrate was concentrated.
  • the resulting residue was suspended in acetonitrile (36 mL).
  • a total of 4.0 mL [l/9th of the volume (0.594 mmol)] of this suspension was transferred to a vial containing l-(2-isopropyl-5-methylphenyl)thiourea (0.136 g, 0.653 mmol) and cesium carbonate (0.387 g, 1.188 mmol).
  • the reaction mixture was allowed to stir at room temperature overnight.
  • the reaction mixture was concentrated onto Celite®. Purification by silica gel flash chromatography (0 - 60% ethyl acetate in hexanes) provided the title compound as a white solid (157 mg, 44%).
  • the title compound was synthesized from l-( 1 -(4-(trifluoromethoxy)phenyl)-l H-l ,2,4-triazol-3- yl)piperidin-3 -amine (C16) and l-(5-chloro-2-isopropylphenyl)thiourea and was isolated as a white solid (86 mg, 40%).
  • the vial was capped and the reaction mixture was stirred in a heating block that was warmed to 70 °C overnight.
  • the reaction mixture was concentrated onto Celite®. Purification by silica gel flash chromatography (10 - 70% ethyl acetate in hexanes) afforded the title compound as a light yellow solid (88 mg, 71%).
  • the title compound was synthesized from l-[(2-isopropyl-5-methyl-phenyl)carbamothioyl]-3-[l-[l-[4- (trifluoromethoxy)phenyl]-l,2,4-triazol-3-yl]-4-piperidyl]urea (A3) and was isolated as a white solid (0.033 g, 65%).
  • the title compound was synthesized from l-(o-tolylcarbamothioyl)-3-[2-[l-[l-[4- (trifluoromethoxy)phenyl]-l,2,4-triazol-3-yl]-4-piperidyl]ethyl]urea (A5) and was isolated as an off-white solid (82 mg, 81%).
  • the title compound was synthesized from l-[(4-methoxy-2-methyl-phenyl)carbamothioyl]-3-[2-[l-[l-[4- (trifluoromethoxy)phenyl]-l,2,4-triazol-3-yl]-4-piperidyl]ethyl]urea (A6) and was isolated as an orange solid (104 mg, 74%).
  • the title compound was synthesized from l-[(2-ethylphenyl)carbamothioyl]-3-[2-[l-[l-[4- (trifluoromethoxy)phenyl]-l,2,4-triazol-3-yl]-4-piperidyl]ethyl]urea (A7) and was isolated as a light yellow solid (79 mg, 72%).
  • the title compound was synthesized from l-[(2-ethyl-6-methyl-phenyl)caibamothioyl]-3-[2-[l-[l-[4- (trifluoromethoxy)phenyl]-l,2,4-triazol-3-yl]-4-piperidyl]ethyl]urea (A8) and was isolated as a white solid (9 mg, 45%).
  • the title compound was synthesized from l-[(2-isopropyl-4-methyl-phenyl)carbamothioyl]-3-[2-[l-[l-[4- (trifluoromethoxy)phenyl]-l,2,4-triazol-3-yl]-4-piperidyl]ethyl]urea (A10) and was isolated as a light yellow solid (105 mg, 77%).
  • the title compound was synthesized from l-[(4-fluoro-2-isopropyl-phenyl)caibamothioyl]-3-[2-[l-[l-[4- (trifluoromethoxy)phenyl]-l,2,4-triazol-3-yl]-4-piperidyl]ethyl]urea (All) and was isolated as a light yellow solid (90 mg, 77%).
  • the title compound was synthesized from l-[(5-chloro-2-isopropyl-phenyl)carbamothioyl]-3-[2-[l-[l-[4- (trifluoromethoxy)phenyl]-l,2,4-triazol-3-yl]-4-piperidyl]ethyl]urea (A12) and was isolated as a light orange solid (83 mg, 66%).
  • the title compound was synthesized from l-[(5-chloro-2-isopropyl-phenyl)carbamothioyl]-3-[l-[l-[4- (trifluoromethoxy)phenyl]-l,2,4-triazol-3-yl]-3-piperidyl]urea (A24) and was isolated as an off-white solid (38 mg, 47%).
  • the title compound was synthesized from l-[(2-isopropyl-5-methyl-phenyl)carbamothioyl]-3-[4-[l-[4- (trifluoromethoxy)phenyl]-l,2,4-triazol-3-yl]cyclohex-3-en-l-yl]urea (Bl) and was isolated as a white solid (0.094 g, 63%) after ethyl acetate-water workup and drying at 50 °C at ⁇ 25 mm Hg.
  • the title compound was synthesized from 2-(4-(l-(4-(trifluoromethoxy)phenyl)-lH-l,2,4-triazol-3- yl)piperazin-l-yl)ethan-l -amine (C24) and (Z)-4-nitrophenyl (3-(2-isopropyl-5-methylphenyl)-4-oxothiazolidin-2- ylidene)carbamate and was isolated as a yellow foam (65 mg, 73%).
  • the title compound was synthesized from 2-(4-(l-(4-(trifluoromethoxy)phenyl)-lH-l,2,4-triazol-3-yl)-3,6- dihydropyridin- 1 (2//)-y I )elhan- 1 -amine (C26) and (Z) -4 -nitrophenyl (3 -(2-isopropyl-5-methylphenyl)-4- oxothiazolidin-2-ylidene)carbamate and was isolated as a yellow foam (20 mg, 19%).
  • Example 43 Preparation of (Z)-l-(2-fluoro-2-(l-(l-(4-(trifluoromethoxy)phenyl)-1//-1,2,4-triazol-3- yl)piperidin-4-yl)ethyl)-3-(3-(2-isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea (A27)
  • the title compound was synthesized from 2-fluoro-2-( l-( 1 -(4-(trifluoroincthoxy)phenyl)-l//-l ,2,4-triazol- 3-yl)piperidin-4-yl)ethan-l-amine hydrochloride (C18) and 2-imino-3-(5-methyl-2 -(2,2,2- trifluoroethoxy)phenyl)thiazolidin-4-one and was isolated as a yellow oil (20 mg, 32%).
  • the title compound was synthesized from 2-(4-( 1 -(4-(trifluoromethoxy)phenyl)-l H-l ,2,4-triazol-3- y l)piperazin- 1 -y l)ethan- 1 -amine (C24) and JV-(5 -methy 1-2 -(3 ,3 , 3 -trifluoropropoxy )pheny l)-2-thiocy anatoacetamide (C49) and was isolated as a clear oil (24 mg, 22%).
  • the title compound was synthesized from 2-fluoro-2-(4-(l-(4-(trifluoromethoxy)phenyl)-177-l,2,4-triazol- 3-yl)cyclohexyl)ethan-l-amine (C43) and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-one and was isolated as a clear oil (20 mg, 43%).
  • the title compound was synthesized from 2-fluoro-2-(4-(l-(4-(trifluoromethoxy)phenyl)-l//-l,2,4-triazol- 3 -yl)cyclo hex-3 -en-l-yl)ethan-l -amine (C42) and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-one and was isolated as a pale yellow oil (35 mg, 62%).
  • the title compound was synthesized from 2-fluoro-2-(4-( I -(4-(trifluoromctho. ⁇ y)phcnyl)-l//-l ,2.4-triazol- 3-yl)cyclohexyl)ethan-l-amine (C43) and jV-(5-methyl-2-(3,3,3-trifluoropropoxy)phenyl)-2-thiocyanatoacetamide (C49) and was isolated as a single diastereomer (B5) as a white foam (38 mg) and as a mixture of diastereomers (B6) as a clear oil (172 mg). Total yield (210 mg, 37%).
  • the title compound was synthesized from l-(4-(l-(4-(trifluoromethoxy)phenyl)-lW-l,2,4-triazol-3-yl)-3,6- dihydropyridin-l (2//)-yl)propan-2-aminc (C22) and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-one and was isolated as a yellow oil (5 mg, 17%).
  • the title compound was prepared from 4-(l-(4-(trifluoromethoxy)phenyl)-lW-l,2,4-triazol-3-yl)cyclohex- 3 -ene-1 -carbonyl azide (C47) by methods disclosed herein and known in the art and was isolated as a white solid (0.189 g).
  • bioassays against beet armyworm Spodoptera exigua
  • cabbage looper Trichoplusia nt
  • yellow fever mosquito Aedes aegypti
  • beet armyworm and cabbage looper are two good indicator species for a broad range of chewing pests.
  • Beet army worm is a serious pest of economic concern for alfalfa, asparagus, beets, citrus, com, cotton, onions, peas, peppers, potatoes, soybeans, sugar beets, sunflowers, tobacco, and tomatoes, among other crops. It is native to Southeast Asia but is now found in Africa, Australia, Japan, North America, and Southern Europe. The larvae may feed in large swarms causing devastating crop losses. It is known to be resistant to several pesticides.
  • Bioassays on beet armyworm were conducted using a 128-well diet tray assay.
  • One to five second instar BAW larvae were placed in each well (3 mL) of the diet tray that had been previously filled with 1 mL of artificial diet to which 50 pg/cm 2 of the test compound (dissolved in 50 pl. of 90:10 acetone-water mixture) had been applied (to each of eight wells) and then allowed to dry.
  • Trays were covered with a clear self-adhesive cover, vented to allow gas exchange, and held at 25 °C, 14:10 hght-dark for five to seven days. Percent mortality was recorded for the larvae in each well; activity in the eight wells was then averaged.
  • Cabbage looper is a serious pest found throughout the world. It attacks alfalfa, beans, beets, broccoli, Brussel sprouts, cabbage, cantaloupe, cauliflower, celery, collards, cotton, cucumbers, eggplant, kale, lettuce, melons, mustard, parsley, peas, peppers, potatoes, soybeans, spinach, squash, tomatoes, turnips, and watermelons, among other crops. This species is very destructive to plants due to its voracious appetite. The larvae consume three times their weight in food daily. The feeding sites are marked by large accumulations of sticky, wet, fecal material, which may contribute to higher disease pressure thereby causing secondary problems on the plants in the site. It is known to be resistant to several pesticides.
  • Bioassays on cabbage looper were conducted using a 128-well diet tray assay.
  • CL Tricholoplusia ni: Lepidoptera
  • One to five second instar CL larvae were placed in each well (3 mL) of the diet tray that had been previously filled with 1 mL of artificial diet to which 50 pg/cm 2 of the test compound (dissolved in 50 pL of 90: 10 acetonewater mixture) had been applied (to each of eight wells) and then allowed to dry. Trays were covered with a clear self-adhesive cover, vented to allow gas exchange, and held at 25 °C, 14:10 light-dark for five to seven days. Percent mortality was recorded for the larvae in each well; activity in the eight wells is then averaged.
  • GPA is the most significant aphid pest of peach trees, causing decreased growth, shriveling of the leaves, and the death of various tissues. It is also hazardous because it acts as a vector for the transport of plant viruses, such as potato virus Y and potato leafroll virus to members of the nightshade/potato family Solanaceae, and various mosaic viruses to many other food crops.
  • GPA attacks such plants as broccoli, burdock, cabbage, carrot, cauliflower, daikon, eggplant, green beans, lettuce, macadamia, papaya, peppers, sweet potatoes, tomatoes, watercress, and zucchini, among other crops. GPA also attacks many ornamental crops such as carnation, chrysanthemum, flowering white cabbage, poinsettia, and roses.
  • GPA has developed resistance to many pesticides. Currently, it is a pest that has the third largest number of reported cases of insect resistance (Sparks et aL). Consequently, because of the above factors control of this pest is important. Furthermore, molecules that control this pest (GPA), which is known as a sap-feeding pest, are useful in controlling other pests that feed on the sap from plants.
  • the seedlings were infested with 20-50 GPA (wingless adult and nymph stages) one day prior to chemical application.
  • Test molecules (2 mg) were dissolved in 2 mL of acetone/methanol (1:1) solvent, forming stock soludons of 1000 ppm test molecule.
  • the stock solutions were diluted 5X with 0.025% Tween 20 in water to obtain the solution at 200 ppm test molecule.
  • a hand-held aspirator-type sprayer was used for spraying a solution to both sides of cabbage leaves until runoff.
  • YFM prefers to feed on humans during the daytime and is most frequently found in or near human habitations.
  • YFM is a vector for transmitting several diseases. It is a mosquito that can spread the dengue fever and yellow fever viruses. Yellow fever is the second most dangerous mosquito-borne disease after malaria. Yellow fever is an acute viral hemorrhagic disease and up to 50% of severely affected persons without treatment will die from yellow fever. There are an estimated 200,000 cases of yellow fever, causing 30,000 deaths worldwide each year. Dengue fever is a nasty, viral disease; it is sometimes called "breakbone fever” or "break-heart fever” because of the intense pain it can produce. Dengue fever kills about 20,000 people annually.
  • DMSO dimethyl sulfoxide
  • a master plate of assembled compounds contained 15 pL per well. To this plate, 135 pL of a 90:10 water/acetone mixture was added to each well.
  • a robot Biomek® NXP Laboratory Automation Workstation
  • mosquito eggs were placed in Millipore water containing liver powder to begin hatching (4 g into 400 mL). After the “daughter” plates were created using the robot, they were infested with 220 pL of the liver powder/larval mosquito mixture (about 1 day-old larvae). After plates were infested with mosquito larvae, a non-evaporative lid was used to cover the plate to reduce drying. Plates were held at room temperature for 3 days prior to grading. After 3 days, each well was observed and scored based on mortality.
  • the compounds disclosed herein can be in the form of pesticidally acceptable acid addition salts.
  • an amine function can form salts with hydrochloric, hydrobromic, sulfuric, phosphoric, acetic, benzoic, citric, malonic, salicylic, malic, fumaric, oxalic, succinic, tartaric, lactic, gluconic, ascorbic, maleic, aspartic, benzenesulfonic, methanesulfonic, ethanesulfonic, hydroxymethanesulfonic, and hydroxyethanesulfonic acids.
  • an acid function can form salts including those derived from alkali or alkaline earth metals and those derived from ammonia and amines.
  • preferred cations include sodium, potassium, magnesium, and aminium cations.
  • the salts are prepared by contacting the free base form with a sufficient amount of the desired acid to produce a salt.
  • the free base forms may be regenerated by treating the salt with a suitable dilute aqueous base solution such as dilute aqueous NaOH, potassium carbonate, ammonia, and sodium bicarbonate.
  • a pesticide is modified to a more water soluble form e g., 2,4-dichlorophenoxy acetic acid dimethyl amine salt is a more water soluble form of 2,4-dichlorophenoxy acetic acid, a well-known herbicide.
  • the compounds disclosed herein can also form stable complexes with solvent molecules that remain intact after the non-complexed solvent molecules are removed from the compounds. These complexes are often referred to as "solvates.”
  • Certain compounds disclosed in this document can exist as one or more stereoisomers.
  • the various stereoisomers include geometric isomers, diastereomers, and enantiomers.
  • the compounds disclosed herein include racemic mixtures, individual stereoisomers, and optically active mixtures. It will be appreciated by those skilled in the art that one stereoisomer may be more active than the others.
  • Individual stereoisomers and optically active mixtures may be obtained by selective synthetic procedures, by conventional synthetic procedures using resolved starting materials, or by conventional resolution procedures.
  • pesticides are formulated into, for example, baits, concentrated emulsions, dusts, emulsifiable concentrates, iumigants, gels, granules, microencapsulations, seed treatments, suspension concentrates, suspoemulsions, tablets, water soluble liquids, water dispersible granules or dry flowables, wettable powders, and ultra-low volume solutions.
  • Pesticides are applied most often as aqueous suspensions or emulsions prepared from concentrated formulations of such pesticides.
  • Such water-soluble, water-suspendable, or emulsifiable formulations are either solids, usually known as wettable powders, or water dispersible granules, or liquids usually known as emulsifiable concentrates, or aqueous suspensions.
  • Wettable powders which may be compacted to form water dispersible granules, comprise an intimate mixture of the pesticide, a carrier, and surfactants.
  • the concentration of the pesticide is usually from about 10% to about 90% by weight.
  • the carrier is usually chosen from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, or the purified silicates.
  • Effective surfactants comprising from about 0.5% to about 10% of the wettable powder, are found among sulfonated lignins, condensed naphthalenesulfonates, naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates, and nonionic surfactants such as ethylene oxide adducts of alkyl phenols.
  • Emulsifiable concentrates of pesticides comprise a convenient concentration of a pesticide, such as from about 50 to about 500 grams per liter of liquid dissolved in a carrier that is either a water miscible solvent or a mixture of water-immiscible organic solvent and emulsifiers.
  • Useful organic solvents include aromatics, especially xylenes and petroleum fractions, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha.
  • Other organic solvents may also be used, such as the terpenic solvents including rosin derivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol.
  • Suitable emulsifiers for emulsifiable concentrates are chosen from conventional anionic and nonionic surfactants.
  • Aqueous suspensions comprise suspensions of water-insoluble pesticides dispersed in an aqueous carrier at a concentration in the range from about 5% to about 50% by weight.
  • Suspensions are prepared by finely grinding the pesticide and vigorously mixing it into a carrier comprised of water and surfactants. Ingredients, such as inorganic salts and synthetic or natural gums, may also be added, to increase the density and viscosity of the aqueous carrier. It is often most effective to grind and mix the pesticide at the same time by preparing the aqueous mixture and homogenizing it in an implement such as a sand mill, ball mill, or piston-type homogenizer.
  • Pesticides may also be applied as granular compositions that are particularly useful for applications to the soil.
  • Granular compositions usually contain from about 0.5% to about 10% by weight of the pesticide, dispersed in a carrier that comprises clay or a similar substance.
  • Such compositions are usually prepared by dissolving the pesticide in a suitable solvent and applying it to a granular carrier which has been pre-formed to the appropriate particle size, in the range of from about 0.5 to about 3 mm.
  • Such compositions may also be formulated by making a dough or paste of the carrier and compound and crashing and drying to obtain the desired granular particle size.
  • Dusts containing a pesticide are prepared by intimately mixing the pesticide in powdered form with a suitable dusty agricultural carrier, such as kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1% to about 10% of the pesticide. They can be applied as a seed dressing or as a foliage application with a dust blower machine.
  • a suitable dusty agricultural carrier such as kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1% to about 10% of the pesticide. They can be applied as a seed dressing or as a foliage application with a dust blower machine.
  • a pesticide in the form of a solution in an appropriate organic solvent, usually petroleum oil, such as the spray oils, which are widely used in agricultural chemistry.
  • Pesticides can also be applied in the form of an aerosol composition.
  • the pesticide is dissolved or dispersed in a carrier, which is a pressure-generating propellant mixture.
  • the aerosol composition is packaged in a container from which the mixture is dispensed through an atomizing valve.
  • Pesticide baits are formed when the pesticide is mixed with food or an attractant or both. When the pests eat the bait, they also consume the pesticide. Baits may take the form of granules, gels, flowable powders, liquids, or solids. They are used in pest harborages.
  • Fumigants are pesticides that have a relatively high vapor pressure and hence can exist as a gas in sufficient concentrations to kill pests in soil or enclosed spaces.
  • the toxicity of the fumigant is proportional to its concentration and the exposure time. They are characterized by a good capacity for diffusion and act by penetrating the pest’s respiratoiy system or being absorbed through the pest’s cuticle. Fumigants are applied to control stored product pests under gas proof sheets, in gas sealed rooms or buildings or in special chambers. Pesticides can be microencapsulated by suspending the pesticide particles or droplets in plastic polymers of various types.
  • microcapsules By altering the chemistry of the polymer or by changing factors in the processing, microcapsules can be formed of various sizes, solubility, wall thicknesses, and degrees of penetrability. These factors govern the speed with which the active ingredient within is released, which in turn, affects the residual performance, speed of action, and odor of the product.
  • Oil solution concentrates are made by dissolving pesticide in a solvent that will hold the pesticide in solution.
  • Oil solutions of a pesticide usually provide faster knockdown and kill of pests than other formulations due to the solvents themselves having pesticidal action and the dissolution of the waxy covering of the integument increasing the speed of uptake of the pesticide.
  • Other advantages of oil solutions include better storage stability, better penetration of crevices, and better adhesion to greasy surfaces.
  • Another embodiment is an oil-in-water emulsion, wherein the emulsion comprises oily globules which are each provided with a lamellar liquid crystal coating and are dispersed in an aqueous phase, wherein each oily globule comprises at least one compound which is agriculturally active, and is individually coated with a monolameliar or oligolamellar layer comprising: (1) at least one nonionic lipophilic surface-active agent, (2) at least one nonionic hydrophilic surface-active agent and (3) at least one ionic surface-active agent, wherein the globules having a mean particle diameter of less than 800 nanometers.
  • a monolameliar or oligolamellar layer comprising: (1) at least one nonionic lipophilic surface-active agent, (2) at least one nonionic hydrophilic surface-active agent and (3) at least one ionic surface-active agent, wherein the globules having a mean particle diameter of less than 800 nanometers.
  • the compounds disclosed herein when used in a formulation can also contain other components.
  • these components include, but are not limited to, (this is a non-exhaustive and non-mutually exclusive list) wetters, spreaders, stickers, penetrants, buffers, sequestering agents, drift reduction agents, compatibility agents, anti-foam agents, cleaning agents, and emulsifiers. A few components are described forthwith.
  • a wetting agent is a substance that when added to a liquid increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading.
  • Wetting agents are used for two main lunctions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates; and during mixing of a product with water in a spray tank to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible granules.
  • wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations are: sodium lauiyl sulfate; sodium dioctyl sulfosuccinate; alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates.
  • a dispersing agent is a substance which adsorbs onto the surface of a particles and helps to preserve the state of dispersion of the particles and prevents them from reaggregating.
  • Dispersing agents are added to agrochemical formulations to facilitate dispersion and suspension during manufacture, and to ensure the particles redisperse into water in a spray tank. They are widely used in wettable powders, suspension concentrates and water- dispersible granules.
  • Surfactants that are used as dispersing agents have the ability to adsorb strongly onto a particle surface and provide a charged or steric barrier to reaggregation of particles. The most commonly used surfactants are anionic, nonionic, or mixtures of the two types.
  • dispersing agents For wettable powder formulations, the most common dispersing agents are sodium lignosulfonates. For suspension concentrates, very good adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulfonate formaldehyde condensates. Tristyrylphenol ethoxylate phosphate esters are also used. Nonionics such as alkylarylethylene oxide condensates and EO-PO block copolymers are sometimes combined with anionics as dispersing agents for suspension concentrates. In recent years, new types of veiy high molecular weight polymeric surfactants have been developed as dispersing agents.
  • hydrophobic backbones and a large number of ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant.
  • These high molecular weight polymers can give very good long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points onto the particle surfaces.
  • dispersing agents used in agrochemical formulations are: sodium lignosulfonates; sodium naphthalene sulfonate formaldehyde condensates; tristyrylphenol ethoxylate phosphate esters; aliphatic alcohol ethoxylates; alkyl ethoxylates; EO-PO block copolymers; and graft copolymers.
  • An emulsifying agent is a substance which stabilizes a suspension of droplets of one liquid phase in another liquid phase. Without the emulsifying agent the two liquids would separate into two immiscible liquid phases.
  • the most commonly used emulsifier blends contain alkylphenol or aliphatic alcohol with twelve or more ethylene oxide units and the oil-soluble calcium salt of dodecylbenzenesulfonic acid.
  • a range of hydrophile-lipophile balance (“HLB”) values from 8 to 18 will normally provide good stable emulsions. Emulsion stability can sometimes be improved by the addition of a small amount of an EO-PO block copolymer surfactant.
  • a solubilizing agent is a surfactant which will form micelles in water at concentrations above the critical micelle concentration. The micelles are then able to dissolve or solubilize water-insoluble materials inside the hydrophobic part of the micelle.
  • the type of surfactants usually used for solubilization are nonionics: sorbitan monooleates; sorbitan monooleate ethoxylates; and methyl oleate esters.
  • Surfactants are sometimes used, either alone or with other additives such as mineral or vegetable oils as adjuvants to spray -tank mixes to improve the biological performance of the pesticide on the target.
  • the types of surfactants used for bioenhancement depend generally on the nature and mode of action of the pesticide. However, they are often nonionics such as: alkyl ethoxylates; linear aliphatic alcohol ethoxylates; aliphatic amine ethoxylates.
  • a carrier or diluent in an agricultural formulation is a material added to the pesticide to give a product of the required strength.
  • Carriers are usually materials with high absorptive capacities, while diluents are usually materials with low absorptive capacities. Carriers and diluents are used in the formulation of dusts, wettable powders, granules, and water-dispersible granules.
  • Organic solvents are used mainly in the formulation of emulsifiable concentrates, ULV (ultra-low volume) formulations, and to a lesser extent granular formulations. Sometimes mixtures of solvents are used.
  • the first main groups of solvents are aliphatic paraffinic oils such as kerosene or refined paraffins.
  • the second main group and the most common comprises the aromatic solvents such as xylene and higher molecular weight fractions of C9 and CIO aromatic solvents.
  • Chlorinated hydrocarbons are useful as cosolvents to prevent ciystallization of pesticides when the formulation is emulsified into water. Alcohols are sometimes used as cosolvents to increase solvent power.
  • Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and suspoemulsions to modify the rheology or flow properties of the liquid and to prevent separation and settling of the dispersed particles or droplets.
  • Thickening, gelling, and anti-settling agents generally fall into two categories, namely water-insoluble particulates, and water-soluble polymers. It is possible to produce suspension concentrate formulations using clays and silicas. Examples of these types of materials, include, but are limited to, montmorillonite, e g., bentonite; magnesium aluminum silicate; and attapulgite. Water-soluble polysaccharides have been used as thickening-gelling agents for many years.
  • polysaccharides most commonly used are natural extracts of seeds and seaweeds or are synthetic derivatives of cellulose. Examples of these types of materials include, but are not limited to, guar gum; locust bean gum; carrageenam; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC).
  • SCMC carboxymethyl cellulose
  • HEC hydroxyethyl cellulose
  • Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide. Another good anti-settling agent is xanthan gum.
  • preservation agents are used to eliminate or reduce their effect.
  • examples of such agents include, but are not limited to: propionic acid and its sodium salt; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium salt; p-hydroxybcnzoic acid sodium salt; methyl p-hydroxybenzoate: and l,2-benzisothiazalin-3-one (BIT).
  • anti-foam agents are often added either during the production stage or before filling into bottles.
  • silicones are usually aqueous emulsions of dimethyl polysiloxane while the non-silicone anti-foam agents are water-insoluble oils, such as octanol and nonanol, or silica.
  • the function of the anti-foam agent is to displace the surfactant from the air-water interface.
  • Green agents can reduce the overall environmental footprint of crop protection formulations.
  • Green agents are biodegradable and generally derived from natural and/or sustainable sources, e.g., plant and animal sources. Specific examples are vegetable oils, seed oils, and esters thereof, also alkoxylated alkyl poly glucosides.
  • the compounds disclosed herein can be used to control pests.
  • the compounds disclosed herein can be used to control pests of the Phylum Nematoda.
  • the compounds disclosed herein can be used to control pests of the Phylum Arthropoda. In another embodiment, the compounds disclosed herein can be used to control pests of the Subphylum Chelicerata.
  • the compounds disclosed herein can be used to control pests of the Class Arachnida.
  • the compounds disclosed herein can be used to control pests of the Subphylum Myriapoda.
  • the compounds disclosed herein can be used to control pests of the Class Symphyla.
  • the compounds disclosed herein can be used to control pests of the Subphylum Hexapoda.
  • the compounds disclosed herein can be used to control pests of the Class Insecta.
  • the compounds disclosed herein can be used to control Coleoptera (beetles).
  • the compounds disclosed herein can be used to control Dermaptera (earwigs).
  • the compounds disclosed herein can be used to control Dictyoptera (cockroaches).
  • the compounds disclosed herein can be used to control Diptera (true flies).
  • the compounds disclosed herein can be used to control Hemiptera (true bugs).
  • the compounds disclosed herein can be used to control Homoptera (aphids, scales, whiteflies, leafhoppers).
  • the compounds disclosed herein can be used to control Hymenoptera (ants and wasps).
  • the compounds disclosed herein can be used to control Isoptera (termites).
  • the compounds disclosed herein can be used to control Lepidoptera (moths and butterflies).
  • the compounds disclosed herein can be used to control Mallophaga (chewing lice).
  • the compounds disclosed herein can be used to control Orthoptera (grasshoppers, locusts, and crickets).
  • the compounds disclosed herein can be used to control Phthiraptera (sucking lice).
  • the compounds disclosed herein can be used to control Siphonaptera (fleas).
  • the compounds disclosed herein can be used to control Thysanoptera (thrips).
  • the compounds disclosed herein can be used to control Thysanura (bristletails).
  • the compounds disclosed herein can be used to control Acarina (mites and ticks).
  • the compounds disclosed herein can be used to control Nematoda (nematodes).
  • the compounds disclosed herein can be used to control Symphyla (symphylans).
  • Controlling pests of Phyla Nematoda, Arthropoda, and/or Mollusca generally means that pest populations, pest activity, or both, are reduced in a locus. This can come about when:
  • pests are exterminated in, or around, a locus.
  • pest populations, activity, or both are desirably reduced more than fifty percent, preferably more than 90 percent, and most preferably more than 98 percent.
  • the locus is not in, or on, a human; consequently, the locus is generally a non-human locus.
  • the locus to which a molecule of Formula One is applied can be any locus that is inhabited, or that may become inhabited, or that may be traversed, by a pest of Phyla Nematoda, Arthropoda, and/or Mollusca.
  • the locus can be:
  • Particular crop areas to use a molecule of Formula One include areas where apples, com, sunflowers, cotton, soybeans, canola, wheat, rice, sorghum, barley, oats, potatoes, oranges, alfalfa, lettuce, strawberries, tomatoes, peppers, crucifers, pears, tobacco, almonds, sugar beets, beans and other valuable crops are growing or the seeds thereof are going to be planted. It is also advantageous to use ammonium sulfate with a molecule of Formula One when growing various plants.
  • the actual amount of pesticide to be applied to loci of pests is generally not critical and can readily be determined by those skilled in the art. In general, concentrations from about 0.01 grams of pesticide per hectare to about 5000 grams of pesticide per hectare are expected to provide good control.
  • the locus to which a pesticide is applied can be any locus inhabited by an pest, for example, vegetable crops, fruit and nut trees, grape vines, ornamental plants, domesticated animals, the interior or exterior surfaces of buildings, and the soil around buildings.
  • Controlling pests generally means that pest populations, activity, or both, are reduced in a locus. This can come about when: pest populations are repulsed from a locus; when pests are incapacitated in or around a locus; or pests are exterminated, in whole or in part, in or around a locus. Of course, a combination of these results can occur.
  • pest populations, activity, or both are desirably reduced more than fifty percent, preferably more than 90 percent.
  • Baits are placed in the ground where, for example, termites can come into contact with the bait. Baits can also be applied to a surface of a building, (horizontal, vertical, or slant surface) where, for example, ants, termites, cockroaches, and flies, can come into contact with the bait.
  • Systemic movement of pesticides in plants may be utilized to control pests on one portion of the plant by applying the pesticides to a different portion of the plant.
  • control of foliar-feeding insects can be controlled by drip irrigation or furrow application, or by treating the seed before planting.
  • Seed treatment 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 or other insecticidal toxins, those expressing herbicide resistance, such as “Roundup Ready” seed, or those with “stacked” foreign genes expressing insecticidal toxins, herbicide resistance, nutritionenhancement, or any other beneficial traits.
  • seed treatments with the compounds disclosed herein can further enhance the ability of a plant to better withstand stressful growing conditions. This results in a healthier, more vigorous plant, which can lead to higher yields at harvest time.
  • the compounds disclosed herein can be used with plants genetically transformed to express specialized traits, such as Bacillus thuringiensis or other insecticidal toxins, or those expressing herbicide resistance, or those with “stacked” foreign genes expressing insecticidal toxins, herbicide resistance, nutrition-enhancement, or any other beneficial traits.
  • specialized traits such as Bacillus thuringiensis or other insecticidal toxins, or those expressing herbicide resistance, or those with “stacked” foreign genes expressing insecticidal toxins, herbicide resistance, nutrition-enhancement, or any other beneficial traits.
  • Table 3 Biological Data for Compounds in Tables 1 A and IB A25 A A C c
  • substituted furanyl, substituted phenyl, substituted pyridazinyl, substituted pyridyl, substituted pyrimidinyl, or substituted thienyl wherein said substituted furanyl, substituted phenyl, substituted pyridazinyl, substituted pyridyl, substituted pyrimidinyl, and substituted thienyl have one or more substituents independently selected from H, F, Cl, Br, I, CN, OH, SH, NOz, oxo, thioxo, NR’R 5 ', Ci-Cg alkyl, Ci-Cs haloalkyl, Cj-Cg cycloalkyl, Cs-Cg halocycloalkyl, Cs-Cs cycloalkoxy, Ch-Cg halocycloalkoxy, Ci-C 8 alkoxy, Ci-Q haloalkoxy, Ch-Cg alkenyl, Ch-C
  • Het is a 5- or 6-membered, saturated or unsaturated, heterocyclic ring, containing one or more heteroatoms independently selected from nitrogen, sulfur, or oxygen, and where said heterocyclic ring may also be substituted with one or more substituents independently selected from H, F, Cl, Br, I, CN, OH, SH, NO2, oxo, thioxo, NR x R y , Ci-C 8 alkyl, Ci-C 8 haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 3 -C 8 cycloalkoxy, C 3 -C 8 halocycloalkoxy, Ci-C 8 alkoxy, Ci-C 8 haloalkoxy, C 3 -C 8 alkenyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 haloalkenyl, C 3 -C 8 alkynyl, S(
  • a 6-membered saturated or partially unsaturated carbocyclic ring optionally substituted with one or more substituents independently selected from H, Cl, Br, F, I, CN, oxo, Ci-Ce alkyl, Ci-Ce -haloalkyl, Ci-Ce alkoxy, Ci-Cg haloalkoxy, Ci-Ce alkylthio, Ci-Cs haloalkylthio, C2-C6 alkenyl, C 2 -Ce haloalkenyl, and C 2 -Ce haloalkenyl;
  • (D) L is a linker selected from
  • each of R a , R b , R c , R d , R e , and R f is selected from H, F, Cl, Br, I, CN, OH, SH, NO 2 , oxo, thioxo,
  • each of Q 1 and Q 2 is independently selected from O or S;
  • R 3 is selected from C 3 -C 8 cycloalkyl, phenyl, (Ci-C 8 alkyl)phenyl, (Ci-C 8 alkyl)-O-phenyl, (C 2 -C 8 alkenyl)- O-phenyl, (Het-1), (Ci-C 8 alkyl)(Het-l), (Ci-C 8 alkyl)O(Het-l), wherein the C 3 -C 8 cycloalkyl, phenyl, (Ci-C 8 alkyl)phenyl, (Ci-C 8 alkyl)-O-phenyl, (C 2 -C 8 alkenyl)-O- phenyl, (Het-1), (Ci-C 8 alkyl)(Het-l), or (Ci-C 8 alkyl)O(Het-l) may be optionally substituted with one or more substituents independently selected from H, F, Cl, Br, I, CN,
  • R 2 and R 4 together may optionally form a 1- to 4-membered saturated or unsaturated, hydrocarbyl link, which may contain one or more heteroatoms selected from nitrogen, sulfur, and oxygen, and together with (Q 2 )(C)(N) forms a 4- to 7-membered cyclic structure, wherein said hydrocarbyl link may optionally be substituted with one or more substituents independently selected from H, F, Cl, Br, I, CN, OH, SH, NO 2 , oxo, thioxo, NR x R y , Ci-C 8 alkyl, Ci-C 8 haloalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 3 -C 8 cycloalkoxy, C 3 -C 8 halocycloalkoxy, Ci-Cs alkoxy, Ci-C 8 haloalkoxy, C 2 -C 8 alkenyl, C 3 -
  • Ar 1 is a phenyl or a substituted phenyl having one or more substituents independently selected from Ci-Ce alkyl, Ci-Ce haloalkyl, and Ci-Ce haloalkoxy;
  • Het is a triazolyl, imidazolyl, pyrrolyl, or pyrazolyl;
  • a 6-membered non-aromatic carbocyclic ring optionally substituted with one or more substituents independently selected fromH, Cl, Br, F, I, CN, oxo, Ci-Ce alkyl, Ci-Ce -haloalkyl, Ci-Cs alkoxy, Ci-Cs haloalkoxy, Ci-Ce alkylthio, Ci-Ce haloalkylthio, G-G, alkenyl, and G-G, haloalkenyl;
  • L is a linker selected from a bond or -CR a R b -CR c R d , wherein each of R a , R b , R c , and R d is selected from H, F, Cl, Br, I, CN, OH, SH, NOz, oxo, thioxo, NR'R' .
  • Ci-Cs alkyl Ci-Cg haloalkyl, Ci-Cs alkoxy, and Ci-Cs haloalkoxy
  • each of R 1 , R 4 , and R 5 is independently selected from H, Ci-Ce alkyl, Ci-Ce haloalkyl, Ci-Ce alkoxy, Ci-Ce haloalkoxy, or phenyl;
  • R 2 is selected from H, Ci-Ce alkyl, or (i);
  • R 2 and R 4 together may form a 1- to 4-membered saturated or unsaturated, hydrocarbyl link, which may contain one or more heteroatoms selected from nitrogen, sulfur, and oxygen, and together with (Q 2 )(C)(N) forms a 4- to 7-membered cyclic structure, wherein said hydrocarbyl link, wherein said hydrocarbyl link group may optionally be substituted with one or more R 6 , wherein each R 6 is independently selected fromH, F, Cl, Br, I, CN, Ci-Cg alkyl, oxo, thioxo, Ci-Cg haloalkyl, Ci-Cg alkoxy, Ci-Ce haloalkoxy, phenyl, and phenoxy;
  • R 3 is selected from phenyl, Ci-Ce alkyl-phenyl, or Ci-Cg alkyl-O-phenyl, wherein each alkyl and phenyl is optionally substituted with one or more substituents independently selected from F, Cl, Br, I, CN, NO2, oxo, thioxo, Ci-Ce alkyl, Ci-Ce haloalkyl, Ci-Ce alkoxy, Ci-Ce haloalkoxy, phenyl, or phenoxy.
  • A is azetidinyl, cyclo hexyl, cyclohexenyl, cyclohexadienyl, pyrrolidinyl, piperidinyl, piperazinyl, tetrahydropyridinyl, substituted cyclohexyl, substituted cyclohexenyl, substituted cyclohexadienyl, substituted pyrrolidinyl, substituted piperidinyl, substituted tetrahydropyridinyl, or substituted piperazinyl.
  • A is a substituted piperidinyl, substituted tetrahydropyridinyl, or substituted piperazinyl having one or more substituents independently selected from H, Cl, Br, F, I, oxo, Ci-Cg alkyl, Ci-Ce -haloalkyl, Ci-Ce alkoxy, and Ci-Ce haloalkoxy.
  • R 3 is a substituted phenyl having one or more substituents independently selected from F, Cl, Br, I, Ci-Ce alkyl, Ci-Cs haloalkyl, Ci-Cs alkoxy, and Ci-Cg haloalkoxy.
  • A is selected from the group consisting of
  • L is a bond, -CR a R b -, -CR a R b -CR c R d -, or -CR a R b -CR c R d -CR e R f , wherein each of R a , R b , R c , R d , R e , and R f is selected from the group consisting of H, F, Cl, and C1-C3 alkyl; each of Q 1 and Q 2 is independently selected from O or S;
  • R 1 , R 2 , and R 5 are each independently selected from the group consisting of H and CH ,: R 3 is a substituted phenyl with 1, 2, 3, 4, or 5 substituents R 7 independently selected from the group consisting of F, Cl, Br, I, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, and C1-C4 haloalkoxy; and
  • R 8 is selected from the group consisting of C1-C4 haloalkyl and C1-C4 haloalkoxy.
  • composition comprising a compound according to any of the previous details and a carrier.
  • a process comprising applying (a) a compound according to any of the previous details Id through 19d inclusive, or (b) a composition according to 20d, to an area to control a pest, in an amount sufficient to control such pest.
  • a process comprising applying (a) a compound according to any of the previous details Id through 19d inclusive, or (b) a composition according to 20d, to a genetically modified plant, or genetically -modified seed, which has been genetically modified to express one or more specialized traits.
  • 24d A process comprising: orally administering or topically applying (a) a compound according to any of the previous details Id through 19d inclusive, or (b) a composition according to 20d, to a non-human animal, to control endoparasites, ectoparasites, or both.
  • a composition comprising a compound according to any of the previous details Id through 19d inclusive and a seed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Zoology (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Insects & Arthropods (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention concerne des composés ayant la structure de formule Un ou de formule Deux : Formule Un, ou Formule Deux. L'invention concerne également des compositions pesticides et leurs utilisations. L'invention concerne par ailleurs des procédés de synthèse des composés de l'invention.
PCT/US2022/075104 2021-08-19 2022-08-18 Molécules ayant certaines utilités pesticides, et intermédiaires, compositions et procédés associés à celles-ci Ceased WO2023023572A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070027034A1 (en) 2005-07-28 2007-02-01 Holger Tank Agricultural compositions comprising an oil-in-water emulsion based on oily globules coated with a lamellar liquid crystal coating
US20140275502A1 (en) 2013-03-13 2014-09-18 Dow Agrosciences Llc Process for the preparation of certain triaryl rhamnose carbamates
WO2014160031A1 (fr) * 2013-03-14 2014-10-02 Dow Agrosciences Llc Molécules ayant certaines utilités pesticides, et des intermédiaires, des compositions et des procédés associés à celles-ci

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070027034A1 (en) 2005-07-28 2007-02-01 Holger Tank Agricultural compositions comprising an oil-in-water emulsion based on oily globules coated with a lamellar liquid crystal coating
US20140275502A1 (en) 2013-03-13 2014-09-18 Dow Agrosciences Llc Process for the preparation of certain triaryl rhamnose carbamates
WO2014160031A1 (fr) * 2013-03-14 2014-10-02 Dow Agrosciences Llc Molécules ayant certaines utilités pesticides, et des intermédiaires, des compositions et des procédés associés à celles-ci

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