OA21278A - Pyridine compounds for controlling invertebrate pests. - Google Patents

Pyridine compounds for controlling invertebrate pests. Download PDF

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OA21278A
OA21278A OA1202200290 OA21278A OA 21278 A OA21278 A OA 21278A OA 1202200290 OA1202200290 OA 1202200290 OA 21278 A OA21278 A OA 21278A
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OAPI
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compound
phenyl
halogen
alkyl
fluoro
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OA1202200290
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Ming Xu
Rachel SLACK
Omar Khaled AHMAD
Twyla A. BRIDDELL
Dominic Ming-Tak Chan
Yuzhong Chen
Jason Charles HAMM
Moumita Kar
Thomas Francis PAHUTSKI Jr.
Thomas Martin Stevenson
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Fmc Corporation
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Abstract

Disclosed arc compounds of Formula 1, including all geometric and stereoisomers, /V-oxides, and salts thereof, Wherein R1, A, R2 , R4, and Q are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound or a composition of the disclosure.

Description

PYRIDINE COMPOUNDS FOR CONTROLLING INVERTEBRATE PESTS
CROSS-REFERENCE TO RELATED APPLICATIONS
This application daims the benefit of U.S. Provisional Application No. 62/967,838 filed January 30, 2020.
FIELD
This disclosure relates to certain pyridine compounds, their A-oxides, salts and compositions suitable for agronomie and nonagronomic uses, and methods of their use for controlling invertebrate pests such as arthropods in both agronomie and nonagronomic environments.
BACKGROUND
The control of invertebrate pests is extremely important in achieving high crop efficiency. Damage by invertebrate pests to growing and stored agronomie crops can cause significant réduction in productivity and thereby resuit in increased costs to the consumer. The control of invertebrate pests in forestry, greenhouse crops, omamentals, nursery crops, stored food and fiber products, livestock, household, turf, wood products, and public and animal 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 hâve different sites of action.
SUMMARY
This disclosure is directed to compounds of Formula 1 (including ail géométrie and stereoisomers), A-oxides, and salts thereof, and compositions containing them and their use for controlling invertebrate pests:
R1
R5 wherein
R1 is F, OR6 or S(O)nR6;
A is N or CR3;
R2 is H, halogen, CN, CrC4 alkyl, CrC4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, Cj-C4 alkoxy or Cj-C4 haloalkoxy;
R3 is H, halogen, CN, C]-C4 alkyl, Cj-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, Cj-C4 alkoxy or CrC4 haloalkoxy;
R4 is a 5- to 6-membered heterocyclic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(=O), C(=S), S(=O) and S(=O)2, each ring optionally substituted with up to 5 substituents independently selected from Rv, and r is the number of the substituents.
each Rv is independently H, cyano, halogen, C]-Cg alkyl, Cj-Cg alkoxy, Cj-Cg haloalkoxy, Cj-Cg haloalkyl, C2-Cg alkenyl, C2-Cg haloalkenyl, C2-Cg alkynyl, C2Cg haloalkynyl, C3-Cg cycloalkyl, C3-Cg halocycloalkyl, C2-Cg cyanoalkyl, CpCg hydroxyalkyl, C4-Cjq alkylcycloalkyl, C4-C1q cycloalkylalkyl, C3-Cg cycloalkenyl, C3-Cg halocycloalkenyl, C2-Cg alkoxyalkyl, C4-C]q cycloalkoxyalkyl, C3-Ci0 alkoxyalkoxyalkyl, C2-Cg alkylthioalkyl, C2-Cg alkylsulfmylalkyl, C3-Cg cycloalkoxy, C3-Cg halocycloalkoxy, C4-C10 cycloalkylalkoxy, C2-Cg alkenyloxy, C2-Cg haloalkenyloxy, C2-Cg alkoxyalkoxy, C2-Cg alkylcarbonyloxy, Cj-Cg alkylthio, Cj-Cg haloalkylthio, C3-C6 cycloalkylthio, Cj-Cg alkylsulfmyl, Cj-Cg haloalkylsulfmyl, CpCg alkylsulfonyl, Cj-Cg haloalkylsulfonyl, C3-Cg cycloalkylsulfonyl, Cj-Cg alkylamino, C2-Cg dialkylamino, C^-Cg haloalkylamino, C2-Cg halodialkylamino or C3-C6 cycloalkylamino;
r is 1, 2, 3, 4 or 5;
R5 is H, halogen, CN, Ci-C4 alkyl, CpC4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, Cj-C4 alkoxy or Cj-C4 haloalkoxy;
R6 is Cj-C4 alkyl, Cj-C4 haloalkyl, C3-C4 cycloalkyl or C3-C4 halocycloalkyl;
Q is a six membered aromatic ring containing ring members selected from carbon atoms and up to 2 nitrogen atoms, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from one or more Rw; and s is the number of the substituents;
Rwis independently H, cyano, halogen, Cj-Cg alkyl, Cj-C6 haloalkyl, Cj-Cg alkoxy, CjCg haloalkoxy, C2-Cg alkenyl, C2-Cg haloalkenyl, C2-Cg alkynyl, C2-C6 haloalkynyl, C3-Cg cycloalkyl, C3-Cg halocycloalkyl, C2-Cg cyanoalkyl, Cj-Cg hydroxyalkyl, C4CjQ alkylcycloalkyl, C4-C4Q cycloalkylalkyl, C3-Cg cycloalkenyl, C3-Cg halocycloalkenyl, C2-Cg alkoxyalkyl, C4-C10 cycloalkoxyalkyl, C3-Cjq alkoxyalkoxyalkyl, C2-Cg alkylthioalkyl, C2-Cg alkylsulfmylalkyl, Cj-Cg alkoxy, Cr Cg haloalkoxy, C3-Cg cycloalkoxy, C3-Cg halocycloalkoxy, C4-C10 cycloalkylalkoxy, C2-Cg alkenyloxy, C2-C6 haloalkenyloxy, C2-Cg alkoxyalkoxy, C2-Cg alkylcarbonyloxy, Cj-Cg alkylthio, Cj-Cg haloalkylthio, C3-Cg cycloalkylthio, Cj-Cg alkylsulfinyl, C^-Cg haloalkylsulfïnyl, C3-Cg cycloalkylsulfmyl, CpCg alkylsulfonyl, Cj-Cg haloalkylsulfonyl, C3-Cg cycloalkylsulfonyl, Cj-Cg alkylamino, C2-C6 dialkylamino, CrCg haloalkylamino, C2-Cg halodialkylamino or C3-Cg cycloalkylamino; or two Rw on adjacent carbon atoms together can form a -OCF2O-, -OCH2O-, -OCF2S-, -OCH2CH2)-, OCF2CF2O- cyclic ether ring;
s is 1, 2, 3, 4 or 5; n is 0, 1 or 2; with the proviso that 1) when R1 is F, R2 is H, A is CR3 wherein R3 is F, R4 is pyrazol-l-yl and R5 is H, Q is other than 4-OCF3-phenyl; and
2) R4 is other than pyridinyl.
This disclosure also provides a composition comprising a compound of Formula 1, an A-oxide or a sait thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. In one embodiment, this disclosure also provides a composition for controlling an invertebrate pest comprising a compound of Formula 1, an Noxide or a sait thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising at least one additional biologically active compound or agent.
This disclosure 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, an A-oxide or a sait thereof, (e.g., as a composition described herein).
This disclosure 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, an TV-oxide or a sait thereof, 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 disclosure 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 disclosure 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 an animal.
This disclosure 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 disclosure 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, an TV-oxide or a sait thereof, (e.g., as a composition described herein). This disclosure also relates to the treated seed (i.e. seed contacted with a compound of Formula 1).
This disclosure also provides a method for increasing vigor of a crop plant comprising contacting the crop plant, the seed from which the crop plant is grown or the locus (e.g., growth medium) of the crop plant with a biologically effective amount of a compound of Formula 1 (e.g., as a composition described herein).
This disclosure further provides a method for protecting an animal from an invertebrate parasitic pest comprising administering to the animal a parasiticidally effective amount of a compound of Formula 1, an TV-oxide or a sait thereof, (e.g., as a composition described herein). This disclosure also provides for the use of a compound of Formula 1, an TV-oxide or a sait thereof, (e.g., as a composition described herein) in protecting an animal from an invertebrate pest.
DETAILED DESCRIPTION
As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains”, “containing,” “characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process or method that comprises a list of éléments is not necessarily limited to only those éléments but may include other éléments not expressly listed or inhérent to such composition, mixture, process or method.
The transitional phrase “consisting of’ excludes any element, step, or ingrédient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of ’ appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other éléments are not excluded from the claim as a whole.
The transitional phrase “consisting essentially of ’ is used to define a composition or method that includes materials, steps, features, components, or éléments, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or éléments do not materially affect the basic and novel characteristic(s) of the claimed disclosure. The term “consisting essentially of ’ occupies a middle ground between “comprising” and “consisting of’.
Where applicants hâve defined an embodiment or a portion thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an embodiment using the terms “consisting essentially of ’ or “consisting of.”
Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or présent) and B is false (or not présent), A is false (or not présent) and B is true (or présent), and both A and B are true (or présent).
Also, the indefmite articles “a” and “an” preceding an element or component of the disclosure are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore “a” or “an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.
As referred to in this disclosure, the term “invertebrate pest” includes arthropods, gastropods, nematodes and helminths of économie importance as pests. The term “arthropod” includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans. The term “gastropod” includes snails, slugs and other Stylommatophora. The term “nematode” includes members of the phylum Nematoda, such as phytophagous nematodes and helminth nematodes parasitizing animais. The term “helminth” includes ail of the parasitic worms, such as roundworms (phylum Nematoda), heartworms (phylum Nematoda, class Secementea), flukes (phylum Platyhelminthes, class Tematoda), acanthocephalans (phylum Acanthocephala), and tapeworms (phylum Platyhelminthes, class Cestoda).
In the context of this disclosure “invertebrate pest control” means inhibition of invertebrate pest development (including mortality, feeding réduction, and/or mating disruption), and related expressions are defined analogously.
The term “agronomie” refers to the production of field; crops such as for food and fiber and includes the growth of maize or corn, soybeans and other legumes, rice, cereal (e.g., wheat, oats, barley, rye and rice), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers and cucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruit (e.g., berries and cherries) and other specialty crops (e.g., canola, sunflower and olives).
The term “nonagronomic” refers to other than field crops, such as horticultural crops (e.g., greenhouse, nursery or omamental 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 végétation management, public health (i.e. human) and animal health (e.g., domesticated animais such as pets, livestock and poultry, undomesticated animais such as wildlife) applications.
The term “crop vigor” refers to rate of growth or biomass accumulation of a crop plant. An “increase in vigor” refers to an increase in growth or biomass accumulation in a crop plant relative to an untreated control crop plant. The term “crop yield” refers to the retum on crop material, in ternis of both quantity and quality, obtained after harvesting a crop plant. An “increase in crop yield” refers to an increase in crop yield relative to an untreated control crop plant.
The term “biologically effective amount” refers to the amount of a biologically active compound (e.g., a compound of Formula 1) sufficient to produce the desired biological effect when applied to (i.e. contacted with) an invertebrate pest to be controlled or its environment, or to a plant, the seed from which the plant is grown, or the locus of the plant (e.g., growth medium) to protect the plant from injury by the invertebrate pest or for other desired effect (e.g., increasing plant vigor).
Nonagronomic applications include protecting an animal from an invertebrate parasitic pest by administering a parasiticidally effective (i.e. biologically effective) amount of a compound of the disclosure, typically in the form of a composition formulated for veterinary use, to the animal to be protected. As referred to in the présent disclosure and daims, the ternis “parasiticidal” and “parasiticidally” refers to observable effects on an invertebrate parasite pest to provide protection of an animal from the pest. Parasiticidal effects typically relate to diminishing the occurrence or activity of the target invertebrate parasitic pest. Such effects on the pest include necrosis, death, retarded growth, diminished mobility or lessened ability to remain on or in the host animal, reduced feeding and inhibition of reproduction. These effects on invertebrate parasite pests provide control (including prévention, réduction or élimination) of parasitic infestation or infection of the animal.
In the above recitations, the term “alkyl”, used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, z-propyl, or the different butyl, pentyl or hexyl isomers. “Alkenyl” includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. “Alkenyl” also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. “Alkynyl” includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. “Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. “Alkylene” dénotés a straight-chain or branched alkanediyl. Examples of “alkylene” include CH2, CH2CH2, CH(CH3), CH2CH2CH2, CH2CH(CH3) and the different butylène isomers. “Alkenylene” dénotés a straight-chain or branched alkenediyl containing one olefmic bond. Examples of “alkenylene” include CH=CH, CH2CH=CH, CH=C(CH3) and the different butenylene isomers. “Alkynylene” dénotés a straight-chain or branched alkynediyl containing one triple bond. Examples of “alkynylene” include C^C, CH2CZC, CZCCH2 and the different butynylene isomers.
“Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. “Alkoxyalkyl” dénotés alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2. “Alkoxyalkoxy” dénotés alkoxy substitution on alkoxy. “Alkenyloxy” includes straight-chain or branched alkenyloxy moieties. Examples of “alkenyloxy” include H2C=CHCH2O, (CH3)2C=CHCH2O, (CH3)CH=CHCH2O, (CH3)CH=C(CH3)CH2O and CH2=CHCH2CH2O. “Alkynyloxy” includes straight-chain or branched alkynyloxy moieties. Examples of “alkynyloxy” include HOCCH20, CH3OCCH20 and CH3OCCH2CH20. “Alkylthio” includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. “Alkylsulfinyl” includes both enantiomers of an alkylsulfmyl group. Examples of “alkylsulfinyl” include CH3S(O)-, CH3CH2S(O)-, CH3CH2CH2S(O)-, (CH3)2CHS(O)- and the different butylsulfinyl, pentylsulfmyl and hexylsulfmyl isomers. Examples of “alkylsulfonyl” include CH3S(O)2-, CH3CH2S(O)2-, CH3CH2CH2S(O)2-, (CH3)2CHS(O)2-, and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. “Alkylthioalkyl” dénotés alkylthio substitution on alkyl. Examples of “alkylthioalkyl” include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2. “Alkylthioalkoxy” dénotés alkylthio substitution on alkoxy. “Alkyldithio” dénotés branched or straight-chain alkyldithio moieties. Examples of “alkyldithio” include CH3SS-, CH3CH2SS-, CH3CH2CH2SS-, (CH3)2CHSS- and the different butyldithio and pentyldithio isomers. “Cyanoalkyl” dénotés an alkyl group substituted with one cyano group. Examples of “cyanoalkyl” include NCCH2, NCCH2CH2 and CH3CH(CN)CH2. “Alkylamino”, “dialkylamino”, “alkenylthio”, “alkenylsulfmyl”, “alkenylsulfonyl”, “alkynylthio”, “alkynylsulfmyl”, “alkynylsulfonyl”, and the like, are defined analogously to the above examples.
“Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term “alkylcycloalkyl” dénotés alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, z-propylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. The term “cycloalkylalkyl” dénotés cycloalkyl substitution on an alkyl moiety. Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups. The term “cycloalkoxy” dénotés cycloalkyl linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy. “Cycloalkylalkoxy” dénotés cycloalkylalkyl linked through an oxygen atom attached to the alkyl chain. Examples of “cycloalkylalkoxy” include cyclopropylmethoxy, cyclopentylethoxy, and other cycloalkyl moieties bonded to straight-chain or branched alkoxy groups. “Cyanocycloalkyl” dénotés a cycloalkyl group substituted with one cyano group. Examples of “cyanocycloalkyl” include 4-cyanocyclohexyl and 3-cyanocyclopentyl. “Cycloalkenyl” includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- and 1,4-cyclohexadienyl.
The term “halogen”, either alone or in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” or “alkyl substituted with halogen” include F3C-, C1CH2-, CF3CH2- and CF3CC12-. The terms “halocycloalkyl”, “haloalkoxy”, “haloalkylthio”, “haloalkenyl”, “haloalkynyl”, and the like, are defined analogously to the term “haloalkyl”. Examples of“haloalkoxy” include CF3O-, CC13CH2O-, HCF2CH2CH2Oand CF3CH2O-, Examples of “haloalkylthio” include CC13S-, CF3S-, CC13CH2S- and C1CH2CH2CH2S-. Examples of “haloalkylsulfmyl” include CF3S(O)-, CC13S(O)-, CF3CH2S(O)21278 and CF3CF2S(O)-. Examples of “haloalkylsulfonyl” include CF3S(O)2-, CC13S(O)2-, CF3CH2S(O)2- and CF3CF2S(O)2-. Examples of “haloalkenyl” include (C1)2C=CHCH2- and CF3CH2CH=CHCH2-, Examples of “haloalkynyl” include HOCCHCl-, CF3OC-, CC13OCand FCH2C=CCH2-. Examples of “haloalkoxyalkoxy” include CF3OCH2O-, C1CH2CH2OCH2CH2O-, C13CCH2OCH2O- as well as branched alkyl dérivatives.
“Alkylcarbonyl” dénotés a straight-chain or branched alkyl moieties bonded to a C(=O) moiety. Examples of “alkylcarbonyl” include CH3C(=O)-, CH3CH2CH2C(=O)- and (CH3)2CHC(=O)-. Examples of “alkoxycarbonyl” include CH3OC(=O)-, CH3CH2OC(=O)-, CH3CH2CH2OC(=O)-, (CH3)2CHOC(=O)- and the different butoxy- or pentoxycarbonyl isomers.
The Chemical abbreviations S(O) and S(=O) as used herein represent a sulfinyl moiety. The Chemical abbreviations SO2, S(O)2 and S(=O)2 as used herein represent a sulfonyl moiety. The Chemical abbreviations C(O) and C(=O) as used herein represent a carbonyl moiety. The Chemical abbreviations CO2, C(O)O and C(=O)O as used herein represent an oxycarbonyl moiety. “CHO” means formyl.
When R4 is a 5- to 6-membered heterocyclic ring substituted with up to 5 substituents independently selected from Rv, the substituents Rv may be attached to the remainder of the compound of Formula 1 through any available ring member of the heterocyclic ring.
When Q is a six membered aromatic ring substituted with up to 5 substituents independently selected from Rw, the substituents Rw may be attached to the remainder of the compound of Formula 1 through any available ring member of the six membered aromatic ring.
The total number of carbon atoms in a substituent group is indicated by the “C—Cj” prefix where i and j are numbers from 1 to 10. For example, Cj-C4 alkylsulfonyl désignâtes methylsulfonyl through butylsulfonyl; C2 alkoxyalkyl désignâtes CH3OCH2-; C3 alkoxyalkyl désignâtes, for example, CH3CH(OCH3)-, CH3OCH2CH2- or CH3CH2OCH2-; and C4 alkoxyalkyl désignâtes the varions isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2- and CH3CH2OCH2CH2-, . When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently seleçted from the group of defined substituents, e.g., [(Rv)r], r is 1, 2, 3, 4 or 5; and E(RW)S], s is 1, 2, 3, 4 or 5. When a group contains a substituent which can be hydrogen, for example Rv or Rw, then when this substituent is taken as hydrogen, it is recognized that this is équivalent to said group being unsubstituted. When one or more positions on a group are said to be “not substituted” or “unsubstituted”, then hydrogen atoms are attached to take up any free valency.
Unless otherwise indicated, a “ring” as a component of Formula 1 (e.g., substituent R4) is carbocyclic or heterocyclic. The term “ring member” refers to an atom or other moiety (e.g., C(=O), C(=S), S(O) or S(O)2) forming the backbone of a ring.
The term “carbocyclic ring” or “carbocycle” dénotés a ring wherein the atoms forming the ring backbone are seleçted only from carbon. The term “heterocyclic ring” or “heterocycle” dénotés a ring in which at least one atom forming the ring backbone is not carbon, e.g., nitrogen, oxygen or sulfur. Typically, a heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfiirs. Unless otherwise indicated, a carbocyclic ring or heterocyclic ring can be a saturated or unsaturated ring. “Saturated” refers to a ring having a backbone consisting of atoms linked to one another by single bonds; unless otherwise specified, the remaining atom valences are occupied by hydrogen atoms. Unless otherwise stated, an “unsaturated ring” may be partially unsaturated or fully unsaturated. The expression “fully unsaturated ring” means a ring of atoms in which the bonds between atoms in the ring are single or double bonds according to valence bond theory and furthermore the bonds between atoms in the ring include as many double bonds as possible without double bonds being cumulative (i.e. no C=C=C or C=C=N). The term “partially unsaturated ring” dénotés a ring comprising at least one ring member bonded to an adjacent ring member through a double bond and which conceptually potentially accommodâtes a number of non-cumulated double bonds between adjacent ring members (i.e. in its fully unsaturated counterpart form) greater than the number of double bonds présent (i.e. in its partially unsaturated form).
Unless otherwise indicated, heterocyclic rings can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
“Aromatic” indicates that each of the ring atoms is essentially in the same plane and has a //-orbital perpendicular to the ring plane, and in which (4n + 2) π électrons, where n is a positive integer, are associated with the ring to comply with Hückel’s rule. When a fully unsaturated carbocyclic ring satisfies Hückel’s rule, then said ring is also called an “aromatic ring” or “aromatic carbocyclic ring”. When a fully unsaturated heterocyclic ring satisfies Hückel’s rule, then said ring is also called a “heteroaromatic ring” or “aromatic heterocyclic ring”.
The term “optionally substituted” in connection with the heterocyclic rings refers to groups which are unsubstituted or hâve at least one non-hydrogen substituent that does not extinguish the biological activity possessed by the unsubstituted analog. As used herein, the following définitions shall apply unless otherwise indicated. The term optionally substituted is used interchangeably with the phrase “substituted or unsubstituted” or with the term “(un)substituted.” Unless otherwise indicated, an optionally substituted group may hâve a substituent at each substitutable position of the group, and each substitution is independent of the other.
When R4 is a 5- or 6-membered nitrogen-containing heterocyclic ring, it may be attached to the remainder of Formula 1 though any available carbon or nitrogen ring atom, unless otherwise described.
As noted above, R4 can be a 5- or 6-membered heterocyclic ring, which may be saturated or unsaturated, optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary. Examples of a 5- or 6-membered unsaturated aromatic heterocyclic ring optionally substituted with from one or more substituents include the rings U-2 through U-61 illustrated in Exhibit 1 wherein Rv is any substituent as defined in the Summary and r is an integer from 1 to 4, limited by the number of available positions on each U group. As U29, U-30, U-36, U-37, U-38, U-39, U-40, U-41, U-42 and U-43 hâve only one available position, for these U groups r is limited to the integer 1, and when Rv being H and r being 1 means that the U group is unsubstituted and a hydrogen is présent at the position indicated by (Rv)r.
U-56 4 (RV)r
U-61
U-58 U-59 U-60
Note that when R4 is a 5- or 6-membered saturated or unsaturated non-aromatic heterocyclic ring optionally substituted with one or more substituents selected from the group of substituents as defined in the Summary, one or two carbon ring members of the heterocycle can optionally be in the oxidized form of a carbonyl moiety.
Examples of a 5- or 6-membered saturated or non-aromatic unsaturated heterocyclic ring include the rings G-l through G-35 as illustrated in Exhibit 2. Note that when the attachment point on the G group is illustrated as floating, the G group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the G group by replacement of a hydrogen atom. The optional substituents corresponding to Rv can be attached to any available carbon or nitrogen by replacing a hydrogen atom. For these G rings, s is typically an integer from 1 to 5, limited by the number of available positions on each G group.
Note that when R4 comprises a ring selected from G-28 through G-35, G2 is selected from O, S or N. Note that when G2 is N, the nitrogen atom can complété its valence by substitution with the substituents corresponding to Rw as defined in the Summary.
Exhibit 2
G-l G-2 G-3 G-4 G-5
Although Rv groups are shown in the structures U-2 through U-61, it is noted that they do not need to be présent since they are optional substituents. Note that when Rv is H attached to an 5 atom, this is the same as if said atom is unsubstituted. The nitrogen atoms that require substitution to fïll their valence are substituted with H. or Rv. Note that when the attachment point between (Rv)r and the U ring is illustrated as floating, (Rv)r can be attached to any available carbon atom or nitrogen atom of the U ring. Note that when the attachment point on the U ring is illustrated as floating, the U group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the U group by replacement of a hydrogen atom. Note that some U rings can only be substituted with less than 4 Rv groups (e.g., U-2 through U-5, U-7 through U-49, and U-52 through U-61).
A wide variety of synthetic methods are known in the art to enable préparation of aromatic and nonaromatic heterocyclic rings and ring Systems; for extensive reviews see the eight volume set of Comprehensive Heterocyclic Chemistry, A. R. Katritzky and C. W. Rees editors-in-chief, Pergamon Press, Oxford, 1984 and the twelve volume set of Comprehensive Heterocyclic Chemistry II, A. R. Katritzky, C. W. Rees and E. F. V. Scriven editors-in-chief, Pergamon Press, Oxford, 1996.
Compounds of this disclosure can exist as one or more stereoisomers. Stereoisomers are isomers of identical constitution but differing in the arrangement of their atoms in space and include enantiomers, diastereomers, cis-trans isomers (also known as géométrie isomers) and atropisomers. Atropisomers resuit from restricted rotation about single bonds where the rotational barrier is high enough to permit isolation of the isomeric species. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit bénéficiai effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively préparé said stereoisomers. For a comprehensive discussion of ail aspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.
The compounds of the disclosure may be présent as a mixture of stereoisomers or individual stereoisomers. For example, two possible enantiomers of Formula 1 are depicted as Formula laa and Formula laa' involving a chiral carbon center identified with an asterisk (*). Analogously, other chiral centers are possible at, for example, R4.
la la'
Molecular depictions drawn herein follow standard conventions for depicting stereochemistry. To indicate stéréo configuration, bonds rising from the plane of the drawing and towards the viewer are denoted by solid wedges wherein the broad end of the wedge is attached to the atom rising from the plane of the drawing towards the viewer. Bonds going below the plane of the drawing and away from the viewer are denoted by dashed wedges wherein the broad end of the wedge is attached to the atom further away from the viewer.
The compounds of the disclosure can exist as stereoisomers due to the possible chiral carbon atoms présent in Formula 1. Thus, this disclosure comprises the individual stereoisomers of the compounds of Formula 1, as well as mixtures of stereoisomers of the compounds of Formula 1.
Compounds of Formula 1 can comprise additional chiral centers. For example, substituents and other molecular constituées such as R4 may themselves contain chiral centers. This disclosure comprises racemic mixtures as well as enriched and essentially pure stéréo configurations at these additional chiral centers.
Compounds of this disclosure can exist as one or more conformational isomers due to restricted rotation about any bonds in Formula 1. This disclosure comprises mixtures of conformational isomers. In addition, this disclosure includes compounds that are enriched in one conformer relative to others.
The more biologically active enantiomer is believed to be Formula la (the R-enantiomer of Formula 1.
This disclosure comprises racemic mixtures of equal amounts of the enantiomers of Formulae la (the R-enantiomer of Formula 1) and la’ (the S-enantiomer of Formula 1). In addition, this disclosure includes mixtures that are enriched in the Formula la enantiomer compared to the racemic mixture of Formulae la and la’. This disclosure also comprises the essentially pure enantiomer of Formula la.
An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula la and Formula la’, wherein the ratio of la to la’ is at least 75:25 (a 50% enantiomeric excess).
An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula la and Formula la’, wherein the ratio of la to la’ is at least 90:10 (an 80% enantiomeric excess of la ).
An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula la and Formula la’, wherein the ratio of la to la’ is at least 95:5 (a 90% enantiomeric excess of la).
An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula la and Formula la’, wherein the ratio of la to la’ is at least 98:2 (a 96% enantiomeric excess of la).
An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula la and Formula la’, wherein the ratio of la to la’ is at least 99:1 (a 98% enantiomeric excess of la).
An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula la and Formula la’, wherein the ratio of la to la’ is essentially 100:0.
An embodiment of this disclosure comprises the compounds of Formula la.
One skilled in the art will appreciate that not ail nitrogen-containing heterocycles can form A-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form A-oxides. One skilled in the art will also recognize that tertiary amines can form A-oxides. Synthetic methods for the préparation of A-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and 3-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as z-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the préparation of A-oxides hâve been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academie Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academie Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academie Press.
One skilled in the art recognizes that because in the environment and under physiological conditions salts of Chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms. Thus a wide variety of salts of the compounds of Formula 1 are useful for control of invertebrate pests. 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. When a compound of Formula 1 contains an acidic moiety such as a carboxylic acid or phénol, salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnésium or barium. Accordingly, the present disclosure comprises compounds selected from Formula 1, A-oxides and suitable salts thereof.
Compounds selected from Formula 1, stereoisomers, tautomers, A-oxides, and salts thereof, typically exist in more than one form, and Formula 1 thus includes ail crystalline and noncrystalline forms of the compounds that Formula 1 represents. Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts. Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types). The term “polymorph” refers to a particular crystalline form of a Chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molécules in the crystal lattice. Although polymorphs can hâve the same Chemical composition, they can also differ in composition due to the presence or absence of co-crystallized water or other molécules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such Chemical, physical and biological properties as crystal shape, density, hardness, color, Chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability. One skilled in the art will appreciate that a polymorph of a compound represented by Formula 1 can exhibit bénéficiai effects (e.g., suitability for préparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound represented by Formula 1. Préparation 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 températures. Compounds of this disclosure may exist as one or more crystalline polymorphs. This disclosure comprises both individual polymorphs and mixtures of polymorphs, including mixtures enriched in one polymorph relative to others. For a comprehensive discussion of polymorphism see R. Hilfiker, Ed., Polymorphism in the Pharmaceutical Industry, Wiley-VCH, Weinheim, 2006.
Embodiments of the present disclosure as described in the Summary include those described below. In the following Embodiments, Formula 1 includes stereoisomers, A-oxides and salts thereof, and référencé to “a compound of Formula 1” includes the définitions of substituents specified in the Summary unless further defined in the Embodiments.
Embodiment 1. A compound of Formula 1 wherein R1 is F, OR6 or SR6.
Embodiment la. A compound of Formula 1 or Embodiment 1 wherein R1 is F.
Embodiment lb. A compound of Formula 1 or Embodiment 1 wherein R1 is OR6.
Embodiment le. A compound of Formula 1 or Embodiment 1 wherein R1 is SR6.
Embodiment 2. A compound of Formula 1 or any one of the preceding Embodiments wherein A is N or CR3.
Embodiment 2a. A compound of Formula 1 or any one of the preceding Embodiments wherein A is N.
Embodiment 2b. A compound of Formula 1 or any one of the preceding Embodiments wherein A is CR3.
Embodiment 3. A compound of Formula 1 or any one of the preceding Embodiments wherein R2 is H, halogen, CN, C1-C4 alkyl, C]-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C]-C4 haloalkoxy.
Embodiment 3 a. A compound of Formula 1 or any one of the preceding Embodiments wherein R2 is H, halogen or Q-C4 alkyl.
Embodiment 3b. A compound of Embodiment 3 wherein R2 is H.
Embodiment 3 c. A compound of Embodiment 3 wherein R2 is halogen.
Embodiment 3d. A compound of Embodiment 3 wherein R2 is C1-C4 alkyl.
Embodiment 4. A compound of Formula 1 or any one of the preceding Embodiments wherein R3 is H, halogen, CN, A-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy.
Embodiment 4a. A compound of Embodiment 4 wherein R3 is H, halogen, CpC4 alkyl, Cp C4 haloalkyl, Cj-C4 alkoxy or Cj-C4 haloalkoxy.
Embodiment 4b. A compound of Embodiment 4a wherein R3 is H or halogen.
Embodiment 4c. A compound of Embodiment 4b wherein R3 is H.
Embodiment 4d. A compound of Embodiment 4a wherein R3 is halogen.
Embodiment 4f. A compound of Embodiment 4d wherein R3 is F.
Embodiment 4g. A compound of Embodiment 4d wherein R3 is Cl.
Embodiment 4h. A compound of Embodiment 4d wherein R3 is Br.
Embodiment 4i. A compound of Embodiment 4a wherein R3 is C1-C4 alkyl.
Embodiment 4j. A compound of Embodiment 4i wherein R3 is Me.
Embodiment 4k. A compound of Embodiment 4a wherein R3 is C1-C4 haloalkyl.
Embodiment 41. A compound of Embodiment 4k wherein R3 is CF3.
Embodiment 5. A compound of Formula 1 or any one of the preceding Embodiments wherein R4 is a 5- to 6-membered heterocyclic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and 10 up to 4 N atoms, wherein up to 2 ring members are independently selected from C(=O), C(=S), S(=O) and S(=O)2, each ring or ring System optionally substituted with up to 5 substituents independently selected from Rv, and r is the number of the substituents.
Embodiment 5a. A compound of Embodiment 5 wherein R4 is selected from U-2 to U-49 or U52 to U61 as shown in Exhibit 1.
Embodiment 5b. A compound of Embodiment 5a wherein R4 is selected from U-2 to U-49.
Embodiment 5c. A compound of Embodiment 5b wherein R4 is selected from U-2, U-3, U4, U-5, U-7, U-9, U-ll, U-12, U-13, U-16, U-21, U-25, U-26, U-27, U-28, U-29, U-31, U-32, U35, U-36, U-37, U-44, U-48 and U-49.
Embodiment 5d. Acompound of Embodiment 5cwhereinR4is selectedfromU-9, U-ll, U32, U-36 and U-44.
Embodiment 5e. A compound of Embodiment 5d wherein R4 is selected from U-9 and U44.
Embodiment 5f. A compound of Embodiment 5e wherein R4 is U-9.
Embodiment 5g. A compound of Embodiment 5d wherein R4 is U-l 1.
Embodiment 5h. A compound of Embodiment 5d wherein R4 is U-32.
Embodiment 5i. A compound of Embodiment 5d wherein R4 is U-36. .
Embodiment 5j. A compound of Embodiment 5d wherein R4 is U-44.
Embodiment 5k. A compound of Embodiment 5 wherein R4 is selected from G-l to G-37 as 15 shown in Exhibit 2.
Exhibit 2
G-6
G-14
G-17
G-16
G-21
G-26
G-34 G-35
N
G-37
Embodiment 51. A compound of Embodiment 5k wherein G2 is O, S or N.
Embodiment 5m. A compound of Embodiment 51 wherein G2 is O.
Embodiment 5n. A compound of Embodiment 51 wherein G2 is S.
Embodiment 5o. A compound of Embodiment 51 wherein G2 is N.
Embodiment 6. A compound of Formula 1 or any one of the preceding Embodiments wherein Rv is independently H, halogen, Cj-Cg alkyl, Cj-Cg haloalkyl, Cj-Cg alkoxy or Cj-Cg haloalkoxy.
Embodiment 6a. A compound of Embodiment 6 wherein Rv is H.
Embodiment 6b. A compound of Embodiment 6 wherein Rv is halogen.
Embodiment 6c. A compound of Embodiment 6 wherein Rv is Cj-Cg alkyl.
Embodiment 6d. A compound of Embodiment 6c wherein Rv is Me.
Embodiment 7. A compound of Formula 1 or any one of Embodiments 5 to 6d wherein r is 1,2, 3, 4 or 5.
Embodiment 7a. A compound of Embodiment 7 wherein r is 1 or 2.
Embodiment 7b. A compound of Embodiment 7 wherein r is 1.
Embodiment 7c. A compound of Embodiment 7 wherein r is 2.
Embodiment 7d. A compound of Embodiment 7 wherein r is 3.
Embodiment 7e. A compound of Embodiment 7 wherein r is 4.
Embodiment 7f. A compound of Embodiment 7 wherein r is 5.
Embodiment 8. A compound of Formula 1 or any one of the preceding Embodiments wherein R5 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C4-C4 alkoxy or Cj-C4 haloalkoxy.
Embodiment 8a. A compound of Embodiment 8 wherein R5 is H, halogen, C4-C4 alkyl, Cp C4 haloalkyl, CI-C4 alkoxy or C1-C4 haloalkoxy.
Embodiment 8b. A compound of Embodiment 8a wherein R5 is H or halogen.
Embodiment 8c. A compound of Embodiment 8b wherein R5 is H.
Embodiment 8d. A compound of Embodiment 8b wherein R5 is halogen.
Embodiment 8e. A compound of Embodiment 8d wherein R5 is F.
Embodiment 8e. A compound of Embodiment 8d wherein R5 is Cl.
Embodiment 8e. A compound of Embodiment 8d wherein R5 is Br.
Embodiment 8e. A compound of Embodiment 8a wherein R5 is Ci-C4 alkyl.
Embodiment 9. A compound of Formula 1 or any one of the preceding Embodiments wherein R6 is Ci-C4 alkyl, CpC4 haloalkyl, C3-C4 cycloalkyl or C3-C4 halocycloalkyl.
Embodiment 9a. A compound of Embodiment 9 wherein R6 is Cj-C4 alkyl or C;-C4 haloalkyl.
Embodiment 9b. A compound of Embodiment 9 wherein R6 is Cj-C4 alkyl.
Embodiment 9c. A compound of Embodiment 9b wherein R6 is Me;
Embodiment 9d. A compound of Embodiment 9 wherein R6 is CpC4 haloalkyl.
Embodiment 9e. A compound of Embodiment 9b wherein R6 is CF3.
Embodiment 10. A compound of Formula 1 or any one of the preceding Embodiments wherein Q is a six membered aromatic ring with 0 to 2 N on the ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw.
Embodiment 10a. A compound of Embodiment 10 wherein Q is a phenyl, pyridinyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw.
Embodiment 10b. A compound of Embodiment 10a wherein Q is a phenyl ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw.
Embodiment 10c. A compound of Embodiment 10a wherein Q is a pyridinyl ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from
Rw.
Embodiment lOd. A compound of Embodiment 10a wherein Q is a pyrimidinyl ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw.
Embodiment 10e. A compound of Embodiment 10a wherein Q is a pyrazinyl ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw.
Embodiment 11. A compound of Formula 1 or any one of Embodiments 9 through 9e wherein Rw is independently H, cyano, halogen, CpCg alkyl, Cj-Cg alkoxy, Cj-Cg haloalkoxy, CpCg haloalkyl, C2-Cg alkenyl, C2-Cg haloalkenyl, C2-Cg alkynyl, C2-Cg haloalkynyl, C2-Cg alkoxyalkoxy, Cj-Cg alkylthio, CpCg haloalkylthio, C3-Cg cycloalkylthio, Cj-Cg alkylsulfinyl, Cj-Cg haloalkylsulfmyl, Cj-Cg alkylsulfonyl, CpCg haloalkylsulfonyl or C3-C6 cycloalkylsulfonyl;
Embodiment lia. A compound of Embodiment 11 wherein Rwis cyano, halogen, CpCg alkyl, Cj-Cg alkoxy, Cj-Cg haloalkoxy, Cj-Cg haloalkyl, C2-Cg alkenyl, C2-C6 haloalkenyl, C2Cg alkynyl, C2-C6 haloalkynyl, CpCg alkylthio, CpCg haloalkylthio, CpCg alkylsulfinyl, CpCg haloalkylsulfmyl, CpCg alkylsulfonyl or CpCg haloalkylsulfonyl.
Embodiment 11b. A compound of Embodiment lia wherein Rwis Cj-Cg haloalkoxy, CtCg haloalkyl, C2-Cg alkenyl, C2-Cg haloalkenyl, C2-Cg alkynyl, C2-Cg haloalkynyl, C|-Cg alkylthio, CpCg haloalkylthio, Cj-Cg alkylsulfinyl, CpCg haloalkylsulfmyl, CpCg alkylsulfonyl, Cq-Cg haloalkylsulfonyl.
Embodiment 11c. A compound of Embodiment 1 lb wherein Rw is Cj-Cg haloalkoxy, Cp Cg haloalkyl, C2-Cg haloalkenyl, C2-Cg haloalkynyl, CpCg haloalkylthio, CpCg haloalkylsulfmyl, CpCg haloalkylsulfonyl.
Embodiment lld. A compound of Embodiment 11c wherein Rw is OCF3, SCF3, CF3, SOCF3 orSO2CF3.
Embodiment 1 le. A compound of Embodiment lld wherein Rwis OCF3.
Embodiment 1 If. A compound of Embodiment 1 Id wherein Rw is SCF3.
Embodiment 11g. A compound ofEmbodiment lld whereinRwis CF3.
Embodiment 1 Ih. A compound of Embodiment 1 Id wherein Rw is SOCF3 or SO2CF3.
Embodiment 12. A compound of Formula 1 or any one of the preceding Embodiments wherein s is 1, 2, 3, 4 or 5.
Embodiment 12a. A compound of Embodiment 12 wherein r is 1 or 2.
Embodiment 12b. A compound of Embodiment 12 wherein r is 1.
Embodiment 12c. A compound of Embodiment 12 wherein r is 2.
Embodiment 12d. A compound of Embodiment 12 wherein r is 3.
Embodiment 12e. A compound of Embodiment 12 wherein r is 4.
Embodiment 12f. A compound of Embodiment 12 wherein r is 5.
Embodiment 13. A compound of Formula 1 or any one of the preceding Embodiments wherein n is 0, 1 or 2.
Embodiment 13a. A compound of Embodiment 13 wherein n is 0.
Embodiment 13b. A compound of Embodiment 13 wherein n is 1.
Embodiment 13 c. A compound of Embodiment 13 wherein n is 2.
Embodiment Al. A compound of any one of Embodiments 1-13c wherein the compound of Formula 1 is a compound of Formula la.
Embodiment A2. A compound of any one of Embodiments 1-13c wherein the compound of Formula 1 is a compound of Formula la’.
Embodiment A3. A composition comprising a compound of Formula la and a compound of Formula la’.
Embodiment A3 a. A composition of Embodiment A3 wherein the ratio of the compound of Formula la to the compound of Formula la’ is greater than 60:40.
Embodiment A3b. A composition of Embodiment A3a wherein the ratio of the compound of Formula la to the compound of Formula la’ is greater than 80:20.
Embodiment A3c. A composition of Embodiment A3 a wherein the ratio of the compound of Formula la to the compound of Formula la’ is greater than 90:10.
Embodiment A3d. A composition of Embodiment A3 a wherein the ratio of the compound of Formula la to the compound of Formula la’ is greater than 99:1.
Embodiment A4. A composition comprising a compound of Formula la’ and a compound of Formula la.
Embodiment A4a. A composition of Embodiment A4 wherein the ratio of the compound of Formula la’ to the compound of Formula la is greater than 60:40.
Embodiment A4b. A composition of Embodiment A4 wherein the ratio of the compound of Formula la’ to the compound of Formula la is greater than 80:20.
Embodiment A4c. A composition of Embodiment A4 wherein the ratio of the compound of Formula la’ to the compound of Formula la is greater than 90:10.
Embodiment A4d. A composition of Embodiment A4 wherein the ratio of the compound of Formula la’ to the compound of Formula la is greater than 99:1.
Embodiment X. 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.
Embodiment XI. A method of Embodiment X wherein the invertebrate pest is a member of Hemiptera.
Embodiment X2. A method of Embodiment XI wherein the member of Hemipteran is a member of the suborder Homoptera.
Embodiment X2a. A method of Embodiment X2 wherein the suborder Homoptera comprises planthoppers from the families Cicadellidae and Delphacidae.
Embodiment X2b. A method of Embodiment X2 wherein the suborder Homoptera comprises aphids from the family Aphididae.
Embodiment X2c. A method of Embodiment X2 wherein the suborder Homoptera comprises whiteflies from the family Aleyrodidae.
Embodiment X3. A method of Embodiment X2 wherein the suborder Homoptera comprises CPH, CMA, GPA and WF.
Embodiment X4. A method of Embodiment X2 wherein the suborder Homoptera comprises Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid or melon aphid), Bemisia tabaci Gennadius (tobacco whitefly, sweetpotato whitefly), Bemisia argentifolii Bellows & Perring (silverleaf whitefly), Dialeurodes citri Ashmead (citrus whitefly) and Trialeurodes vaporariorum Westwood (greenhouse whitefly); Empoasca fabae Harris (potato leafhopper), ι
Laodelphax striatellus Fallen (smaller brown planthopper), Macrosteles quadrilineatus Forbes (aster leafhopper), Nephotettix cincticeps Uhler (green rice leafhopper), Nephotettix nigropictus Stâl (rice leafhopper), Nilaparvata lugens Stâl (brown planthopper), Peregrinus maidis Ashmead (corn planthopper), Sogatella furcifera Horvath (white-backed planthopper), Tagosodes orizicolus Muir (rice delphacid), Typhlocybapomaria McAtee (white apple leafhopper) or Erythroneura spp. (grape leafhoppers).
Embodiment X5. A method of Embodiment XI wherein the Hemipteran is a member of the saborder Heteroptera.
Embodiment X5a. A method of Embodiment X5 wherein the saborder Heteroptera comprises Acrosternum hilare Say (green stink bag), Anasa tristis De Geer (sqaash bag), Blissus leucopterus leucopterus Say (chinch bag), Cimex lectularius Llinnaeas (bed bag) Corythucha gossypii Fabricias (cotton lace bag), Cyrtopeltis modesta Distant (tomato bag), Dichelops melacanthus Dallas (green belly Stink bag), Dysdercus suturellus Herrich-Schâffer (cotton stainer), Euschistus héros Fabricias (Neotropical Brown Stink Bag), Euschistus servus Say (brown stink bag), Euschistus variolarius Palisot de Beaavois (one-spotted stink bag), Graptostethus spp. (complex of seed bags), Halyomorpha halys Stâl (brown marmorated stink bag), Leptoglossus corculus Say (leaf-footed pine seed bag), Lygus lineolaris Palisot de Beaavois (tamished plant bag), Nezara viridula Linnaeas (soathem green stink bag), Oebalus pugnax Fabricias (rice stink bag), Oncopeltus fasciatus Dallas (large milkweed bag), Pseudatomoscelis seriatus Reater (cotton fleahopper).
Embodiment X6. A method of Embodiment X5 wherein the saborder Heteroptera comprises stink bags from the family Pentatomidae.
Embodiment X7. A method of Embodiment X6 wherein the saborder Heteroptera comprises Acrosternum hilare Say (green stink bag), Dichelops melacanthus Dallas (green belly Stink bag), Euschistus héros Fabricias (Neotropical Brown Stink Bag), Euschistus servus Say (brown stink bag), Euschistus variolarius Palisot de Beaavois (one-spotted stink bag), Halymorpha halys Stâl (brown marmorated stink bag), Nezara viridula Linnaeas (soathem green stink bag), Oebalus pugnax Fabricias (rice stink bag).
Embodiment X8. A method of Embodiment X5 wherein the saborder Heteroptera comprises Anasa tristis De Geer (sqaash bag), Blissus leucopterus Say (chinch bag), Cimex lectularius Linnaeas (bed bag), Corythuca gossypii Fabricias (cotton lace bag), Cyrtopeltis modesta Distant (tomato bag), Dysdercus suturellus Herrich-Schaffer (cotton stainer), Graptosthetus spp.
(complex of seed bugs), Leptoglossus corculus Say (leaf-footed pine seed bug), Lygus lineolaris Palisot de Beauvois (tamished plant bug), Oncopeltus fasciatus Dallas (large milkweed bug), or Pseudatomoscelis seriatus Reuter (cotton fleahopper).
Embodiments of this disclosure, including Embodiments 1-X8 above as well as any other embodiments described herein, can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula 1 but also to the starting compounds and intermediate compounds usefiil for preparing the compounds of Formula 1. In addition, embodiments of this disclosure, including Embodiments 1-X8 above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the présent disclosure.
Combinations of Embodiments 1-X8 are illustrated by:
Embodiment A. A compound of Formula 1 wherein
R1 is F;
A is CR3;
R2 is H, halogen, CN, Cj-C4 alkyl, Ci-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;
R3 is H, halogen, CN, C1-C4 alkyl, A-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, A-C4 alkoxy or C1-C4 haloalkoxy;
R4 is a 5- to 6-membered heterocyclic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(=O), C(=S), S(=O) and S(=O)2, each ring or ring System optionally substituted with up to 5 substituents independently selected from Rv, and r is the number of the substituents.
each Rv is independently H, halogen, Cj-C6 alkyl, Cj-Cg haloalkyl, C^-Cg alkoxy or CjC6 haloalkoxy;
r is 1, 2, 3, 4 or 5;
R5 is H, halogen, CN, CrC4 alkyl, CpC4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or A-C4 haloalkoxy;
Q is a six membered aromatic ring with 0 to 2 N on the ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw;
Rwis independently cyano, halogen, CpCg alkyl, Cj-C6 alkoxy, Ci~C6 haloalkoxy, Ci-Cg haloalkyl, C2-C5 alkenyl, C2-C5 haloalkenyl, C2-C5 alkynyl, C2-Cg haloalkynyl, CjC6 alkylthio, Cj-Cg haloalkylthio, Cj-Cg alkylsulfinyl, Cj-Cg haloalkylsulfinyl, CjC6 alkylsulfonyl or CpC6 haloalkylsulfonyl;
s is 1, 2, 3, 4 or 5;
n is 0, 1 or 2.
Embodiment B. A compound of Embodiment A wherein
R2 is H, halogen or C4-C4 alkyl;
R3 is H, halogen, C4-C4 alkyl, C4-C4 haloalkyl, Cy-C^ alkoxy or CZ-C4 haloalkoxy;
R4 is selected from U-2 to U-49 or U52 to U61 as shown in Exhibit 1;
r is 1 or 2;
R5 is H, halogen, C4-C4 alkyl, CpC4 haloalkyl, C^-C^ alkoxy or C4-C4 haloalkoxy;
Rwis Cj-Cg haloalkoxy, CpCg haloalkyl, C2-Cg haloalkenyl, C2-Cg haloalkynyl, CpCg haloalkylthio, CpC6 haloalkylsulfinyl, CpC6 haloalkylsulfonyl.
s is 1 or 2.
Embodiment C. A compound of Embodiment B wherein
R2 is H;
R3 is H or halogen;
R4 is selected from U-2 to U-49;
Rv is H;
R5 is H or halogen;
Q is a phenyl, pyridinyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw;
Rwis OCF3, SCF3, CF3, SOCF3 or SO2CF3.
Embodiment D. A compound of Embodiment B wherein
R2 is H;
R3 is H or halogen;
R4 is selected from U-2 to U-49;
Rv is CrC6 alkyl;
R5 is H;
Q is a phenyl, pyridinyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw;
Embodiment E. A compound of Embodiment C wherein
R3 is halogen;
R4 is selected from U-2, U-3, U-4, U-5, U-7, U-9, U-ll, U-12, U-13, U-16, U-21, U-25, U26, U-27, U-28, U-29, U-31, U-32, U-35, U-36, U-37, U-44, U-48 and U-49;
R5 is H;
Q is a phenyl, pyridinyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw.
Embodiment F. A compound of Embodiment E wherein
R3 is F;
R4 is selected from U-9, U-l 1, U-32, U-36 and U-44;
Q is a phenyl ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw.
Embodiment G. A compound of Embodiment F wherein
R4 is selected from U-9 and U-44.
Embodiment H. A compound of Embodiment G wherein
R4 is selected from the group of U-9.
Embodiment I. A compound of Embodiment G wherein
R4 is selected from the group of U-44.
Embodiment J. A compound of Embodiment B wherein
R2 is CrC4 alkyl;
R3 is H or halogen;
R4 is seleçted from U-2 to U-49;
Rv is H;
r is 2;
R5 is H;
Q is a phenyl, pyridinyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently seleçted from Rw;
Rwis OCF3, SCF3, CF3, SOCF3 or SO2CF3.
Embodiment AA. A compound of Formula 1 wherein
R1 is OR6;
A is CR3;
R2 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;
R3 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;
R4 is a 5- to 6-membered heterocyclic ring, each ring containing ring members seleçted from carbon atoms and 1 to 4 heteroatoms independently seleçted from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently seleçted from C(=O), C(=S), S(=O) and S(=O)2, each ring or ring System optionally substituted with up to 5 substituents independently seleçted from Rv, and r is the number of the substituents.
each Rv is independently H, halogen, Cj-Cg alkyl, C1-C6 haloalkyl, Cj-Cg alkoxy or CjC$ haloalkoxy;
r is 1, 2, 3, 4 or 5;
R5 is H, halogen, CN, C1-C4 alkyl, CpC4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;
R6 is C]-C4 alkyl;
Q is a six membered aromatic ring with 0 to 2 N on the ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently seleçted from Rw;
Rwis independently cyano, halogen, CpCg alkyl, Cj-Cg alkoxy, Cj-Cg haloalkoxy, CpCg haloalkyl, C2-C6 alkenyl, C2-Cg haloalkenyl, C2-Cg alkynyl, C2-Cg haloalkynyl, Cp Cg alkylthio, CpCg haloalkylthio, CpC6 alkylsulfinyl, CpCg haloalkylsulfinyl, Cp Cg alkylsulfonyl or CpC6 haloalkylsulfonyl;
s is 1, 2, 3, 4 or 5;
n is 0, 1 or 2.
Embodiment BB. A compound of Embodiment AA wherein
R2 is H, halogen or CpC4 alkyl;
R3 is H, halogen, CpC4 alkyl, CpC4 haloalkyl, C4-C4 alkoxy or C4-C4 haloalkoxy;
R4 is selected from U-2 to U-49 or U52 to U61 as shown in Exhibit 1;
r is 1 or 2;
R5 is H, halogen, CpC4 alkyl, CpC4 haloalkyl, C1-C4 alkoxy or C4-C4 haloalkoxy;
R6 is Me;
Rwis Cj-Cg haloalkoxy, CpCg haloalkyl, C2-Cg haloalkenyl, C2-Cg haloalkynyl, CpCg haloalkylthio, CpCg haloalkylsulfinyl, CpCg haloalkylsulfonyl.
s is 1 or 2.
Embodiment CC. A compound of Embodiment BB wherein
R2 is H;
R3 is H or halogen;
R4 is selected from U-2 to U-49;
Rv is H;
r is 2;
R5 is H or halogen;
Q is a phenyl, pyridinyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw;
Rwis OCF3, SCF3, CF3, SOCF3 or SO2CF3.
Embodiment DD. A compound of Embodiment BB wherein
R2 is H;
R3 is H or halogen;
R4 is selected from U-2 to U-49;
Rv is Cj-Cg alkyl;
R5 is H;
Q is a phenyl, pyridinyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw.
Embodiment EE. A compound of Embodiment CC wherein
R3 is halogen;
R4is selected from U-2, U-3, U-4, U-5, U-7, U-9, U-ll, U-12, U-13, U-16, U-21, U-25, U26, U-27, U-28, U-29, U-31, U-32, U-35, U-36, U-37, U-44, U-48 and U-49;
R5 is H;
Q is a phenyl, pyridinyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw.
Embodiment FF. A compound of Embodiment EE wherein
R3 is F;
R4 is selected from U-9 and U-44;
Q is a phenyl ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw.
Embodiment GG. A compound of Embodiment FF wherein
R4 is selected from the group of U-9.
Embodiment HH. A compound of Embodiment FF wherein
R4 is selected from the group of U-44.
Embodiment AAA. A compound of Formula 1 wherein
R1 is SR6;
A is CR3;
R2 is H, halogen, CN, CrC4 alkyl, CrC4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, Ci~C4 alkoxy or Ci~C4 haloalkoxy;
R3 is H, halogen, CN, CpC4 alkyl, C4-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or CJ-C4 haloalkoxy;
R4 is a 5- to 6-membered heterocyclic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(=O), C(=S), S(=O) and S(=O)2, each ring or ring System optionally substituted with up to 5 substituents independently selected from Rv, and r is the number of the substituents.
each Rv is independently H, halogen, C^-Cg alkyl, Cj-Cg haloalkyl, Cj-Cg alkoxy or CjCg haloalkoxy;
r is 1, 2, 3, 4 or 5;
R5 is H, halogen, CN, CpC4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, Y-C4 alkoxy or C1-C4 haloalkoxy;
R6 is CpC4 alkyl;
Q is a six membered aromatic ring with 0 to 2 N on the ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw;
Rwis independently cyano, halogen, CpCg alkyl, Cj-Cg alkoxy, Cj-Cg haloalkoxy, CpCg haloalkyl, C2-Cg alkenyl, C2-Cg haloalkenyl, C2-Cg alkynyl, C2-Cg haloalkynyl, Cp Cg alkylthio, CpCg haloalkylthio, CpCg alkylsulfînyl, CpCg haloalkylsulfinyl, Cp Cg alkylsulfonyl or CpCg haloalkylsulfonyl;
s is 1, 2, 3, 4 or 5; n is 0, 1 or 2.
Embodiment BBB. A compound of Embodiment AAA wherein
R2 is H, halogen or CpC4 alkyl;
R3 is H, halogen, CpC4 alkyl, CpC4 haloalkyl, Cj-C4 alkoxy or C]-C4 haloalkoxy;
R4 is selected from U-2 to U-49 or U52 to U61 as shown in Exhibit 1 ;
r is 1 or 2;
R5 is H, halogen, CpC4 alkyl, CpC4 haloalkyl, C]-C4 alkoxy or C^C^ haloalkoxy;
R6 is Me;
Rwis Cj-Cg haloalkoxy, CpCg haloalkyl, C2-Cg haloalkenyl, C2-Cg haloalkynyl, CpCg haloalkylthio, CpCg haloalkylsulfinyl, CpCg haloalkylsulfonyl.
s is 1 or 2.
Embodiment CCC. A compound of Embodiment BBB wherein
R2 is H;
R3 is H or halogen;
R4 is selected from U-2 to U-49;
Rv is H;
r is 2;
R5 is H;
Q is a phenyl, pyridinyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw;
Rwis OCF3, SCF3, CF3, SOCF3 or SO2CF3.
Embodiment DDD. A compound of Embodiment BBB wherein
R2 is H;
R3 is H or halogen;
R4 is selected from U-2 to U-49;
Rv is CpCg alkyl;
R5 is H;
Q is a phenyl, pyridinyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw;
Embodiment EEE. A compound of Embodiment CCC wherein
R3 is halogen;
R4 is selected from U-2, U-3, U-4, U-5, U-7, U-9, U-l 1, U-12, U-13, U-16, U-21, U-25, U26, U-27, U-28, U-29, U-31, U-32, U-35, U-36, U-37, U-44, U-48 and U-49;
R5 is H;
Q is a phenyl, pyridinyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw. .
Embodiment FFF. A compound of Embodiment EEE wherein
R3 is F;
R4 is selected from U-9 and U-44;
Q is a phenyl ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw.
Embodiment GGG. A compound of Embodiment FFF wherein
R4 is selected from the group of U-9.
Embodiment HHH. A compound of Embodiment FFF wherein
R4 is selected from the group of U-44.
Spécifie embodiments include compounds of Formula 1 selected from the group consisting of:
3-Fhioro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2//-l,2,3-triazol-2-yl)pyridine;
3-Chloro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyI]-5-(2//-1,2,3-triazol-2-yl)pyridine;
3-Fluoro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(2//-l,2,3-triazol-2yl)pyridine;
3-Fluoro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2-oxazolyl)pyridine;
3-Fluoro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2//-l,2,3-triazol-2yl)pyridine;
3-Chloro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2//-l,2,3-triazol-2yl)pyridine;
3-Fhioro-4-[fhioro[4-(trifluoromethyl)phenyl]methyl]-5-(2//-l,2,3-triazol-2-yl)pyridine;
3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2-oxazolyl)pyridine;
3-Fluoro-4-[fluoro[4-[(trifluoromethyl)sulfinyl]phenyl]methyl]-5-(2//-l,2,3-triazol-2yl)pyridine;
3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(5-oxazolyl)pyridine;
3-Fhioro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(3-methyl-l,2,4-oxadiazol-5yl)pyridine;
3-Fhjoro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(2//-l,2,3-triazol-2yl)pyridine;
3-ChIoro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(2//-l,2,3-triazol-2yl)pyridine;
3-Bromo-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(227-l,2,3-triazol-2yl)pyridine; and
3-Fluoro-4-[methoxy[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(l,2,4-oxadiazol-3yl)pyridine.
More spécifie embodiments include compounds of Formula l selected from the group consisting of:
3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2//-l,2,3-triazol-2-yl)pyridine
3-Chloro-4-[fhioro[4-(trifluoromethoxy)phenyl]methyl]-5-(2/f-l,2,3-triazol-2-yl)pyridine 3-Fluoro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(2//-l,2,3-triazol-2yl)pyridine
3-Fluoro-4-[fluoro [4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2-oxazolyl)pyridine
3-Fluoro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2/7-1,2,3-triazol-2yl)pyridine
3-Bromo-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2//-l,2,3-triazol-2yl)pyridine
More spécifie embodiments include compounds of Formula 1 selected from the group consisting of:
3-Fhioro-4-[fhioro[4-(trifhioromethoxy)phenyl]methyl]-5-(2Z/-l,2,3-triazol-2-yl)pyridine;
3-Chloro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2Z/-l,2,3-triazol-2-yl)pyridine;
3-Chloro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2//-l,2,3-triazol-2yl)pyridine;
3-Fluoro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(2//-l,2,3-triazol-2yl)pyridine;
3-Fluoro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2-oxazolyl)pyridine;
3-Fluoro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2//-l,2,3-triazol-2yl)pyridine;
3-Bromo-4-[fhioro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2Z/-l,2,3-triazol-2yl)pyridine.
More spécifie embodiments include compounds of Formula 1 selected from the group consisting of:
3-Fluoro-4-[fluoro[4-(trifluoromethyl)phenyl]methyl]-5-(277-l,2,3-triazol-2-yl)pyridine;
3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2-oxazolyl)pyridine;
3-Fluoro-4-[fluoro[4-[(trifluoromethyl)sulfmyl]phenyl]methyl]-5-(2/7-l,2,3-triazol-2yl)pyridine;
3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(5-oxazolyl)pyridine;
3-Fluoro-4-[fluoro [4-(trifluoromethoxy)phenyl]methyl]-5-(3-methyl-1,2,4-oxadiazol-5yl)pyridine;
3-Chloro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(2/7-l,2,3-triazol-2yl)pyridine; and
3-Fluoro-4-[methoxy[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(l,2,4-oxadiazol-3yl)pyridine.
3-Fluoro-4-[methoxy[4-(trifIuoromethoxy)phenyl]methyl]-5-(2A-l,2,3-triazol-2yl)pyridine;
Embodiment Yl. A composition comprising a compound of Formula 1 or any one of the preceding embodiments and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising at least one additional biologically active compound or agent.
Embodiment Y2. The composition of embodiment Yl wherein the at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acephate, acequinocyl, acetamiprid, acrinathrin, afidopyropen, amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, benfuracarb, bensultap, bifenthrin, bifenazate, bistrifluron, borate, bromantraniliprole, buprofezin, carbaryl, carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cycloxaprid, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalodiamide, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dichlorantraniliprole, dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide, flucythrinate, flufenerim, flufenoxuron, flufenoxystrobin, fluensulfone, fluopyram, flupyradifurone, fluvalinate, tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide, heptafluthrin, hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidal soaps, isofenphos, lufenuron, malathion, meperfluthrin, metaflumizone, metaldehyde, methamidophos, methidathion, methiocarb, methomyl, methoprene, methoxychlor, methoxyfenozide, metofluthrin, monocrotophos, monofluorothrin, nicotine, tV-[ 1,1 -dimethyl-2-(methylthio)ethyl]-7-fluoro-2-(3-pyridinyl)-277indazole-4-carboxamide, 7V-[ 1,1 -dimethyl-2-(methylsulfinyl)ethyl]-7-fluoro-2-(3-pyridinyl)-277indazole-4-carboxamide, 7V-[l,l-dimethyl-2-(methylsulfonyl)ethyl]-7-fluoro-2-(3-pyridinyl)-277indazole-4-carboxamide, N-(l-methylcyclopropyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide, 7V-[ 1 -(difluoromethyl)cyclopropyl]-2-(3-pyridinyl)-2/7-indazole-4-carboxamide, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, propargite, protrifenbute, pyflubumide, pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl, pyrifluquinazon, pyriminostrobin, pyriprole, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulprofos, sulfoxaflor, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, tetrachlorantraniliprole, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tioxazafen, tolfenpyrad, tralomethrin, triazamate, trichlorfon, triflumezopyrim, triflumuron, Bacillus thuringiensis delta-endotoxins, entomopathogenic bacteria, entomopathogenic viruses and entomopathogenic fungi.
Embodiment Y3. The composition of embodiment Y2 wherein the at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acetamiprid, acrinathrin, afidopyropen, amitraz, avermectin, azadirachtin, benfuracarb, bensultap, bifenthrin, buprofezin, carbaryl, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zetacypermethrin, cyromazine, deltamethrin, dieldrin, dinotefiiran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenitrothion, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide, flufenoxuron, flufenoxystrobin, fluensulfone, flupiprole, flupyradifurone, fluvalinate, formetanate, fosthiazate, heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, meperfluthrin, metaflumizone, methiocarb, methomyl, methoprene, methoxyfenozide, metofluthrin, monofluorothrin, nitenpyram, nithiazine, novaluron, oxamyl, pyflubumide, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriminostrobin, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide, tetramethrin, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate, triflumezopyrim, triflumuron, Bacillus thuringiensis delta-endotoxins, ail strains of Bacillus thuringiensis and ail strains of nuclear polyhedrosis viruses.
Embodiment Y4. The composition of any one of embodiments Y1-Y3 further comprising a liquid fertilizer.
Embodiment Y5. The composition of Embodiment Y4 wherein the liquid fertilizer is aqueous-based.
Embodiment Y6. A soil drench formulation comprising the composition of any one of embodiments Y1-Y3.
Embodiment Y7. A spray composition comprising the composition of any one of embodiments Y1-Y3 and apropellant.
Embodiment Y8. A bait composition, comprising the composition of any one of embodiments Y1-Y3, one or more food materials, optionally an attractant, and optionally a humectant.
Embodiment Y9. A trap device for controlling an invertebrate pest, comprising: the bait composition of Embodiment Y8 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.
Embodiment Y10. A composition comprising the composition of any of Embodiments Y1-Y3 wherein the composition is a solid composition selected from dusts, powders, granules, pellets, prills, pastilles, tablets, and filled films.
Embodiment Y11. The composition of Embodiment Y10 wherein the composition is water-dispersible or water-soluble.
Embodiment Y12. A liquid or dry formulation comprising the composition of any one of Embodiments Y1-Y3 for use in a drip irrigation System, furrow during planting, handheld sprayer, backpack sprayer, boom sprayer, ground sprayer, aerial application, unmanned aerial vehicle, or a seed treatment.
Embodiment Y13. The liquid or dry formulation of Embodiment Y12 wherein said formulation is sprayed at an ultra-low volume.
Of note is that compounds of this disclosure are characterized by favorable metabolic and/or soil residual patterns and exhibit activity controlling a spectrum of agronomie and nonagronomic invertebrate pests. .
Of particular note, for reasons of invertebrate pest control spectrum and économie importance, protection of agronomie crops from damage or injury caused by invertebrate pests by controlling invertebrate pests are embodiments of the disclosure. Compounds of this disclosure because of their favorable translocation properties or systemicity in plants also protect foliar or other plant parts which are not directly contacted with a compound of Formula 1 or a composition comprising the compound.
Also noteworthy as embodiments of the présent disclosure are compositions comprising a compound of any of the preceding Embodiments, as well as any other embodiments described herein, and any combinations thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said compositions optionally further comprising at least one additional biologically active compound or agent.
Further noteworthy as embodiments of the présent disclosure are compositions for controlling an invertebrate pest 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. Embodiments of the disclosure further include methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of any of the preceding Embodiments (e.g., as a composition described herein).
Embodiments of the disclosure 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 disclosure 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 disclosure also include a spray composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of any of the preceding Embodiments and a propellant. Embodiments of the disclosure further include a bait composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of any of the preceding Embodiments, one or more food materials, optionally an attractant, and optionally a humectant. Embodiments of the disclosure 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 disclosure also include methods for protecting a seed from an invertebrate pest comprising contacting the seed with a biologically effective amount of a compound of any of the preceding Embodiments.
Embodiments of the disclosure also include methods for protecting an animal from an invertebrate parasitic pest comprising administering to the animal a parasiticidally effective amount of a compound of any of the preceding Embodiments.
Embodiments of the disclosure 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, an A-oxide or a sait thereof, (e.g., as a composition described herein), provided that the methods are not methods of medical treatment of a human or animal body by therapy.
This disclosure 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, an A-oxide or a sait thereof, 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.
One or more of the following methods and variations as described in Schemes 1-11 can be used to préparé the compounds of Formula 1. The définitions of R1, R2, R3, R4, R5, A and Q in the compounds of Formulae 1-18 below are as defined above in the Summary of the Disclosure unless otherwise noted. Compounds of Formulae la-ld are varions subsets of the compounds of Formula 1, and ail substituents for Formulae la-ld are as defined above for Formula 1 unless otherwise indicated. Ambient or room température is defined as about 20-25 °C.
As shown in Scheme 1, compounds of Formula la (compounds of Formula 1 wherein R4 is attached to the rest of the molécule through a carbon atom) can be prepared by contacting compounds of Formula 2a wherein X is Cl, Br or I with boronic acids or organotin compounds of Formula 3 in the presence of a palladium catalyst. A wide variety of palladium-containing compounds and complexes are useful as catalysts for the présent method. Examples of palladiumcontaining compounds and complexes useful as catalysts in the method of Scheme 1 include Pd(OAc)2 (palladium(II) acetate), PdCl2 (palladium(II) chloride), PdCl2(PPh3)2 bis(triphenylphosphine)palladium(II) dichloride, Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium(O), Pd(C5H7O2)2 (palladium(II) acetylacetonate) and Pd2(dba)3 tris (dibenzylideneacetone)dipalladium(O). Also as shown in Scheme 1, compounds of Formula lb (compounds of Formula 1 wherein R4 is attached to the rest of the molécule through a nitrogen atom) can be prepared by contacting compounds of Formula 2a (wherein X is Cl, Br or I) with compounds of Formula 4 (a heterocyclic compound with an NH as a ring member wherein the H can be replaced by another functional group during a Chemical reaction) in the presence of a copper catalyst or a palladium catalyst. For recent review articles and books about this type of functional group transformation; see, for example, F. Bellina et al., Synthesis 2004, 15, 24192440; P. Espinet and A. M. Echavarren, Angewandte Chemie, International Edition 2004, 43, 4704-4734; and J. J. Li, G. W. Gribble, editors, Palladium in Heterocyclic Chemistry: A Guide for the Synthetic Chemist. 2000. K. W. Anderson et al., Angewandte Chemie, International Edition 2006, 45, 6523-6527.
Scheme 1
1b wherein R4 is connected to the rest of the compound through a nitrogen atom
As shown in Scheme 2, compounds of Formula 1b can also be prepared by contacting compounds of Formula 2b (wherein X is F or Cl) with compounds of Formula 4 in the presence 5 of a base, such as K.2CO3 or Cs2CO3. A wide variety of known general procedures are reasonably believed to be readily adaptable by one skilled in the art to the method of Scheme 2, for example, see, J. D. Culshaw et al., Synlett 2012, 23, 1816-1820. The method of Scheme 2 is illustrated by Synthesis Example 1, Step C.
Scheme 2
wherein X is F or Cl wherein R4 is connected to the rest of the compound through a nitrogen atom
Altematively, as shown in Scheme 3, compounds of Formula la can be prepared by constructing a heterocyclic ring via compounds of Formula 5 wherein R10 is CN, COCH3, or CHO. The methods to form a heterocyclic ring through these functional groups are known in the literature. A variety of known general procedures are reasonably believed to be readily adaptable by one skilled in the art to the method of Scheme 3, for example, see, World Patent Publication WO 2012/002577; World Patent Publication WO 2012/087938; M. H. Gezginci et al.; J. Med. Chem. 2001, 44, 1560-1563; K. Gobbis, J. Heterocyclic Chem. 2009, 46, 1271-1279. The method of Scheme 3 is illustrated by synthesis Example 2, Step D.
Scheme 3
wherein R10 is CN, COCH3, CHO or any other groups which may proceed similarly to form the desired heterocycles
la wherein R4 is connected to the rest of the compound through a carbon atom
As shown in Scheme 4, a compound of Formula 5 can be prepared by converting the X group in a compound of Formula 6 to the R10 group in a compound of Formula 5 via functional group transformation reactions. A variety of general procedures are well known in the literature, for example, see, M. Hatsuda, M. Seki, Tetrahedron, 2005, 61, 9908-9917; D. Xu et al., Tetrahedron Letters, 2008, 6104-6107; A. Brennfuehrer, et al., Tetrahedron, 2007, 63, 6252-6258. The method of Scheme 4 is illustrated by synthesis Example 2, Step C.
Scheme 4
wherein X is Br or I wherein R10 is CN, COCH3, CHO or any other groups which may proceed similarly to form the desired heterocycles
As shown in Scheme 5, compounds of Formula 6 can be prepared by contacting the corresponding alcohols of Formula 7 with fluorination reagents such as (diethylamino)sulfur 5 trifluoride (DAST) or bis(2-methoxyethyl)aminosulfur trifluoride (Deoxo-Fluor) in haloalkane solvents, such as dichloromethane or chloroform from -78 °C to room température. A general procedure is known in the art, for example, see, Lal, G. S. et al. J. Org. Chem. 1999, 64, 7048. The method of Scheme 5 is illustrated by synthesis Example 1, Step B.
Scheme 5
Fluorination reagent
As shown in Scheme 6, compounds of Formula le (wherein R1 is OR6) can be prepared by reacting corresponding alcohols of Formula 7 with compounds of Formula 8 of R6Br or R6! in the 15 presence of a base. Compounds of Formula ld (wherein R1 is SR6) can be prepared by converting corresponding alcohols of Formula 7 to their corresponding chloride compounds using SOC12, followed by reacting the chloride compounds with thiol compounds of Formula 9 of R6SH. This method is well known in the literature, for example, see, Qingzhong Hu et al. J. Med. Chem. 2010, 53, 5749; World Patent Publication WO 2009/034976. The method of Scheme 6 is ilhistrated by synthesis Example 2, Step B.
Scheme 6
1) R6Br or R6! (8) and a base for le
2) SOC12, then R6SH (9) for Id
R1
R5 le or Id le wherein R1 is OR6
Id wherein R1 is SR6
As shown in Scheme 7, compounds of Formula 7 are readily available from nucleophilic addition of compounds of Formula 11 with the aldéhydes of Formula 10. The nucleophiles of Formula 11 can be generated by varions Chemical approaches. For example, the metal-halogen exchange reaction of a haloaromatic compound QX' (wherein X' is preferred to be Br or I) with nbutyllithium or z-propylmagnesium bromide, typically at a température between about -100 and about -20 °C, can generate the nucleophiles of Formula 11 in situ. A wide variety of general procedures for conducting métal halogen exchange followed by reaction with electrophiles are known in the art and can be readily adapted for the présent method. For related general procedures see, for example, M. Schlosser, Angew. Chem. Int. Ed. 2004, 43,2 and P. Knochel et al., Synthesis, 2002, 565. In addition, the nucleophiles of Formula 11 can be prepared via Grignard reaction of the corresponding bromide or iodide QBr or QI with magnésium. Some of the nucleophiles of Formula 11 are commercially available, for example, 4-tert-butylphenylmagnesium bromide or 4(trifluoromethoxy)phenylmagnesium bromide. Most of the aldéhydes of Formula 10 are commercially available or known compounds in the Chemical literature.
Scheme 7
wherein X is F or Cl
M+Q’
M is Li or MgX'
As shown in Scheme 8, treating compounds of Formula 12 (wherein X is F or Cl) with a base, such as lithium diisopropylamide, 2,2,6,6-tetramethylpiperidinyl magnésium chloride 5 lithium chloride complex etc. in ether solvents, such as THF, diethyl ether or dioxanes at a température between -100 °C to -10 °C will generate the desired anions in situ. By quenching the above anions with aldéhydes of Formula 13, compounds of Formula 7 can be prepared. This method is well known in literature, see for example, R. J. Mattson, et al. J. Org. Chem., 1990, 55, 3410. The method of Scheme 8 is illustrated by synthesis Examples 1 and 2, Step A.
Scheme 8
O
wherein X is F or CI wherein X is F or CI
As shown in Scheme 9, compounds of Formula 7 can also be prepared by réduction of the corresponding carbonyl compounds of Formula 14. By treating compounds of Formula 14 in solvents, such as methanol, éthanol or ethers (such as tetrahydrofuran) with a variety of reducing 15 agents, such as sodium borohydride, borane-dimethylsulfide, compounds of Formula 7 can be prepared. Altematively, the réduction of the carbonyl compounds of Formula 14 can be accomplished by catalytic hydrogénation. Several general procedures of these transformations are known in the art; see, for example, D. Douglas, et al., J. Med. Chem 2009, 52,4694; M. Moriyasu, et al., Synlett 1997, 5, 273.
Scheme 9
reducing agent or catalytic hydrogénation
As shown in Scheme 10, compounds of Formula 14 can be prepared from CN substituted aromatic compounds of Formula 15a (wherein Y is CN) or Weinreb amides of Formula 15b (wherein Y is CONMeOMe). Reactions of compounds ofFormula 16 with compounds ofFormula 15a or 15b can provide carbonyl compounds of Formula 14. Compounds of Formula 16 can be prepared using a similar chemistry which generates the corresponding anions in situ as described in Scheme 8. For related référencés see, for example: U.S. Patent Application Publication US 2008/280891 and Bêla, et al. European J. Org. Chem. 2004 17, 3623-3632. Many of the compounds of Formula 17 and 15 are commercially available or readily available from literature synthetic methods.
Scheme 10
O
15a wherein Y is CN wherein M is Li or MgX 15b wherein Y is CONMe(OMe)
Altematively, as shown in Scheme 11, compounds of Formula 14 can also be prepared from 4-halopyridine or pyrimidine compounds of Formula 17 (wherein Z is Br or I and X is other than Br or I). The palladium-catalyzed cross-coupling reaction of the compounds of Formula 17, carbon monoxide and boronic acids of Formula 18 can provide an alternative way to préparé compounds of Formula 14. Treating a mixture of 4-halopyridine or pyrimidine compounds of Formula 17 and boronic acids of Formula 18 in the presence of palladium catalyst (such as bis(triphenylphosphine)palladium(II) dichloride, or tetrakis(triphenylphosphine)-palladium(0)) with a base (such as potassium carbonate, sodium carbonate or césium carbonate) at a température of about 80 to 150 °C in ethereal solvents (such as tetrahydrofuran or dioxane) under pressurized carbon monoxide atmosphère from 1 to 50 bar will provide the desired carbonyl compounds of Formula 14. A detailed experimental procedure is given in Couve-Bonnair et. al., Tetrahedron Lett. 2001, 42, 3689-3691. Most of the compounds of Formula 17 and boronic acids of Formula 18 are commercially available or readily available from the Chemical literature.
Scheme 11
wherein Z is Br or I;
and X is other than Br or I
HO.
B—Q HOZ
It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula 1 may not be compatible with certain functionalities présent in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in Chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complété the synthesis of compounds of Formula 1. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to préparé the compounds of Formula 1.
One skilled in the art will also recognize that compounds of Formula 1 and the intermediates described herein can be subjected to varions electrophilic, nucleophilic, radical, organometallic, oxidation, and réduction reactions to add substituents or modify existing substituents.
Without further élaboration, it is believed that one skilled in the art using the preceding description can utilize the présent disclosure to its fullest extent. The following Synthesis Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Steps in the following Synthesis Examples illustrate a procedure for each step in an overall synthetic transformation, and the starting material for each step may not hâve necessarily been prepared by a particular préparative run whose procedure is described in other
Examples or Steps. Ambient or room température is defined as about 20-25 °C. Percentages are by weight except for chromatographie solvent mixtures or where otherwise indicated. Parts and percentages for chromatographie solvent mixtures are by volume unless otherwise indicated. MP LC refers to medium pressure liquid chromatography on silica gel. ^HNMR spectra are reported in ppm downfield from tetramethylsilane; “s” means singlet, “d” means doublet, “dd” means doublet of doublets, “ddd” means doublet of doublet of doublets, “t” means triplet, “m” means multiplet, and “br s” means broad singlet. For mass spectral data, the numerical value reported is the molecular weight of the parent molecular ion (M) formed by addition of H+ (molecular weight of 1) to the molécule to give a M+l peak observed by mass spectrometry using atmospheric pressure Chemical ionization (AP+).
Schemes 1 through 11 illustrate methods to préparé compounds of Formula 1 having a variety of substituents. Compounds of Formula 1 having substituents other than those particularly noted for Schemes 1 through 11 can be prepared by general methods known in the art of synthetic organic chemistry, including methods analogous to those described for Schemes 1 to 11.
SYNTHESIS EXAMPLE 1
Préparation of 3 -fhioro-4-[fluoro-[4-(trifluoromethylsulfinyl)phenyl]methyl]-5-(triazol-2yl)pyridine (compound 67)
Step A: Préparation of (3,5-difluoro-4-pyridvl)-r4-(trifluoromethylsulfanyl)phenvl1methanol
To a stirred solution of 3,5-difluoro-pyridine (1.20 g, 10.4 mmol) in THF (20 mL) was added a freshly prepared lithium diisopropylamide solution (11.4 mmol in 10 mL of THF and n-Hexanes) slowly at -20 °C. After stirring for 1 hr at -20 to -10 °C, the reaction mixture was added a solution of 4-(trifluoromethylsulfanyl)benzaldehyde (2.15 g, 10.4 mmol) in THF (10 mL) at -20 °C. After stirring for another 1 hr at -20 to -10 °C, the reaction mixture was quenched by saturated NH4C1 aqueous solution, then diluted with water and extracted with ethyl acetate. The combined organic phases were washed with water and saturated aqueous NaCl solution, dried with anhydrous sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel using hexanes/ethyl acetate as eluent to afford the title product as a pale white solid (1.36 g, 4.2 mmol). 1H NMR (CDCI3) δ 8.34 (s, 2H), 7.66 (d, 2H), 7.48 (d, 2H), 6.29 (s, 1H).
Step B: Préparation of 3,5-difluoro-4-[fluoro-r4-(trifluoromethvlsulfanyl)phenvl1methyl1 pyridine
To a stirred solution of (3,5-difluoro-4-pyridyl)-[4-(trifluoromethylsulfanyl)phenyl] methanol (i.e. the product of Step A) (650 mg, 2.02 mmol) in dichloromethane (25 mL) was added bis(2-methoxyethyl)aminosulfiir trifluoride (0.55 mL, 2.96 mmol) at -78 °C. After stirring for 2 hrs, the reaction mixture was diluted with saturated aqueous NaHCO3 solution slowly and extracted with dichloromethane. The combined organic phases were washed with water and saturated aqueous NaCl solution, dried with anhydrous sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel using hexanes/ethyl acetate (80:20 to 40:60) as eluent to afford the title compound, a compound of the présent disclosure, as a paleyellow oil (490 mg, 1.52 mmol).
1H NMR (CDC13) δ 8.41 (d, 2H), 7.70 (d, 2H), 7.49 (d, 2H), 6.88 (d, 1H).
Step C: Préparation of 3-fluoro-4-rfluoro-r4-(trifluoromethylsulfanyl)phenyl1methyll-5-(triazol2-yDpyridine
A mixture of 3,5-difluoro-4-[fluoro-[4-(trifluoromethylsulfanyl)phenyl]methyl] pyridine (i.e. the product of Step B) (300 mg, 0.93 mmol), 1,2,3-triazole (64 mg, 0.93 mmol) and K2CO3 (205 mg, 1.49 mmol) in DMF (4 mL) was stirred at 100 °C for 2 hrs. Then the reaction mixture was cooled to room température, partitioned between water and ethyl acetate. The organic phase was washed with water and saturated aqueous NaCl solution, dried with anhydrous sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel using hexanes/ethyl acetate as eluent to afford the title product as a white solid (80 mg, 0.22 mmol). 1H NMR (CDC13) δ 8.96 (s, 1H), 8.57 (s, 1H), 7.96 (s, 2H), 7.68 (d, 2H), 7.60 (d, 2H), 7.24 (d, 1H).
Step D: Préparation of 3-fluoro-4-rfluoro-r4-(trifluoromethylsulfinyl)phenyl1methvl1-5-(triazol2-yl)pyridine
To a stirred solution of 3-fluoro-4-[fluoro-[4-(trifluoromethylsulfanyl)phenyl]methyl]-5(triazol-2-yl)pyridine (i.e. the product of Step C) (100 mg, 0.27 mmol) in dichloromethane (3 mL) was added 3-chloroperoxybenzoic acid (91 mg, less than 77% purity) at 0 °C. The reaction mixture was slowly warmed to room température and stirred for 3 hrs. Then the reaction mixture was quenched with aqueous solution of NaHSO3 and partitioned between water and dichloromethane. The organic phase was washed with water and saturated aqueous NaCl solution, dried with anhydrous sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel using hexanes/ethyl acetate as eluent to afford the title product as a colorless sticky oil (30 mg, 0.08 mmol).
Ih NMR (CDC13) δ 9.00 (s, 1H), 8.59 (s, 1H), 7.98 (s, 2H), 7.83 (s, 4H), 7.30 (d, 1H).
SYNTHESIS EXAMPLE 2
Préparation of 3-[5-fluoro-4-[methoxy-[4-(trifhioromethylsulfanyl)phenyl]methyl]-3-pyridyl]1,2,4-oxadiazole (compound 83)
Step A: Préparation of (3-bromo-5-fluoro-4-pvridyl)-r4-(trifluoromethylsulfanyl)phenyll methanol
To a stirred solution of 3-bromo-5-fluoro-pyridine (4.40 g, 25 mmol) in THF (20 mL) was added a freshly prepared lithium diisopropylamide solution (26 mmol in 20 mL of THF and nHexanes) slowly at -20 °C. After stirring for 1 hr at -20 to -10 °C, the reaction mixture was added a solution of 4-(trifluoromethylsulfanyl)benzaldehyde (4.85 g, 23.5 mmol) in THF (10 mL) at -20 °C. After stirring for another 1 hr at -20 to -10 °C, the reaction mixture was quenched with saturated NH4C1 aqueous solution, then diluted with water and extracted with ethyl acetate. The combined organic phases were washed with water and saturated aqueous NaCl solution, dried with anhydrous sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel using hexanes/ethyl acetate as eluent to afford the title product as a pale-yellow oil (6.95 g, 18.2 mmol).
1H NMR (CDCI3) δ 8.56 (s, 1H), 8.36 (s, 1H), 7.65 (d, 2H), 7.47 (d, 2H), 6.39 (d, 1H), 3.66 (d, 1H).
Step B: Préparation of 3-bromo-5-fluoro-4-rmethoxy-r4-(trifluoromethylsulfanvl)phenyl] methyllpyridine
To a stirred solution of (3-bromo-5-fluoro-4-pyridyl)-[4-(trifluoromethylsulfanyl) phenyl]methanol (i.e. the product of Step A) (1.26 g, 3.30 mmol) in dry THF (10 mL) was added sodium hydride (165 mg, 4.12 mmol, 60% in minerai oil) at 0 °C. The resulting mixture was stirred at room température for 1 hr and then treated with methyl iodide (0.24 mL, 3.96 mmol). After stirring at room température for another 1.5 hrs, the reaction mixture was treated with water and extracted with ethyl acetate/hexanes (1:1). The combined organic phases were washed with water and saturated aqueous sodium chloride solution, dried with anhydrous sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel using hexanes/ethyl acetate (90:10 to 60:40) as eluent to afford the title compound as a pale-yellow oil (1.10 g, 2.80 mmol).
1H NMR (CDC13) δ 8.60 (s, 1H), 8.37 (s, 1H), 7.63 (d, 2H), 7.52 (d, 2H), 5.95 (s, 1H), 3.47 (s, 3H).
Step C: Préparation of 5-fluoro-4-rmethoxy-r4-(trifluoromethylsulfanyl)phenyl1methyl] pyridine-3-carbonitrile
A mixture of 3-bromo-5-fluoro-4-[methoxy[4-(trifluoromethylsulfanyl)phenyl]-methyl] pyridine (i.e. the product of Step B) (1.0 g, 2.52 mmol), Zn(CN)2 (325 mg, 2.76 mmol), Pd(PPh3)4 (291 mg, 0.25 mmol) in 7V,7V-dimethylforamide (5 mL) in a vial under nitrogen atmosphère was subjected for a reaction under microwave at 150 °C for 10 min. Then the reaction mixture was partitioned between water and ethyl acetate. The organic layer was washed with water and saturated aqueous sodium chloride solution, dried with anhydrous sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel using hexanes/ethyl acetate (90:10 to 60:40) as eluent to afford the title compound as a yellow oil (0.80 g, 2.42 mmol).
1H NMR (CDCI3) δ 8.72 (s, 1H), 8.63 (s, 1H), 7.67 (d, 2H), 7.59 (d, 2H), 5.79 (s, 1H), 3.50 (s, 3H).
Step D: Préparation of 3-r5-fluoro-4-rmethoxy-r4-(trifluoromethvlsulfanyl)phenyl1methyll-3pyridyll-l,2,4-oxadiazole
A mixture of 5-fluoro-4-[methoxy-[4-(trifluoromethylsulfanyl)phenyl]methyl]pyridine-3carbonitrile (i.e. the product of Step C) (0.27 g, 0.82 mmol), hydroxylamine (0.25 mL, 3.78 mmol, 50% in H2O) in EtOH (5 ml) was stirred at room température for 48 hrs. The reaction mixture was then concentrated under reduced pressure. The residue was added trimethylorthoformate (0.5 mL) and one drop of concentrated hydrochloride acid. Then the mixture was stirred at 80 °C for 1 hr. The reaction mixture was cooled to room température, then partitioned between water and ethyl acetate. The organic layer was washed with water and saturated aqueous sodium chloride solution, dried with anhydrous sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel using hexanes/ethyl acetate (90:10 to 60:40) as eluent to afford the title compound as a pale yellow oil (0.17 g, 0.46 mmol).
1H NMR (CDC13) δ 8.96 (s, 1H), 8.91 (s, 1H), 8.57 (s, 1H), 7.62 (d, 2H), 7.57 (d, 2H), 6.29 (s, 1H), 3.39 (s, 3H).
SYNTHESIS EXAMPLE 3
Préparation of 3-fluoro-4-[(R)-methoxy-[4-(trifluoromethoxy)phenyl]methyl]-5-(triazol-2 yl)pyridine (compound 125)
Step A: Préparation of (3,5-difluoro-4-pvridvl)-r4-(trifluoromethoxy)phenyl~|methanol
To a solution of compound 3,5-difluoro-pyridine (40 g, 0.347 mol, 1.0 eq.) in THF (400 ml) was added LDA2 M in THF (191.3 mL, 0.381 mol, 1.1 eq.) slowly at-78 °C under N2 atmosphère. Then the reaction mixture was stirred for 30 min then added compound 4(trifluoromethoxy)benzaldehyde (72.4 g, 0.381 mol, 1.1 eq.) at -78 °C and stirred for 2h at -78 °C. Reaction monitored by TLC, the reaction mixture was quenched with Sat. Aq NH4CI extracted with EtOAc (3x 500 ml) then dried over anhydrous Na2SO4 and concentrated under reduced pressure. Obtained crude was purified by column chromatography using 100-200 silica gel, eluted with 40% ethyl acetate/ pet ether to afford the title product as an off white semi solid (70 g, 66% yield).
1H NMR (d6-DMSO) δ 8.49 (s, 2H), 7.51 (d, 2H), 7.35 (d, 2H), 6.59 (d, IH), 6.16 (d, IH).
Step B: Préparation of (3,5-difluoro-4-pyridyl)-r4-(trifluoromethoxy)phenyl1methanone
A solution of compound (3,5-difluoro-4-pyridyl)-[4-(trifluoromethoxy)phenyl] methanol (i.e. the product of Step A) (70.0 g, 0.229 mol, 1.0 eq) in dichloromethane (700 ml) was added activated MnO2 (199 g, 2.29 mol, 10 eq.) at rt under N2 atmosphère then stirred for 16 h. Reaction monitored by TLC the reaction mixture was filtered through the celite bed, and washed with dichloromethane (200 mL). The solvent was concentrated under reduced pressure to get crude solid. Obtained crude was purified by column chromatography using 100-200 silica gel, eluted with 30% ethyl acetate/ pet ether to afford the title compound as an off white solid (65 g, 93% yield).
iH NMR (d6-DMSO) δ 8.80 (s, 2H), 8.07 (d, 2H), 7.60 (d, 2H).
Step C: Préparation of r3-fluoro-5-(triazol-2-yl)-4-pyridvl1-r4-(trifluoromethoxy)phenyl1 methanone
To a solution of compound (3,5-difluoro-4-pyridyl)-[4-(trifluoromethoxy)phenyl] methanone (i.e. the product of Step B) (65 g, 0.214 mol, 1.0 eq) in DMF (650 ml) was added K2CO3 (29.6 g, 0.214 mol, 1.0 eq) and 1,2,3-triazole ( 14.8 g, 0.214 mol, 1.0 eq.) at rt under N2 atmosphère. Then the reaction mixture was stirred for 48 h. Reaction monitored by TLC. The reaction mixture was poured into ice cold water (1000 ml) and extracted with EtOAc (3x 300 ml).
Then the organic layer was washed with brine (2x 200 ml) & ice water (200 ml) then dried over anhydrous Na2SÛ4 and concentrated under reduced pressure. Obtained crude was purified by column chromatography using 100-200 silica gel, eluted to provide the title product as an off white solid (19 g, 25% yield).
Ih NMR (d6-DMSO) δ 9.29 ( s, 1H), 8.91 (s,lH), 8.11 (s, 2H), 8.00 (d, 2H), 7.51 (d, 2H).
Step D: Préparation of (R)-r3-fluoro-5-(triazol-2-yl)-4-pyridyl]-r4-(trifluoromethoxv)phenyl] methanol
To a solution of (S)-(-)-a, a-diphenyl-2-pyrrolidinemethanol (2.73 g, 0.011 mol, 0.2 eq) in THF (190 ml) was added B(OMe)3 (12.4 g, 0.012 mmol, 0.22 eq.) at rt then stirred for Ih at rt under N2 atmosphère. Then added borane dimethyl sulfide (6.16 g, 0.081 mol, 1.5 eq.) slowly at 0 °C, meanwhile floating and exothermic was observed. Then added compound [3-fluoro-5-(triazol2-yl)-4-pyridyl]-[4-(trifluoromethoxy)phenyl]methanone (i.e. the product of Step C) (19 g, 0.054 mol, 1.0 eq) (dissolved in THF 30 ml) at 0-5 °C then allowed to rt and stirred for 3 h. Reaction monitored by TLC. After completion of the reaction, it was cooled to 0 °C then reaction mixture was quenched with 2N HCl (80 ml) slowly drop wise meanwhile vigorous gas évolution and exothermic was observed, then extracted with ethyl acetate (3x200 ml), the organic layer was dried over anhydrous Na2SÜ4 and concentrated to get crude. Obtained crude was purified by column chromatography using 100-200 silica gel, eluted with 30% ethyl acetate/ pet ether to provide the title product as colourless liquid (8.2 g, 43% yield). Chiral HPLC analysis with Chiralpak IF (4.6*250mm)5u column indicated the product had 95% ee as the R configuration. The R absolute configuration is assigned according to the literature, see: Moriyasu Masui & Takayuki Shioiri, Synlett, 1997, 273-274.
Step E: Préparation of 3-fluoro-4-r(R)-methoxy-r4-(trifhioromethoxy)phenyllmethyll-5-(triazol2-yl)pyridine
To a solution of (R)-[3-fluoro-5-(triazol-2-yl)-4-pyridyl]-[4-(trifluoromethoxy)phenyl] methanol compound (8.2 g, 0.023 mol, 1.0 eq) in THF was added NaH (1.0 g, 0.046 mol, 2.0 eq) portion wise at 0 °C mean while floating was observed then stirred for 5 min at 0 °C then added Mel (4.93 g, 0.034 mol, 1.5 eq) at 0 °C. Then stirred for 2h at rt. Reaction monitored by TLC. The reaction mixture was poured into ice water (50 ml) and extracted with ethyl acetate (2x 100 ml). Then the organic layer was dried over anhydrous Na2SÜ4 and concentrated under reduced pressure. Obtained crude solid was purified by column chromatography using 100-200 silica gel, eluted with
20% ethyl acetate/ pet ether to get the title product as colourless liquid (6.0 g 70.5% yield). Chiral HPLC analysis indicated the product had 93% ee, [a]25 = -175.6 0 (MeOH, 0.4%).
Ih NMR (d6-DMSO) δ 8.81 ( s, 1H), 8.78 (s,lH), 8.32 (s, 2H), 7.51 (d, 2H), 7.37 (d, 2H), 5.66 (s, 1H), 3.21 (s, 3H).
By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 42N can be prepared. The following abbreviations are used in the Tables which follow: t means tertiary, 5 means secondary, n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, z-Pr means isopropyl, Bu means butyl, 10 Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, S Et means ethylthio, -CN means cyano, Ph means phenyl, Py means pyridinyl, -NO2 means nitro, TMS means trimethylsilyl, S(O)Me means methylsulfînyl, and S(O)2Me means methylsulfonyl.
Fragments Q-l through Q-19 shown below are referred to in Tables IA to 981. The 15 structures of fragments Q-l through Q-19 are illustrated in Exhibit 3. The wavy line dénotés the attachment point of the fragment to the remainder of the molécule.
Exhibit 3
Q-16
Q-17
Q-18
F
Q-19
Tables 1A-42A pertain to the structure shown below.
R1
TABLE IA
R1 is F, A is CH, R2 is H and R5 is H.
Q 4-chlorophenyl 4-bromophenyl 4-iodophenyl 4-nitrophenyl 4-cyanophenyl 4-(CF3)phenyl 4-(OCF3)phenyl 4-(.s-Bu)phenyl 4-(7-Bu)phenyl 4-(CMe2CH2CH3)phenyl 4-(S-z-Pr)phenyl 4-(SCH2CF3)phenyl
Q 3-(CF3)phenyl 3-(OCF3)phenyl 3-(.s-Bu)phenyl 3-(7-Bu)phenyl 3-(CMe2CH2CH3)phenyl 3-(S-z-Pr)phenyl 3-(SCH2CF3)phenyl 3-(CF(CF3)2)phenyl 2-F, 4-(Z-Bu)phenyl 2-C1,4-(Z-Bu)phenyl 2-Me, 4-(/-Bu)phenyl
3-F, 4-(/-Bu)phenyl
Q
3-C1,4-(CF3)phenyl
3-Br, 4-(CF3)phenyl
3-Me, 4-(CF3)phenyl
2,6-diF, 4-(CF3)phenyl
2,6-diCl, 4-(CF3)phenyl 2-F, 4-(OCF3)phenyl 2-C1,4-(OCF3)phenyl 2-Me, 4-(OCF3)phenyl
3-F, 4-(OCF3)phenyl 3-C1, 4-(OCF3)phenyl 3-Br, 4-(OCF3)phenyl 3-Me, 4-(OCF3)phenyl
Q Q Q
4-(SCHF2)phenyl 4-(S(O)CHF2)phenyl 4-(SO2CHF2)phenyl 4-(CF(CF3)2)phenyl 3-chlorophenyl 3-bromophenyl 3-iodophenyl 3-nitrophenyl 3-cyanophenyl 4-(SCF3)phenyl 4-(S(O)CF3)phenyl 4-(SO2CF3)phenyl 4-(CF2CF3)phenyl 4-(CF2CF2CF3)phenyl 4-(OCF2CF3)phenyl 2-F, 4-(SCF3)phenyl 2-C1,4-(SCF3)phenyl 2-Me, 4-(SCF3)phenyl 3-F, 4-(SCF3)phenyl 3-C1,4-(SCF3)phenyl 3-Br, 4-(SCF3)phenyl 3-Me, 4-(SCF3)phenyl 2,6-diF, 4-(SCF3)phenyl 2,6-diCl, 4-(SCF3)phenyl 3-C1,4-(i-Bu)phenyl 3-Br, 4-(Z-Bu)phenyl 3-Me, 4-(/-Bu)phenyl 2,6-diF, 4-(/-Bu)phenyl 2,6-diCl, 4-(/-Bu)phenyl ' 2-F, 4-(CF3)phenyI 2-C1,4-(CF3)phenyl 2-Me, 4-(CF3)phenyl 3-(SCF3)phenyl 3-(S(O)CF3)phenyl 3-(SO2CF3)phenyl 3-(CF2CF3)phenyl 3-(CF2CF2CF3)phenyl 3-(OCF2CF3)phenyl 2-F, 4-(OCF2CF3)phenyl 2-Cl, 4-(OCF2CF3)phenyl 2-Me, 4-(OCF2CF3)phenyl 3-F, 4-(OCF2CF3)phenyl 3-C1,4-(OCF2CF3)phenyl 3-Br, 4-(OCF2CF3)phenyl 3-Me, 4-(OCF2CF3)phenyl 2,6-diF, 4-(OCF2CF3)phenyl 2,6-diCl, 4-(OCF2CF3)phenyl 3-F, 4-(CF3)phenyl 2,6-diF, 4-(OCF3)phenyl 2,6-diCl, 4-(OCF3)phenyl 2-F, 4-(CF2CF3)phenyl 2-C1,4-(CF2CF3)phenyl 2-Me, 4-(CF2CF3)phenyl 3-F, 4-(CF2CF3)phenyl 3-C1, 4-(CF2CF3)phenyl 3-Br, 4-(CF2CF3)phenyl 3-Me, 4-(CF2CF3)phenyl Q-l Q-2 Q-3 Q-4 Q-5 Q-6 Q-7 Q-8 Q-9 Q-10 Q-ll Q-12 Q-13 Q-14 Q-15 . Q-16 Q-17 Q-18 Q-19
The présent disclosure also includes Tables 2A through 42A, each of which is constructed the same as Table 1A above except that the row heading in Table 1A (i.e. “A is CH, R4 is H and R5 is H.”) below the Markush structure is replaced with the respective row heading shown below.
For example, in Table 2A the row heading is “R1 is F, A is CF, R4 is H and R5 is H, and Q is as defined in Table IA above. Thus, the first entry in Table 2A specifically discloses 4-((4chlorophenyl)-fluoro-methyl] -3 -fluoro-5-(triazol-2-yl) pyridine.
Table Table Headings Table Table Headings
2A RI is F, A is CF 23A RI is OCH3, A is C-z-Pr
3A RI is F, A is CCI 24A RI is OCH3, A is C-c-Pr
4A RI is F, A is CBr 25A RI is OCH3, A is C-CF3
5A RI is F, A is CI 26A RI is OCH3, A is C-OMe
6A RI is F, A is CMe 27A RI is OCH3, A is C-OEt
7A RI is F, A is CEt 28A RI is OCH3, A is N
8A RI is F, A is C-n-Pr 29A RI is SCH3, A is CH
9A RI is F, A is C-z-Pr 30A RI is SCH3, A is CF
10A RI is F, A is C-c-Pr 31A RI is SCH3, A is CCI
HA RI is F, A is CCF3 32A RI is SCH3, A is CBr
12A RI is F, A is COMe 33A RI is SCH3, A is CI
13A RI is F, A is C-OEt 34A Ri is SCH3, A is CMe
14A RI is F, A is N 35A RI is SCH3, A is CEt
15A RI is OCH3, A is CH 36A RI is SCH3, A is C-n-Pr
16A RI is OCH3, A is CF 37A RI is SCH3, A is C-z-Pr
17A RI is OCH3, A is CCI 38A RI is SCH3, A is C-c-Pr
18A RI is OCH3, A is CBr 39A RI is SCH3, A is C-CF3
19A RI is OCH3, A is CI 40A RI is SCH3, A is C-OMe
20A RI is OCH3, A is CMe 41A RI is SCH3, A is C-OEt
21A RI is OCH3, A is CEt 42A RI is SCH3j A is N
22A RI is OCH3, A is C-n-Pr
TABLE IB
Table IB is identical to Table 1 A, except that the Chemical structure in the Table IB heading is replaced with the following structure:
R1
For example, the first compound in Table IB is the structure shown immediately above wherein R1 is F, A is CH, R2 is H, R5 is H, and Q is 4-chlorophenyl.
TABLES 2B-42B
Tables 2B through 42B are constructed in a similar manner as Tables 2A through 42A.
TABLE IC
Table IC is identical to Table 1 A, except that the Chemical structure in the Table IB heading is replaced with the following structure:
R1
For example, the first compound in Table IC is the structure shown immediately above wherein R1 is F, A is CH, R2 is H, R5 is H, and Q is 4-chlorophenyl.
TABLES 2C-42C
Tables 2C through 42C are constructed in a similar manner as Tables 2A through 42A.
TABLE ID
Table ID is identical to Table 1 A, except that the Chemical structure in the Table ID heading is replaced with the following structure:
For example, the first compound in Table ID is the structure shown immediately above wherein R1 is F, A is CH, R2 is H, R5 is H, and Q is 4-chlorophenyl.
TABLES 2D-42D
Tables 2D through 42D are constructed in a similar manner as Tables 2A through 42A.
TABLE 1E
Table 1E is identical to Table 1 A, except that the Chemical structure in the Table 1E heading is replaced with the following structure:
For example, the First compound in Table 1D is the structure shown immediately above wherein R1 is F, A is CH, R2 is H, R5 is H, and Q is 4-chlorophenyl.
TABLES 2E-42E
Tables 2E through 42E are constructed in a similar manner as Tables 2A through 42A.
TABLE 1F
Table 1F is identical to Table 1 A, except that the Chemical structure in the Table 1F heading is replaced with the following structure:
For example, the first compound in Table 1F is the structure shown immediately above wherein R1 is F, A is CH, R2 is H, R5 is H, and Q is 4-chlorophenyl.
TABLES 2F-42F
Tables 2F through 42F are constructed in a similar manner as Tables 2A through 42A.
TABLE IG
Table IG is identical to Table 1 A, except that the Chemical structure in the Table IG heading is replaced with the foliowing structure:
For example, the first compound in Table IG is the structure shown immediately above wherein R1 is F, A is CH, R2 is H, R5 is H, and Q is 4-chlorophenyl.
TABLES 2G-42G
Tables 2G through 42G are constructed in a similar manner as Tables 2A through 42A.
TABLE 1H
Table 1H is identical to Table 1 A, except that the Chemical structure in the Table 1H heading is replaced with the foliowing structure:
For example, the first compound in Table 1H is the structure shown immediately above wherein R1 is F, A is CH, R2 is H, R5 is H, and Q is 4-chlorophenyl.
TABLES 2H-42H
Tables 2H through 42H are constructed in a similar manner as Tables 2A through 42A.
TABLE II
Table II is identical to Table 1 A, except that the Chemical structure in the Table 1H heading is replaced with the following structure:
For example, the first compound in Table II is the structure shown immediately above wherein R1 is F, A is CH, R2 is H, R5 is H, and Q is 4-chlorophenyl.
TABLES 21-421
Tables 21 through 421 are constructed in a similar manner as Tables 2A through 42A.
TABLE U
Table 1J is identical to Table 1 A, except that the Chemical structure in the Table 1J heading is replaced with the following structure:
For example, the first compound in Table U is the structure shown immediately above wherein R1 is F, A is CH, R2 is H, R5 is H, and Q is 4-chlorophenyl.
TABLES 2J-42J
Tables 2J through 42J are constructed in a similar manner as Tables 2A through 42A.
TABLE 1K
Table 1K is identical to Table IA, except that the Chemical structure in the Table 1K heading is replaced with the following structure:
R1
For example, the first compound in Table 1K is the structure shown immediately above wherein R1 is F, A is CH, R2 is H, R5 is H, and Q is 4-chlorophenyl.
TABLES 2K-42K
Tables 2K through 42K are constructed in a similar manner as Tables 2A through 42A.
TABLE IL
Table IL is identical to Table 1 A, except that the Chemical structure in the Table IL heading is replaced with the following structure:
For example, the first compound in Table IL is the structure shown immediately above wherein R1 is F, A is CH, R2 is H, R5 is H, and Q is 4-chlorophenyl.
TABLES 2L-42L
Tables 2L through 42L are constructed in a similar manner as Tables 2A through 42A.
TABLE IM
Table IM is identical to Table 1 A, except that the Chemical structure in the Table IM heading is replaced with the following structure:
For example, the first compound in Table IM is the structure shown immediately above wherein R1 is F, A is CH, R2 is H, R5 is H, and Q is 4-chlorophenyl.
TABLES 2M-42M
Tables 2M through 42M are constructed in a similar manner as Tables 2A through 42A.
TABLE IN
Table IN is identical to Table 1 A, except that the Chemical structure in the Table IN heading is replaced with the following structure:
For example, the first compound in Table IN is the structure shown immediately above wherein RI is F, A is CH, R2 is H, R5 is H, and Q is 4-chlorophenyl.
TABLES 2N-42N
Tables 2N through 42N are constructed in a similar manner as Tables 2A through 42A.
A compound of this disclosure will generally be used as an invertebrate pest control active ingrédient in a composition, i.e. formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serves as a carrier. The formulation or composition ingrédients are selected to be consistent with the physical properties of the active ingrédient, mode of application and environmental factors such as soil type, moisture and température.
Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrâtes), suspensions, émulsions (including microemulsions, oil in water émulsions, flowable concentrâtes and/or suspoemulsions) and the like, which optionally can be thickened into gels. The general types of aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated émulsion, microemulsion, oil in water émulsion, flowable concentrate and suspoemulsion. The general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.
The general types of solid compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, which can be water-dispersible (“wettable”) or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. Active ingrédient can be (micro)encapsulated and further formed into a suspension or solid formulation; altematively, the entire formulation of active ingrédient can be encapsulated (or “overcoated”). Encapsulation can control or delay release of the active ingrédient. An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.
Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water, but occasionally another suitable medium like an aromatic or paraffinic hydrocarbon or vegetable oil. Spray volumes can range from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation Systems or metered into the furrow during planting. Liquid and solid formulations can be applied onto seeds of crops and other désirable végétation as seed treatments before planting to protect developing roots and other subterranean plant parts and/or foliage through systemic uptake.
The formulations will typically contain effective amounts of active ingrédient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
Weight Percent
Active Ingrédient Diluent Surfactant
Water-Dispersible and Watersoluble Granules, Tablets and Powders 0.001-90 0-99.999 0-15
Oil Dispersions, Suspensions, Emulsions, Solutions (including Emulsifiable Concentrâtes) 1-50 40-99 0-50
Dusts 1-25 70-99 0-5
Granules and Pellets 0.001-99 5-99.999 0-15
High Strength Compositions 90-99 0-10 0-2
Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook 5 of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.
Liquid diluents include, for example, water, A,7V-dirnethylalkanamides (e.g.,
7V,N-dimethylfonnamide), limonene, dimethyl sulfoxide, À-alkylpyrrolidones (e.g.,
7V-methylpyrrolidinone), alkyl phosphates (e.g., triethylphosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylène 10 carbonate, paraffins (e.g., white minerai oils, normal paraffms, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycérine, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acétates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobomyl acetate, other esters such 15 as alkylated lactate esters, dibasic esters alkyl and aryl benzoates, γ-butyrolactone, and alcohols, which can be linear, branched, saturated or unsaturated, such as methanol, éthanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol and benzyl alcohol. Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C6-C22), such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
The solid and liquid compositions of the présent disclosure often include one or more surfactants. When added to a liquid, surfactants (also known as “surface-active agents”) generally modify, most often reduce, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilie groups in a surfactant molécule, surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.
Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful for the présent compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylène oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycérides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phénol ethoxylates and dodecyl phénol ethoxylates (prepared from the phénols and ethylene oxide, propylene oxide, butylène oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenol (including those prepared from ethylene oxide, propylene oxide, butylène oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based dérivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters and polyethoxylated glycerol fatty acid esters; other sorbitan dérivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, graft or comb polymers and star polymers; polyethylene glycols (pegs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar-derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.
Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate dérivatives; lignin and lignin dérivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phénol ethoxylates; protein-based surfactants; sarcosine dérivatives; styryl phénol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides such as vVJV-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkyl naphthalene; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their dérivatives such as dialkyl sulfosuccinate salts.
Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylène oxide or mixtures thereof); amine salts such as amine acétates and diamine salts; quatemary ammonium salts such as quatemary salts, ethoxylated quatemary salts and diquatemary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.
Also useful for the présent compositions are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon ’s Emulsifiers and Détergents, annual American and International Editions published by McCutcheon’s Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Détergents, Seventh Edition, John Wiley and Sons, New York, 1987.
Compositions of this disclosure may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants). Such formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sédimentation of active ingrédients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobiais), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formera or stickers), évaporation (évaporation retardants), and other formulation attributes. Film formers include, for example, polyvinyl acétates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of formulation auxiliaires and additives include those listed in McCutcheon’s Volume 2: Functional Materials, annual International and North American éditions published by McCutcheon’s Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222.
The compound of Formula 1 and any other active ingrédients are typically incorporated into the présent compositions by dissolving the active ingrédient in a solvent or by grinding in a liquid or dry diluent. Solutions, including emulsifiable concentrâtes, can be prepared by simply mixing the ingrédients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water. Active ingrédient slurries, with particle diameters of up to 2,000 pm can be wet milled using media mills to obtain particles with average diameters below 3 pm. Aqueous slurries can be made into finished suspension concentrâtes (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 pm range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomération techniques. See Browning, “Agglomération”, Chemical Engineering, December 4, 1967, pp 147—48, Perry’s Chemical Engineer’s Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
For further informationregarding the art of formulation, seeT. S. Woods, “The Formulator’s Toolbox - Product Forms for Modem Agriculture” in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10X1; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8th Ed., Blackwell
Scientific Publications, Oxford, 1989; and Developments in formulation technology, P JB Publications, Richmond, UK, 2000.
In the following Examples, ail formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Tables A-B. Without further élaboration, it is believed that 5 one skilled in the art using the preceding description can utilize the présent disclosure to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except where otherwise indicated.
Example A High Strength Concentrate compound 8 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%
Example B Wettable Powder compound 14 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%
Example C
Granule compound 19 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; 90.0%
U.S.S. No. 25-50 sieves) Example D Extruded Pellet compound 78 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%
Example E
Emulsifiable Concentrate compound 3 10.0% polyoxyethylene sorbitol hexoleate 20.0%
C6-Cio fatty acid methyl ester 70.0%
Example F
Microemulsion compound 86 5.0% polyvinylpyrrolidone-vinyl acetate copolymer 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water 20.0%
Example G
Seed Treatment compound 20 20.00% polyvinylpyrrolidone-vinyl acetate copolymer 5.00% montan acid wax 5.00% calcium ligninsulfonate 1.00% polyoxyethylene/polyoxypropylene block copolymers 1.00% stearyl alcohol (POE 20) 2.00% polyorganosilane 0.20% colorant red dye 0.05% water 65.75%
Example H
Fertilizer Stick compound 32 2.5% pyrrolidone-styrene copolymer 4.8% tristyrylphenyl 16-ethoxylate 2.3% talc 0.8% corn starch 5.0% slow-release fertilizer 36.0% kaolin 38.0% water 10.6% η
Example I
Suspension Concentrate compound 67 35% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1%
1,2-benzisothiazolin-3-one 0.1 % water 53.7%
Example J
Emulsion in Water compound 34 10.0% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1%
1,2-benzisothiazolin-3-one 0.1 % aromatic petroleum based hydrocarbon 20.0 water 58.7%
Example K
Oil Dispersion compound 39 25% polyoxyethylene sorbitol hexaoleate 15% organically modified bentonite clay 2.5% fatty acid methyl ester 57.5%
Example L
Suspo émulsion compound 16 10.0% imidacloprid 5.0%
butyl polyoxyethylene/polypropylene block copolymer 4.0%
stearic acid/polyethylene glycol copolymer 1.0%
styrene acrylic polymer 1.0%
xanthan gum 0.1%
propylene glycol 5.0%
silicone based defoamer 0.1%
1,2-benzisothiazolin-3 -one 0.1%
aromatic petroleum based hydrocarbon 20.0%
water 53.7%
Compounds of this disclosure exhibit activity against a wide spectrum of invertebrate pests. These pests include invertebrates inhabiting a variety of environments such as, for example, plant foliage, roots, soil, harvested crops or other foodstuffs, building structures or animal integuments. These pests include, for example, invertebrates feeding on foliage (including leaves, stems, flowers and fruits), seeds, wood, textile fibers or animal blood or tissues, and thereby causing injury or damage to, for example, growing or stored agronomie crops, forests, greenhouse crops, omamentals, nursery crops, stored foodstuffs or fiber products, or houses or other structures or their contents, or being harmful to animal health or public health. Those skilled in the art will appreciate that not ail compounds are equally effective against ail growth stages of ail pests.
These présent compounds and compositions are thus useful agronomically for protecting field crops from phytophagous invertebrate pests, and also nonagronomically for protecting other horticultural crops and plants from phytophagous invertebrate pests. This utility includes protecting crops and other plants (i.e. both agronomie and nonagronomic) that contain genetic material introduced by genetic engineering (i.e. transgenic) or modified by mutagenesis to provide advantageous traits. Examples of such traits include tolérance to herbicides, résistance to phytophagous pests (e.g., insects, mites, aphids, spiders, nematodes, snails, plant-pathogenic fungi, bacteria and viruses), improved plant growth, increased tolérance of adverse growing conditions such as high or low températures, low or high soil moisture, and high salinity, increased flowering or fruiting, greater harvest yields, more rapid maturation, higher quality and/or nutritional value of the harvested product, or improved storage or process properties of the harvested products. Transgenic plants can be modified to express multiple traits. Examples of plants containing traits provided by genetic engineering or mutagenesis include varieties of corn, cotton, soybean and potato expressing an insecticidal Bacillus thuringiensis toxin such as YIELD GARD®, KNOCKOUT®, STARLINK®, BOLLGARD®, NuCOTN® and NEWLEAF®,
INVICTA RR2 PRO™, and herbicide-tolerant varieties of corn, cotton, soybean and rapeseed such as ROUNDUP READY®, LIBERTY LINK®, IMI®, STS® and CLEARFIELD®, as well as crops expressing /V-acetyltransferase (GAT) to provide résistance to glyphosate herbicide, or crops containing the HRA gene providing résistance to herbicides inhibiting acetolactate synthase (ALS). The présent compounds and compositions may exhibit enhanced effects with traits introduced by genetic engineering or modified by mutagenesis, thus enhancing phenotypic expression or effectiveness of the traits or increasing the invertebrate pest control effectiveness of the présent compounds and compositions. In particular, the présent compounds and compositions may exhibit enhanced effects with the phenotypic expression of proteins or other natural products toxic to invertebrate pests to provide greater-than-additive control of these pests.
Compositions of this disclosure can also optionally comprise plant nutrients, e.g., a fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium, magnésium, iron, copper, boron, manganèse, zinc, and molybdenum. Of note are compositions comprising at least one fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium and magnésium. Compositions of the présent disclosure which further comprise at least one plant nutrient can be in the form of liquids or solids. Of note are solid formulations in the form of granules, small sticks or tablets. Solid formulations comprising a fertilizer composition can be prepared by mixing the compound or composition of the présent disclosure with the fertilizer composition together with formulating ingrédients and then preparing the formulation by methods such as granulation or extrusion. Altematively solid formulations can be prepared by spraying a solution or suspension of a compound or composition of the présent disclosure in a volatile solvent onto a previous prepared fertilizer composition in the form of dimensionally stable mixtures, e.g., granules, small sticks or tablets, and then evaporating the solvent.
Nonagronomic uses refer to invertebrate pest control in the areas other than fields of crop plants. Nonagronomic uses of the présent compounds and compositions include control of invertebrate pests in stored grains, beans and other foodstuffs, and in textiles such as clothing and carpets. Nonagronomic uses of the présent compounds and compositions also include invertebrate pest control in omamental plants, forests, in yards, along roadsides and railroad rights of way, and on turf such as lawns, golf courses and pastures. Nonagronomic uses of the présent compounds and compositions also include invertebrate pest control in houses and other buildings which may be occupied by humans and/or companion, farm, ranch, zoo or other animais. Nonagronomic uses of the présent compounds and compositions also include the control of pests such as termites that can damage wood or other structural materials used in buildings.
Nonagronomic uses of the présent compounds and compositions also include protecting human and animal health by controlling invertebrate pests that are parasitic or transmit infectious diseases. The controlling of animal parasites includes controlling extemal parasites that are parasitic to the surface of the body of the host animal (e.g., shoulders, armpits, abdomen, inner part of the thighs) and internai parasites that are parasitic to the inside of the body of the host animal (e.g., stomach, intestine, lung, veins, under the skin, lymphatic tissue). Extemal parasitic or disease transmitting pests include, for example, chiggers, ticks, lice, mosquitoes, flies, mites and fleas. Internai parasites include heartworms, hookworms and helminths. Compounds and compositions of the présent disclosure are suitable for systemic and/or non-systemic control of infestation or infection by parasites on animais. Compounds and compositions of the présent disclosure are particularly suitable for combating extemal parasitic or disease transmitting pests. Compounds and compositions of the présent disclosure are suitable for combating parasites that infest agricultural working animais, such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalos, rabbits, hens, turkeys, ducks, geese and bees; pet animais and domestic animais such as dogs, cats, pet birds and aquarium fish; as well as so-called experimental animais, such as hamsters, guinea pigs, rats and mice. By combating these parasites, fatalities and performance réduction (in ternis of méat, milk, wool, skins, eggs, honey, etc.) are reduced, so that applying a composition comprising a compound of the présent disclosure allows more économie and simple husbandry of animais. ·
Examples of agronomie or nonagronomic invertebrate pests include eggs, larvae and adults of the order Lepidoptera, such as armyworms, cutworms, loopers, and heliothines in the family Noctuidae (e.g., pink stem borer (Sesamia inferens Walker), corn stalk borer (Sesamia nonagrioides Lefebvre), Southern armyworm (Spodoptera eridania Cramer), fall armyworm (Spodoptera frugiperda J. E. Smith), beet armyworm {Spodoptera exigua Hübner), cotton leafworm (Spodoptera littoralis Boisduval), yellowstriped armyworm (Spodoptera ornithogalli Guenée), black cutworm (Agrotis ipsilon Hufhagel), velvetbean Caterpillar (Anticarsia gemmatalis Hübner), green fruitworm (Lithophane antennata Walker), cabbage armyworm (Barathra brassicae Linnaeus), soybean looper (Pseudoplusia includens Walker), cabbage looper (Trichoplusia ni Hübner), tobacco budworm (Heliothis virescens Fabricius)); borers, casebearers, webworms, coneworms, cabbageworms and skeletonizers from the family Pyralidae (e.g., European corn borer (Ostrinia nubilalis Hübner), navel orangeworm (Amyelois transitella Walker), corn root webworm (Crambus caliginosellus Clemens), sod webworms (Pyralidae: Crambinaé) such as sod worm (Herpetogramma licarsisalis Walker), sugarcane stem borer (Chilo infuscatellus Snellen), tomato small borer (Neoleucinodes elegantalis Guenée), green leafroller {Cnaphalocrocis medinalis Guenée), grape leaffolder {Desmia funeralis Hübner), pickleworm {Diaphania nitidalis Stoll), cabbage center grub {Hellula hydralis Guenée), yellow stem borer (Scirpophaga incertidas Walker), white stem borer {Scirpophaga innotata Walker), top shoot borer {Scirpophaga nivella Fabricius), dark-headed rice borer {Chilo polychrysus Meyrick), striped riceborer {Chilo suppressalis Walker), cabbage cluster Caterpillar {Crocidolomia binotalis Zeller)); leafrollers, budworms, seed worms, and fruit worms in the family Tortricidae (e.g., codling moth {Cydia pomonella Linnaeus), grape berry moth {Paralobesia viteana Clemens), oriental fruit moth {Grapholita molesta Busck), citrus false codling moth {Cryptophlebia leucotreta Meyrick), citrus borer {Gymnandrosoma aurantianum Lima), redbanded leafroller {Argyrotaenia velutinana Walker), obliquebanded leafroller {Choristoneura rosaceana Harris), light brown apple moth {Epiphyas postvittana Walker), European grape berry moth {Eupoecilia ambiguella Hübner), apple bud moth {Pandemis pyrusana Kearfott), omnivorous leafroller {Platynota stultana Walsingham), barred fruit-tree tortrix {Pandemis cerasana Hübner), apple brown tortrix {Pandemis heparana Denis & Schiffermüller)); and many other economically important lepidoptera (e.g., diamondback moth {Plutella xylostella Linnaeus), pink bollworm {Pectinophora gossypiella Saunders), gypsy moth {Lymantria dispar Linnaeus), peach fruit borer {Carposina niponensis Walsingham), peach twig borer {Anarsia lineatella Zeller), potato tuberworm {Phthorimaea operculella Zeller), spotted teniform leafininer {Phyllonorycter blancardella Fabricius), Asiatic apple leafininer {Lithocolletis ringoniella Matsumura), rice leaffolder {Lerodea eufala Edwards), apple leafininer {Leucoptera scitella Zeller)); eggs, nymphs and adults of the order Blattodea including cockroaches from the families Blattellidae and Blattidae (e.g., oriental cockroach {Blatta orientalis Linnaeus), Asian cockroach {Blatella asahinai Mizukubo), German cockroach {Blattella germanica Linnaeus), brownbanded cockroach {Supella longipalpa Fabricius), American cockroach {Periplaneta americana Linnaeus), brown cockroach {Periplaneta brunnea Burmeister), Madeira cockroach {Leucophaea maderae Fabricius)), smoky brown cockroach {Periplaneta fuliginosa Serville), Australian Cockroach {Periplaneta australasiae Fabr.), lobster cockroach {Nauphoeta cinerea Olivier) and smooth cockroach {Symploce pallens Stephens)); eggs, foliar feeding, fruit feeding, root feeding, seed feeding and vesicular tissue feeding larvae and adults of the order Coleoptera including weevils from the families Anthribidae, Bruchidae, and Curculionidae (e.g., boll weevil {Anthonomus grandis Boheman), rice water weevil {Lissorhoptrus oryzophilus Kuschel), granary weevil {Sitophilus granarius Linnaeus), rice weevil {Sitophilus oryzae Linnaeus)), annual bluegrass weevil {Listronotus maculicollis Dietz), bluegrass billbug {Sphenophorus parvulus Gyllenhal), hunting billbug {Sphenophorus venatus vestitus Chittenden), Rocky Mountain billbug {Sphenophorus cicatristriatus Fahraeus)); flea beetles, cucumber beetles, rootworms, leaf beetles, potato beetles, and leafininers in the family Chrysomelidae (e.g., Colorado potato beetle (Leptinotarsa decemlineata Say), western corn rootworm (Diabrotica virgifera LeConte)); chafers and other beetles from the family Scarabaeidae (e.g., Japanese beetle (Popillia japonica Newman), oriental beetle (Anomala orientalis Waterhouse, northem masked chafer (Cyclocephala borealis Arrow), Southern masked chafer (Cyclocephcda immaculata Olivier or C. lurida Bland), dung beetle and white grub (Aphodius spp.), black turfgrass ataenius (Ataenius spretulus Haldeman), green June beetle (Cotinis nitida Linnaeus), Asiatic garden beetle (Maladera castanea Arrow), May/June beetles (Phyllophaga spp.) and European chafer (Rhizotrogus majalis Razoumowsky)); carpet beetles from the family Dermestidae; wireworms from the family Elateridae; bark beetles from the family Scolytidae and flour beetles from the family Tenebrionidae.
In addition, agronomie and nonagronomic pests include: eggs, adults and larvae of the order Dermaptera including earwigs from the family Forficulidae (e.g., European earwig (Forficula auricularia Linnaeus), black earwig (Chelisoches morio Fabricius)); eggs, immatures, adults and nymphs of the order Hemiptera such as, plant bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g. Empoasca spp.) from the family Cicadellidae, bed bugs (e.g., Cimex lectularius Linnaeus) from the family Cimicidae, planthoppers from the families Fulgoridae and Delphacidae, treehoppers from the family Membracidae, psyllids from the families Liviidae, Psyllidae, and Triozidae, whiteflies from the family Aleyrodidae, aphids from the family Aphididae, phylloxéra from the family Phylloxeridae, mealybugs from the family Pseudococcidae, scales from the families Coccidae, Diaspididae and Margarodidae, lace bugs from the family Tingidae, stink bugs from the family Pentatomidae, chinch bugs (e.g., hairy chinch bug (Blissus leucopterus hirtus Montandon) and Southern chinch bug (Blissus insularis Barber)) and other seed bugs from the family Lygaeidae, spittlebugs from the family Cercopidae squash bugs from the family Coreidae, and red bugs and cotton stainers from the family Pyrrhocoridae.
Agronomie and nonagronomic pests also include : eggs, larvae, nymphs and adults of the order Acari (mites) such as spider mites and red mites in the family Tetranychidae (e.g., European red mite (Panonychus ulmi Koch), twospotted spider mite (Tetranychus urticae Koch), McDaniel spider mite (Tetranychus medanieli McGregor)); fiat mites in the family Tenuipalpidae (e.g., citrus fiat mite (Brevipalpus lewisi McGregor)); rust and bud mites in the family Eriophyidae and other foliar feeding mites and mites important in human and animal health, i.e. dust mites in the family Epidermoptidae, follicle mites in the family Demodecidae, grain mites in the family Glycyphagidae; ticks in the family Ixodidae, commonly known as hard ticks (e.g., deer tick (Ixodes scapularis Say), Australian paralysis tick (Ixodes holocyclus Neumann), American dog tick (Dermacentor variabilis Say), lone star tick (Amblyomma americanum Linnaeus)) and ticks in the family Argasidae, commonly known as soft ticks (e.g., relapsing fever tick (Ornithodores turicata Duges), common fowl tick (Argas radiatus Raillet)); scab and itch mites in the families Psoroptidae, Pyemotidae, and Sarcoptidae; eggs, adults and immatures of the order Orthoptera including grasshoppers, locusts and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differentialis Thomas), American grasshoppers (e.g., Schistocerca americana Drury), desert locust (Schistocerca gregaria Forsskâl), migratory locust (Locusta migratoria Linnaeus), bush locust (Zonocerus spp.), house cricket (Acheta domesticus Linnaeus), mole crickets (e.g., tawny mole cricket (Scapteriscus vicinus Scudder) and Southern mole cricket (Scapteriscus borellii Giglio-Tos)); eggs, adults and immatures of the order Diptera including leaftniners (e.g., Liriomyza spp. such as serpentine vegetable leaftniner (Liriomyza sativae Blanchard)), midges, fruit flies (Tephritidae), frit flies (e.g., Oscinella frit Linnaeus), soil maggots, house flies (e.g., Musca domèstica Linnaeus), lesser house flies (e.g., Fannia canicularis Linnaeus, F. femoralis Stein), stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, hom flies, blow flies (e.g., Chrysomya spp., Phormia spp.), and other muscoid fly pests, horse flies (e.g., Tabanus spp.), bot flies (e.g., Gasterophilus spp., Oestrus spp.), cattle grubs (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.), keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g., Prosimulium spp., Simulium spp.), biting midges, sand flies, sciarids, and other Nematocera; eggs, adults and immatures of the order Thysanoptera including onion thrips (Thrips tabaci Lindeman), flower thrips (Frankliniella spp.), and other foliar feeding thrips; insect pests of the order Hymenoptera including ants of the Family Formicidae including the Florida carpenter ant (Camponotus floridanus Buckley), red carpenter ant (Camponotus ferrugineus Fabricius), black carpenter ant (Camponotus pennsylvanicus De Geer), white-footed ant (Technomyrmex albipes F. Smith), big headed ants (Pheidole sp.), ghost ant (Tapinoma melanocephalum Fabricius); Pharaoh ant (Monomorium pharaonis Linnaeus), little fire ant (Wasmannia auropunctata Roger), fire ant (Solenopsis geminata Fabricius), red imported fire ant (Solenopsis invicta Buren), Argentine ant (Iridomyrmex humilis Mayr), crazy ant (Paratrechina longicornis Latreille), pavement ant (Tetramorium caespitum Linnaeus), comfield ant (Lasius alienus Fôrster) and odorous house ant (Tapinoma sessile Say). Other Hymenoptera including bees (including carpenter bees), homets, yellow jackets, wasps, and sawflies (Neodiprion spp.; Cephus spp.); insect pests of the order Isoptera including termites in the Termitidae (e.g., Macrotermes sp., Odontotermes obesus Rambur), Kalotermitidae (e.g., Cryptotermes sp.), and Rhinotermitidae (e.g., Reticulitermes sp., Coptotermes sp., Heterotermes tenuis Hagen) families, the eastem subterranean termite (Reticulitermes flavipes Kollar), western subterranean termite (Reticulitermes hesperus Banks), Formosan subterranean termite (Coptotermes formosanus Shiraki), West Indian drywood termite (Incisitermes immigrans Snyder), powder post termite {Cryptotermes brevis Walker), drywood termite (Incisitermes snyderi Light), southeastem subterranean termite (Reticulitermes virginicus Banks), western drywood termite (Incisiterm.es minor Hagen), arboreal termites such as Nasutitermes sp. and other termites of économie importance; insect pests of the order Thysanura such as silverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobia domestica Packard); insect pests of the orders Mallophaga and Phthiraptera, and including the head louse (Pediculus humanus capitis De Geer), body louse (Pediculus humanus Linnaeus), chicken body louse (Menacanthus stramineus Nitzsch), dog biting louse (Trichodectes canis De Geer), fluff louse (Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank), short-nosed cattle louse (Haematopinus eurysternus Nitzsch), long-nosed cattle louse (Linognathus vituli Linnaeus) and other sucking and chewing parasitic lice that attack man and animais; insect pests of the order Siphonoptera including the oriental rat flea (Xenopsylla cheopis Rothschild), cat flea (Ctenocephalides felis Bouché), dog flea (Ctenocephalides canis Curtis), hen flea (Ceratophyllus gallinae Schrank), sticktight flea (Echidnophaga gallinacea Westwood), human flea (Pidex irritons Linnaeus) and other fleas afflicting mammals and birds. Additional arthropod pests covered include: spiders in the order Araneae such as the brown recluse spider (Loxosceles reclusa Gertsch & Mulaik) and the black widow spider (Latrodectus mactans Fabricius), and centipedes in the order Scutigeromorpha such as the house centipede (Scutigera coleoptrata Linnaeus).
Examples of invertebrate pests of stored grain include larger grain borer (Prostephanus truncatus Hom), lesser grain borer (Rhyzopertha dominica Fabricius), rice weevil (Sitophilus oryzae Linnaeus), maize weevil (Sitophilus zeamais Motschulsky), cowpea weevil (Callosobruchus maculatus Fabricius), red flour beetle (Tribolium castaneum Herbst), granary weevil (Sitophilus granarius Linnaeus), Indian meal moth (Plodia interpunctella Hübner), Mediterranean flour beetle (Ephestia kuehniella Zeller) and fiat or rusty grain beetle (Cryptolestes ferrugineus Stephens).
Compounds of the présent disclosure may hâve activity on members of the Classes Nematoda, Cestoda, Trematoda, and Acanthocephala including economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida such as but not limited to economically important agricultural pests (i.e. root knot nematodes in the genus Meloidogyne, lésion nematodes in the genus Pratylenchus, stubby root nematodes in the genus Trichodorus, etc.) and animal and human health pests (i.e. ail economically important flukes, tapeworms, and roundworms, such as Strongylus vulgaris in horses, Toxocara canis in dogs,
Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs, Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.).
Compounds of the disclosure may hâve activity against pests in the order Lepidoptera (e.g., Alabama argillacea Hübner (cotton leaf worm), Archips argyrospila Walker (huit tree leaf roller), A. rosana Linnaeus (European leaf roller) and other Archips species, Chilo suppressalis Walker (rice stem borer), Cnaphalocrocis medinalis Guenée (rice leaf roller), Crambus caliginosellus Clemens (corn root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Earias insulana Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoverpa armigera Hübner (Old World bollworm), Helicoverpa zea Boddie (corn earworm), Heliothis virescens Fabricius (tobacco budworm), Herpetogramma licarsisalis Walker (sod webworm), Lobesia botrana Denis & Schiffermüller (grape berry moth), Pectinophora gossypiella Saunders (pink bollworm), Phyllocnistis citrella Stainton (citrus leafininer), Pieris brassicae Linnaeus (large white butterfly), Pieris rapae Linnaeus (small white butterfly), Plutella xylostella Linnaeus (diamondback moth), Spodoptera exigua Hübner (beet armyworm), Spodoptera litura Fabricius (tobacco cutworm, cluster Caterpillar), Spodoptera frugiperda J. E. Smith (fall armyworm), Trichoplusia ni Hübner (cabbage looper) and Tuta absoluta Meyrick (tomato leafininer)).
Compounds of the disclosure hâve significant activity on members from the order Hemiptera including: Acyrthosiphonpisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer (apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solani Kaltenbach (foxglove aphid), Chaetosiphon fragaefolii Cockerell (strawberry aphid), Diuraphis noxia Kurdjumov/Mordvilko (Russian wheat aphid), Dysaphis plantaginea Passerini (rosy apple aphid), Eriosoma lanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffroy (mealy plum aphid), Lipaphis pseudobrassicae Davis (tumip aphid), Metopolophium dirrhodum Walker (rosegrain aphid), Macrosiphum euphorbiae Thomas (potato aphid), Myzus persicae Sulzer (peachpotato aphid, green peach aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigus spp. (root aphids and gall aphids), Rhopalosiphum maidis Fitch (corn leaf aphid), Rhopalosiphumpadi Linnaeus (bird cherry-oat aphid), Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius (English grain aphid), Therioaphis maculata Buckton (spotted alfalfa aphid), Toxoptera aurantii Boyer de Fonscolombe (black citrus aphid), and Toxoptera citricidus Kirkaldy (brown citrus aphid); Adelges spp. (adelgids); Phylloxéra devastatrix Pergande (pecan phylloxéra); Bemisia tabaci Gennadius (tobacco whitefly, sweetpotato whitefly), Bemisia argentifolii Bellows & Perring (silverleaf whitefly), Dialeurodes citri Ashmead (citrus whitefly) and Trialeurodes vaporariorum Westwood (greenhouse whitefly); Empoasca fabae Harris (potato leafhopper), Laodelphax striatellus Fallén (smaller brown planthopper), Macrosteles quadrilineatus Forbes (aster leafhopper), Nephotettix cincticeps Uhler (green rice leafhopper), Nephotettix nigropictus Stâl (rice leafhopper), Nilaparvata Ingens Stâl (brown planthopper), Peregrinus maidis Ashmead (corn planthopper), Sogatella furcifera Horvâth (white-backed planthopper), Tagosodes orizicolus Muir (rice delphacid), Typhlocyba pomaria McAtee (white apple leafhopper), Erythroneura spp. (grape leafhoppers); Magicidada septendecim Linnaeus (periodical cicada); Icerya purchasi Maskell (cottony cushion scale), Quadraspidiotus perniciosus Comstock (San José scale); Planococcus citri Risso (citrus mealybug); Pseudococcus spp. (other mealybug complex); Cacopsylla pyricola Foerster (pear psylla), Trioza diospyri Ashmead (persimmon psylla).
Compounds of this disclosure also hâve activity on members from the order Hemiptera including: Acrosternum hilare Say (green stink bug), Anasa tristis De Geer (squash bug), Blissus leucopterus leucopterus Say (chinch bug), Cimex lectularius Linnaeus (bed bug) Corythucha gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-Schâffer (cotton stainer), Euschistus servus Say (brown stink bug), Euschistus variolarius Palisot de Beauvois (one-spotted stink bug), Graptostethus spp. (complex of seed bugs), Halyomorpha halys Stâl (brown marmorated stink bug), Leptoglossus corculus Say (leaffooted pine seed bug), Lygus lineolaris Palisot de Beauvois (tamished plant bug), Nezara viridula Linnaeus (southem green stink bug), Oebalus pugnax Fabricius (rice stink bug), Oncopeltus fasciatus Dallas (large milkweed bug), Pseudatomoscelis seriatus Reuter (cotton fleahopper). Other insect orders controlled by compounds of the disclosure include Thysanoptera (e.g., Frankliniella occidentalis Pergande (western flower thrips), Scirtothrips citri Moulton (citrus thrips), Scirtothrips variabilis Beach (soybean thrips), and Thrips tabaci Lindeman (onion thrips); and the order Coleoptera (e.g., Leptinotarsa decemlineata Say (Colorado potato beetle), Epilachna varivestis Mulsant (Mexican bean beetle) and wireworms of the généra Agriotes, Athous or Limonius).
Of note is use of compounds of this disclosure for controlling western flower thrips (Frankliniella occidentalis'). Of note is use of compounds of this disclosure for controlling potato leafhopper (Empoasca fabae). Of note is use of compounds of this disclosure for controlling cotton melon aphid (Aphis gossypii). Ofnote is use of compounds ofthis disclosure for controlling green peach aphid (Myzus persicae). Of note is use of compounds of this disclosure for controlling sweetpotato whitefly (Bemisia tabaci).
Compounds of the présent disclosure may also be useful for increasing vigor of a crop plant. This method comprises contacting the crop plant (e.g., foliage, flowers, fruit or roots) or the seed from which the crop plant is grown with a compound of Formula 1 in amount sufficient to achieve the desired plant vigor effect (i.e. biologically effective amount). Typically the compound of Formula 1 is applied in a formulated composition. Although the compound of Formula 1 is often applied directly to the crop plant or its seed, it can also be applied to the locus of the crop plant, i.e. the environment of the crop plant, particularly the portion of the environment in close enough proximity to allow the compound of Formula 1 to migrate to the crop plant. The locus relevant to this method most commonly comprises the growth medium (i.e. medium providing nutrients to the plant), typically soil in which the plant is grown. Treatment of a crop plant to increase vigor of the crop plant thus comprises contacting the crop plant, the seed from which the crop plant is grown or the locus of the crop plant with a biologically effective amount of a compound of Formula 1.
Increased crop vigor can resuit in one or more of the following observed effects: (a) optimal crop establishment as demonstrated by excellent seed germination, crop emergence and crop stand; (b) enhanced crop growth as demonstrated by rapid and robust leaf growth (e.g., measured by leaf area index), plant height, number of tillers (e.g., for rice), root mass and overall dry weight of végétative mass of the crop; (c) improved crop yields, as demonstrated by time to flowering, duration of flowering, number of flowers, total biomass accumulation (i.e. yield quantity) and/or fruit or grain grade marketability of produce (i.e. yield quality); (d) enhanced ability of the crop to withstand or prevent plant disease infections and arthropod, nematode or mollusk pest infestations; and (e) increased ability of the crop to withstand environmental stresses such as exposure to thermal extremes, suboptimal moisture or phytotoxic Chemicals.
The compounds of the présent disclosure may increase the vigor of treated plants compared to untreated plants by killing or otherwise preventing feeding of phytophagous invertebrate pests in the environment of the plants. In the absence of such control of phytophagous invertebrate pests, the pests reduce plant vigor by consuming plant tissues or sap, or transmiting plant pathogens such as viruses. Even in the absence of phytophagous invertebrate pests, the compounds of the disclosure may increase plant vigor by modifying metabolism of plants. Generally, the vigor of a crop plant will be most significantly increased by treating the plant with a compound of the disclosure if the plant is grown in a nonideal environment, i.e. an environment comprising one or more aspects adverse to the plant achieving the full genetic potential it would exhibit in an idéal environment.
Of note is a method for increasing vigor of a crop plant wherein the crop plant is grown in an environment comprising phytophagous invertebrate pests. Also of note is a method for increasing vigor of a crop plant wherein the crop plant is grown in an environment not comprising phytophagous invertebrate pests. Also of note is a method for increasing vigor of a crop plant wherein the crop plant is grown in an environment comprising an amount of moisture less than idéal for supporting growth of the crop plant. Of note is a method for increasing vigor of a crop plant wherein the crop is ri ce. Also of note is a method for increasing vigor of a crop plant wherein the crop is maize (corn). Also of note is a method for increasing vigor of a crop plant wherein the crop is soybean.
Compounds of this disclosure can also be mixed with one or more other biologically active compounds or agents including insecticides, fungicides, nematocides, bactéricides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agronomie and nonagronomic utility. Thus, the présent disclosure also pertains to a composition comprising a biologically effective amount of a compound of Formula 1, at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, and at least one additional biologically active compound or agent. For mixtures of the présent disclosure, the other biologically active compounds or agents can be formulated together with the présent compounds, including the compounds of Formula 1, to form a premix, or the other biologically active compounds or agents can be formulated separately from the présent compounds, including the compounds of Formula 1, and the two formulations combined together before application (e.g., in a spray tank) or, altematively, applied in succession.
Examples of such biologically active compounds or agents with which compounds of this disclosure can be formulated are insecticides such as abamectin, acephate, acequinocyl, acetamiprid, acrinathrin, afidopyropen ([(3S,4A,4a7?,6S,6a5',12Â,12aS,12bS)-3[(cyclopropylcarbonyl)oxy]-l,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12btrimethyl-11 -oxo-9-(3-pyridinyl)-2J7, 1177-naphtho [2,1 -è]pyrano [3,4-e]pyran-4-yl]methyl cyclopropanecarboxylate), amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, benfuracarb, bensultap, bifenthrin, bifenazate, bistrifluron, borate, buprofezin, cadusafos, carbaryl, carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin, cyantraniliprole (3-bromo-l-(3chloro-2-pyridinyl)-yV-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-l//-pyrazole-5carboxamide), cyclaniliprole (3-bromo-7V-[2-bromo-4-chloro-6-[[(lcyclopropylethyl)amino] carbonyl]phenyl] -1 -(3-chloro-2-pyridinyl)- l/f-pyrazole-5carboxamide), cycloprothrin, cycloxaprid ((55,8A)-l-[(6-chloro-3-pyridinyl)methyl]-2,3,5,6,7,821278 hexahydro-9-nitro-5,8-Epoxy-177-imidazo[l,2-a]azepine) cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alphacypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flometoquin (2-ethyl-3,7-dimethyl6-[4-(trifluoromethoxy)phenoxy]-4-quinolinyl methyl carbonate), flonicamid, flubendiamide, flucythrinate, flufenerim, flufenoxuron, flufenoxystrobin (methyl (a£)-2-[[2-chloro-4(trifluoromethyl)phenoxy]methyl]-a-(methoxymethylene)benzeneacetate), flufensulfone (5chloro-2-[(3,4,4-trifluoro-3-buten-l-yl)sulfonyl]thiazole), fluhexafon, fluopyram, flupiprole (1[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[(2-methyl-2-propen-l-yl)amino]-4[(trifluoromethyl)sulfmyl]-177-pyrazole-3-carbonitrile), flupyradifurone (4-[[(6-chloro-3pyridinyl)methyl](2,2-difluoroethyl)amino]-2(517)-furanone), fluvalinate, tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide, heptafluthrin ([2,3,5,6-tetrafluoro-4(methoxymethyl)phenyl] methyl 2,2-dimethyl-3 - [( 1 Z)-3,3,3 -trifluoro-1 -propen-1 yl]cyclopropanecarboxylate), hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidal soaps, isofenphos, lufenuron, malathion, meperfluthrin ([2,3,5,6tetrafluoro-4-(methoxymethyl)phenyl]methyl (1Λ,35)-3-(2,2-dichloroethenyl)-2,2dimethylcyclopropanecarboxylate), metaflumizone, metaldehyde, methamidophos, methidathion, methiodicarb, methomyl, methoprene, methoxychlor, metofluthrin, methoxyfenozide, metofluthrin, monocrotophos, monofluorothrin ([2,3,5,6-tetrafluoro-4(methoxymethyl)phenyl]methyl 3 -(2-cyano-1 -propen-1 -yl)-2,2dimethylcyclopropanecarboxylate), nicotine, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, propargite, protrifenbute, pyflubumide (1,3,5-trimethyl-/7-(2methyl-1 -oxopropyl)-7V- [3 -(2-methylpropyl)-4-[2,2,2-trifluoro-1 -methoxy-1 (trifluoromethyl)ethyl]phenyl]-177-pyrazole-4-carboxamide), pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl, pyrifluquinazon, pyriminostrobin (methyl (a£)-2-[[[2-[(2,4dichlorophenyl)amino]-6-(trifluoromethyl)-4-pyrimidinyl]oxy]methyl]-a(methoxymethylene)benzeneacetate), pyriprole, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulprofos, sulfoxaflor (N[methyloxido [ 1 -[6-(trifluoromethyl)-3 -pyridinyl] ethyl] -k4-sulfanylidene] cyanamide), tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethylfluthrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl 2,2,3,321278 tetramethylcyclopropanecarboxylate), tetraniliprole, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tioxazafen (3-phenyl-5-(2-thienyl)-l,2,4-oxadiazole), tolfenpyrad, tralomethrin, triazamate, trichlorfon, triflumezopyrim (2,4-dioxo-l-(5-pyrimidinylmethyl)-3-[3(trifluoromethyl)phenyl]-2/7-pyrido[l,2-a]pyrimidinium inner sait), triflumuron, Bacillus thuringiensis delta-endotoxins, entomopathogenic bacteria, entomopathogenic viruses and entomopathogenic fungi.
Of note are insecticides such as abamectin, acetamiprid, acrinathrin, afidopyropen, amitraz, avermectin, azadirachtin, benfuracarb, bensultap, bifenthrin, buprofezin, cadusafos, carbaryl, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenitrothion, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide, flufenoxuron, flufenoxystrobin, flufensulfone, flupiprole, flupyradifurone, fluvalinate, formetanate, fosthiazate, heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, meperfluthrin, metaflumizone, methiodicarb, methomyl, methoprene, methoxyfenozide, metofluthrin, monofluorothrin, nitenpyram, nithiazine, novaluron, oxamyl, pyflubumide, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriminostrobin, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide, tetramethrin, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate, triflumezopyrim, triflumuron, Bacillus thuringiensis delta-endotoxins, ail strains of Bacillus thuringiensis and ail strains of nucleo polyhedrosis viruses.
One embodiment of biological agents for mixing with compounds of this disclosure include entomopathogenic bacteria such as Bacillus thuringiensis, and the encapsulated delta-endotoxins of Bacillus thuringiensis such as MVP® and MVPII® bioinsecticides prepared by the CellCap® process (CellCap®, MVP® and MVPII® are trademarks of Mycogen Corporation, Indianapolis, Indiana, USA); entomopathogenic fungi such as green muscardine fungus; and entomopathogenic (both naturally occurring and genetically modified) viruses including baculovirus, nucleopolyhedro virus (NPV) such as Helicoverpa zea nucleopolyhedrovirus (HzNPV), Anagrapha falcifera nucleopolyhedrovirus (AfNPV); and granulosis virus (GV) such as Cydia pomonella granulosis virus (CpGV).
One embodiment of biological agents for mixing with compounds of this disclosure include one or a combination of (i) a bacterium of the genus Actinomycètes, Agrobacterium, Arthrobacter,
Alcaligenes, Aureobacterium, Azobacter, Bacillus, Beijerinckia, Bradyrhizobium, Brevibacillus, Burkholderia, Chromobacterium, Clostridium, Clavibacter, Comamonas, Corynebacterium, Curtobacterium, Enterobacter, Flavobacterium, Gluconobacter, Elydrogenophaga, Klebsiella, Methylobacterium, Paenibacillus, Pasteuria, Photorhabdus, Phyllobacterium, Pseudomonas, Rhizobium, Serratia, Sphingobacterium, Sténotrophomonas, Streptomyces, Variovorax, or Xenorhabdus, for example a bacterium of Bacillus amyloliquefaciens, Bacillus cereus, Bacillus firmus, Bacillus, licheniformis, Bacillus pumilus, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Bradyrhizobium japonicum, Chromobacterium subtsugae, Pasteuria nishizawae, Pasteuria penetrans, Pasteuria usage, Pseudomonas fluorescens, and Streptomyces lydicus', (ii) a fungus such as green muscardine fungus; (iii) a virus including baculovirus, nucleopolyhedro virus such as Helicoverpa zea nucleopolyhedrovirus, Anagrapha falcifera nucleopolyhedrovirus; granulosis virus such as Cydia pomonella granulosis virus.
Of particular note is such a combination where the other invertebrate pest control active ingrédient belongs to a different Chemical class or has a different site of action than the compound of Formula 1. In certain instances, a combination with at least one other invertebrate pest control active ingrédient having a similar spectrum of control but a different site of action will be particularly advantageous for résistance management. Thus, a composition of the présent disclosure can further comprise a biologically effective amount of at least one additional invertebrate pest control active ingrédient having a similar spectrum of control but belonging to a different Chemical class or having a different site of action. These additional biologically active compounds or agents include, but are not limited to, acetylcholinesterase (AChE) inhibitors such as the carbamates methomyl, oxamyl, thiodicarb, triazamate, and the organophosphates chlorpyrifos; GABA-gated chloride channel antagonists such as the cyclodienes dieldrin and endosulfan, and the phenylpyrazoles ethiprole and fipronil; sodium channel modulators such as the pyrethroids bifenthrin, cyfluthrin, ôeto-cyfluthrin, cyhalothrin, /azW-cyhalothrin, cypermethrin, deltamethrin, dimefluthrin, esfenvalerate, metofluthrin and profluthrin; nicotinic acetylcholinereceptor (nAChR) agonists such as the neonicotinoids acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid, and thiamethoxam, the sulfoximine sulfoxaflor, the butenolide flupyradifurone, and the mesoionic triflumezopyrim; nicotinic acétylcholine receptor (nAChR) allosteric activators such as the spinosyns spinetoram and spinosad; chloride channel activators such as the avermectins abamectin and emamectin; juvénile hormone mimics such as diofenolan, methoprene, fenoxycarb and pyriproxyfen; chordotonal organ modulators such as pymetrozine, pyrifluquinazon and flonicamid; mite growth inhibitors such as etoxazole; inhibitors of mitochondrial ATP synthase such as propargite; uncouplers of oxidative phosphorylation via disruption of the proton gradient such as chlorfenapyr; nicotinic acétylcholine receptor (nAChR) channel blockers such as the nereistoxin analogs cartap; inhibitors of chitin biosynthesis such as the benzoylureas flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron and triflumuron, and buprofezin; dipteran moulting disrupters such as cyromazine; ecdysone receptor agonists such as the diacylhydrazines methoxyfenozide and tebufenozide; octopamine receptor agonists such as amitraz; mitochondrial complex III électron transport inhibitors such as hydramethylnon and bifenazate; mitochondrial complex I électron transport inhibitors such as pyridaben; voltage-dependent sodium channel blockers such as indoxacarb; inhibitors of acetyl CoA carboxylase such as the tetronic and tetramic acids spirodiclofen, spiromesifen and spirotetramat; mitochondrial complex II électron transport inhibitors such as the β-ketonitriles cyenopyrafen and cyflumetofen; ryanodine receptor modulators such as the anthranilic diamides chlorantraniliprole and cyantraniliprole, diamides such as flubendiamide, and ryanodine receptor ligands such as ryanodine; compounds wherein the target site responsible for biological activity is unknown or uncharacterized such as azadirachtinand pyridalyl; microbial disrupters of insect midgut membranes such as Bacillus thuringiensis and the delta-endotoxins they produce and Bacillus sphaericus', and biological agents including nuclear polyhedrosis (NPV) and other naturally occurring or genetically modified insecticidal viruses.
Further examples of biologically active compounds or agents with which compounds of this disclosure can be formulated are: fongicides such as acibenzolar-S-methyl, aldimorph, ametoctradin, aminopyrifen, amisulbrom, anilazine, azaconazole, azoxystrobin, benalaxyl (including benalaxyl-M), benodanil, benomyl, benthiavalicarb (including benthiavalicarbisopropyl), benzovindiflupyr, bethoxazin, binapacryl, biphenyl, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, carboxin, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, chlozolinate, copper hydroxide, copper oxychloride, copper sulfate, coumoxystrobin, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dichlobentiazox, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole (including diniconazole-M), dinocap, dipymetitrone, dithianon, dithiolanes, dodemorph, dodine, econazole, etaconazole, edifenphos, enoxastrobin (also known as enestroburin), epoxiconazole, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, fenaminstrobin, fenarimol, fenbuconazole, fenforam, fenhexamide, fenoxanil, fenpiclonil, fenpicoxamid, fenpropidin, fenpropimorph, fenpyrazamine, fentin acetate, fentin hydroxide, ferbam, ferimzone, flometoquin, florylpicoxamid, fluopimomide, fluazinam, fludioxonil, flufenoxystrobin, fluindapyr, flumorph, fluopicolide, fluopyram, fluoxapiprolin, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fthalide (also known as phthalide), fuberidazole, furalaxyl, furametpyr, hexaconazole, hymexazole, guazatine, imazalil, imibenconazole, iminoctadine albesilate, iminoctadine triacetate, inpyrfluxam, iodicarb, ipconazole, ipfentrifluconazole, ipflufenoquin, isofetamid, iprobenfos, iprodione, iprovalicarb, isoflucypram, isoprothiolane, isopyrazam, isotianil, kasugamycin, kresoxim-methyl, lancotrione, mancozeb, mandipropamid, mandestrobin, maneb, mapanipyrin, mefentrifluconazole, mepronil, meptyldinocap, metalaxyl (including metalaxyl-M/mefenoxam), metconazole, methasulfocarb, metiram, metominostrobin, metyltetraprole, metrafenone, myclobutanil, naftitine, neo-asozin (ferrie methanearsonate), nuarimol, octhilinone, ofurace, orysastrobin, oxadixyl, oxathiapiprolin, oxolinic acid, oxpoconazole, oxycarboxin, oxytetracycline, penconazole, pencycuron, penflufen, penthiopyrad, perfurazoate, phosphorous acid (including salts thereof, e.g., fosetyl-aluminm), picoxystrobin, piperalin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pydiflumetofen (Adepidyn®), pyraclostrobin, pyrametostrobin, pyrapropoyne, pyraoxystrobin, pyraziflumid, pyrazophos, pyribencarb, pyributacarb, pyridachlometyl, pyrifenox, pyriofenone, perisoxazole, pyrimethanil, pyrifenox, pyrrolnitrin, pyroquilon, quinconazole, quinmethionate, quinofumelin, quinoxyfen, quintozene, silthiofam, sedaxane, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, tebufloquin, teclofthalam, tecloftalam, teenazene, terbinafine, tetraconazole, thiabendazole, thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolprocarb, tolyfluanid, triadimefon, triadimenol, triarimol, triazoxide, tribasic copper sulfate, triclopyricarb, tridemorph, trifloxystrobin, triflumizole, trimoprhamide tricyclazole, trifloxystrobin, triforine, triticonazole, uniconazole, validamycin, valifenalate (also known as valifenal), vinclozolin, zineb, ziram, zoxamide and l-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro3 -isoxazolyl] -2-thiazolyl] -1 -piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1 H-pyrazol-1 yl]ethanone; nematocides such as fluopyram, spirotetramat, thiodicarb, fosthiazate, abamectin, iprodione, fhiensulfone, dimethyl disulfide, tioxazafen, 1,3-dichloropropene (1,3-D), metam (sodium and potassium), dazomet, chloropicrin, fenamiphos, ethoprophos, cadusaphos, terbufos, imicyafos, oxamyl, carbofuran, tioxazafen, Bacillusfirmus and Pasteuria nishizawae', bactéricides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad.
In certain instances, combinations of a compound of this disclosure with In certain instances, combinations of a compound of this disclosure with other biologically active (particularly invertebrate pest control) compounds or agents (i.e. active ingrédients) can resuit in an enhanced effect. Reducing the quantity of active ingrédients released in the environment while ensuring effective pest control is always désirable. When enhanced invertebrate pest control occurs at application rates giving agronomically satisfactory levels of invertebrate pest control, such combinations can be advantageous for reducing crop production cost and decreasing environmental load.
Compounds of this disclosure and compositions thereof can be applied to plants genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis deltaendotoxins). Such an application may provide a broader spectrum of plant protection and be advantageous for résistance management. The exogenously applied invertebrate pest control compounds of this disclosure in combination with the expressed toxin proteins may provide an enhanced effect.
General référencés for these agricultural protectants (i.e. insecticides, fungicides, nematocides, acaricides, herbicides and biological agents) include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Famham, Surrey, U.K., 2003 and The BioPesticide Manual, 2nd Edition, L. G. Copping, Ed., British Crop Protection Council, Famham, Surrey, U.K., 2001.
Compounds of this disclosure can be combined or formulated with polynucleotides including, but not limited to, DNA, RNA, and/or chemically modified nucléotides influencing the amount of a particular target through down régulation, interférence, suppression or silencing of the genetically derived transcript that render an insecticidal effect.
For embodiments where one or more of these varions mixing partners are used, the weight ratio of these varions mixing partners (in total) to the compound of Formula 1 is typically between about 1:3000 and about 3000:1. Of note are weight ratios between about 1:300 and about 300:1 (for example ratios between about 1:30 and about 30:1). One skilled in the art can easily détermine through simple expérimentation the biologically effective amounts of active ingrédients necessary for the desired spectrum of biological activity. It will be évident that including these additional components can expand the spectrum of invertebrate pests controlled beyond the spectrum controlled by the compound of Formula 1 alone.
Table A lists spécifie combinations of a compound of Formula 1 with other invertebrate pest control agents illustrative of the mixtures, compositions and methods of the présent disclosure. The first column of Table A lists the spécifie invertebrate pest control agents (e.g., “Abamectin” in the first line). The second column of Table A lists the mode of action (if known) or Chemical class of the invertebrate pest control agents. The third column of Table A lists embodiment(s) of ranges of weight ratios for rates at which the invertebrate pest control agent can be applied relative to a compound of Formula 1 (e.g., “50:1 to 1:50” of abamectin relative to a compound of Formula 1 by weight). Thus, for example, the first line of Table A specifically discloses the combination of a compound of Formula 1 with abamectin can be applied in a weight ratio between 50:1 to 1:50. The remaining Unes of Table A are to be construed similarly. Of further note Table A lists spécifie combinations of a compound of Formula 1 with other invertebrate pest control agents illustrative of the mixtures, compositions and methods of the présent disclosure and includes additional embodiments of weight ratio ranges for application rates.
Table A
Invertebrate Pest Control Agent Mode of Action or Chemical Class Typical Weight Ratio
Abamectin chloride channel activator 50:1 to 1:50
Acetamiprid nicotinic acetylcholinereceptor (nAChR) agonist 150:1 to 1:200
Amitraz octopamine receptor agonists 200:1 to 1:100
Avermectin macrocyclic lactones 50:1 to 1:50
Azadirachtin unknown site of action 100:1 to 1:120
Beta-cyfluthrin sodium channel modulators 150:1 to 1:200
Bifenthrin sodium channel modulators 100:1 to 1:10
Buprofezin chitin biosynthesis inhibitors 500:1 to 1:50
Cartap nicotinic acétylcholine receptor (nAChR) channel blocker 100:1 to 1:200
Chlorantraniliprole ryanodine receptor modulator 100:1 to 1:120
Chlorfenapyr uncouplers of oxidative phosphorylation 300:1 to 1:200
Chlorpyrifos acetylcholinesterase inhibitor 500:1 to 1:200
Clothianidin nicotinic acétylcholine receptor (nAChR) agonist 100:1 to 1:400
Cyantraniliprole Ryanodine receptor modulator 100:1 to 1:120
Cyfluthrin sodium channel modulator 150:1 to 1:200
Cyhalothrin sodium channel modulator 150:1 to 1:200
Cypermethrin sodium channel modulator 150:1 to 1:200
Cyromazine dipteran moulting disrupter 400:1 to 1:50
Deltamethrin sodium channel modulators 50:1 to 1:400
Dieldrin GABA-gated chloride channel antagonist 200:1 to 1:100
Invertebrate Pest Control Agent Mode of Action or Chemical Class Typical Weight Ratio
Dinotefuran nicotinic acétylcholine receptor (nAChR) agonist 150:1 to 1:200
Diofenolan juvénile hormone mimic 150:1 to 1:200
Emamectin chloride channel activator 50:1 to 1:10
Endosulfan GABA-gated chloride channel antagonist 200:1 to 1:100
Esfenvalerate sodium channel modulator 100:1 to 1:400
Ethiprole GABA-regulated chloride channel antagonist 200:1 to 1:100
Fenothiocarb 150:1 to 1:200
Fenoxycarb juvénile hormone mimic 500:1 to 1:100
Fenvalerate sodium channel modulator 150:1 to 1:200
Fipronil GABA-regulated chloride channel antagonist 150:1 to 1:100
Flonicamid sélective hemipteran feeding blocker 200:1 to 1:100
Flubendiamide ryanodine receptor modulator 100:1 to 1:120
Flufenoxuron chitin biosynthesis inhibitor 200:1 to 1:100
Hexaflumuron chitin biosynthesis inhibitor 300:1 to 1:50
Hydramethylnon mitochondrial Complex III électron transport inhibitors 150:1 to 1:250
Imidacloprid nicotinic acétylcholine receptor (nAChR) agonist 1000:1 to 1:1000
Indoxacarb voltage-dependent sodium channel blocker 200:1 to 1:50
Lambda-cyhalothrin sodium channel modulator 50:1 to 1:250
Lufenuron chitin biosynthesis inhibitor 500:1 to 1:250
Metaflumizone voltage-dependent sodium channel blocker 200:1 to 1:200
Methomyl acetylcholinesterase inhibitor 500:1 to 1:100
Methoprene juvénile hormone mimic 500:1 to 1:100
Methoxyfenozide ecdysone receptor agonist 50:1 to 1:50
Nitenpyram nicotinic acétylcholine receptor (nAChR) agonist 150:1 to 1:200
Invertebrate Pest Control Agent Mode of Action or Chemical Class Typical Weight Ratio
Nithiazine nicotinic acétylcholine receptor (nAChR) agonist 150:1 to 1:200
Novaluron chitin biosynthesis inhibitor 500:1 to 1:150
Oxamyl acetylcholinesterase inhibitors 200:1 to 1:200
Pymetrozine sélective hemipteran feeding blocker 200:1 to 1:100
Pyrethrin sodium channel modulator 100:1 to 1:10
Pyridaben mitochondrial Complex I électron transport inhibitor 200:1 to 1:100
Pyridalyl unknown site of action 200:1 to 1:100
Pyriproxyfen juvénile hormone mimic 500:1 to 1:100
Ryanodine ryanodine receptor ligand 100:1 to 1:120
Spinetoram nicotinic acétylcholine receptor (nAChR) allosteric activator 150:1 to 1:100
Spinosad nicotinic acétylcholine receptor (nAChR) allosteric activators 500:1 to 1:10
Spirodiclofen acetyl CoA carboxylase inhibitor 200:1 to 1:200
Spiromesifen acetyl CoA carboxylase inhibitor 200:1 to 1:200
Tebufenozide ecdysone receptor agonist 500:1 to 1:250
Thiacloprid nicotinic acétylcholine receptor (nAChR) agonist 100:1 to 1:200
Thiamethoxam nicotinic acétylcholine receptor (nAChR) agonist 1250:1 to 1:1000
Thiodicarb acetylcholinesterase inhibitors 500:1 to 1:400
Thiosultap-sodium Nicotinic acétylcholine receptor (nAChR) channel blocker 150:1 to 1:100
Tralomethrin sodium channel modulator 150:1 to 1:200
Triazamate acetyl cholinestérase inhibitors 250:1 to 1:100
T riflumezopyrim
Triflumuron chitin synthesis inhibitor 200:1 to 1:100
Bacillus thuringiensis biological agents 50:1 to 1:10
Invertebrate Pest Control Agent Mode of Action or Chemical Class Typical Weight Ratio
Bacillus thuringiensis delta-endotoxin biological agents 50:1 to 1:10
NPV (e.g., Gemstar) biological agents 50:1 to 1:10
Of note is the composition of the présent disclosure wherein the at least one additional biologically active compound or agent is selected from the Invertebrate Pest Control Agents listed in Table A above.
The weight ratios of a compound, including a compound of Formula 1, an TV-oxide or a sait 5 thereof, to the additional invertebrate pest control agent typically are between 1000:1 and 1:1000, with one embodiment being between 500:1 and 1:500, another embodiment being between 250:1 and 1:200 and another embodiment being between 100:1 and 1:50.
Listed below in Tables B1 to B6 are embodiments of spécifie compositions comprising a compound of Formula 1 (compound numbers (Cmpd. No.) refer to compounds in Index Table A) 10 and an additional invertebrate pest control agent.
Table B1
Mixture No. Cmpd. No. and Invertebrate Pest Control Agent Mixture No. Cmpd. No. and Invertebrate Pest Control Agent
Bl-1 8 and Abamectin B1-3 8 8 and Indoxacarb
B1-2 8 and Acetamiprid Bl-39 8 and Lambda-cyhalothrin
Bl-3 8 and Amitraz B1-40 8 and Lufenuron
B1-4 8 and Avermectin Bl-41 8 and Metaflumizone
Bl-5 8 and Azadirachtin B1-42 8 and Methomyl
Bl-6 8 and Bensultap B1-43 8 and Methoprene
Bl-7 8 and Beta-cyfluthrin B1-44 8 and Methoxyfenozide
Bl-8 8 and Bifenthrin B1-45 8 and Nitenpyram
Bl-9 8 and Buprofezin B1-46 8 and Nithiazine
Bl-10 8 and Cartap B1-47 8 and Novaluron
Bl-11 8 and Chlorantraniliprole B1-48 8 and Oxamyl
Bl-12 8 and Chlorfenapyr B1-49 8 and Phosmet
Bl-13 8 and Chlorpyrifos Bl-50 8 and Pymetrozine
Bl-14 8 and Clothianidin Bl-51 8 and Pyrethrin
Bl-15 8 and Cyantraniliprole B1-52 8 and Pyridaben
Bl-16 8 and Cyfluthrin Bl-53 8 and Pyridalyl
Mixture No. Cmpd. No. and Invertebrate Pest Control Agent Mixture No. Cmpd. No. and Invertebrate Pest Control Agent
Bl-17 8 and Cyhalothrin B1-54 8 and Pyriproxyfen
Bl-18 8 and Cypermethrin Bl-55 8 and Ryanodine
Bl-19 8 and Cyromazine Bl-56 8 and Spinetoram
B1-20 8 and Deltamethrin Bl-57 8 and Spinosad
B1-21 8 and Dieldrin Bl-58 8 and Spirodiclofen
B1-22 8 and Dinotefuran Bl-59 8 and Spiromesifen
B1-23 8 and Diofenolan B1-60 8 and Spirotetramat
B1-24 8 and Emamectin Bl-61 8 and Sulfoxaflor
B1-25 8 and Endosulfan B1-62 8 and Tebufenozide
B1-26 8 and Esfenvalerate B1-63 8 and Tefluthrin
B1-27 8 and Ethiprole B1-64 8 and Thiacloprid
B1-28 8 and Fenothiocarb Bl-65 8 and Thiamethoxam
B1-29 8 and Fenoxycarb Bl-66 8 and Thiodicarb
Bl-30 8 and Fenvalerate Bl-67 8 and Thiosultap-sodium
B1-31 8 and Fipronil Bl-68 8 and Tolfenpyrad
Bl-32 8 and Flonicamid Bl-69 8 and Tralomethrin
Bl-33 8 and Flubendiamide B1-70 8 and Triazamate
Bl-34 8 and Flufenoxuron Bl-71 8 and T riflumezopyrim
Bl-35 8 and Hexaflumuron B1-72 8 and Triflumuron
Bl-36 8 and Hydramethylnon B1-73 8 and Bacillus thuringiensis
B1-37 8 and Imidacloprid B1-74 8 and Bacillus thuringiensis delta-endotoxin
B1-75 8 and NPV (e.g., Gemstar)
Table B2
Table B2 is identical to Table Bl, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 14. For example, the first mixture in Table B2 is designated B2-1 and is a mixture of compound 14 and the additional invertebrate 5 pest control agent abamectin.
Table B3
Table B3 is identical to Table Bl, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 19. For example, the first mixture in Table B3 is designated B3-1 and is a mixture of compound 19 and the additional invertebrate 10 pest control agent abamectin.
100
Table B4
Table B4 is identical to Table Bl, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 78. For example, the first mixture in Table B4 is designated B4-1 and is a mixture of compound 78 and the additional invertebrate pest control agent abamectin.
Table B5
Table B5 is identical to Table Bl, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 3. For example, the first mixture in Table B5 is designated B5-1 and is a mixture of compound 3 and the additional invertebrate pest control agent abamectin.
Table B6
Table B6 is identical to Table Bl, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 86. For example, the first mixture in Table B6 is designated B6-1 and is a mixture of compound 86 and the additional invertebrate pest control agent abamectin.
The spécifie mixtures listed in Tables Bl to B6 typically combine a compound of Formula 1 with the other invertebrate pest agent in the ratios specified in Table A.
Listed below in Tables Cl to C6 are spécifie mixtures comprising a compound of Formula 1 (compound numbers (Cmpd. No.) refer to compounds in Index Table A) and an additional invertebrate pest control agent. Tables Cl to Cl9 further list spécifie weight ratios typical of the mixtures of Tables Cl to Cl9. For example, the first weight ratio entry of the first line of Table Cl specifically discloses the mixture of Compound 1 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.
Table Cl
101
Mixture No. Cmpd. No. and Invertebrate Pest Control Agent Typical Mixture Ratios (by weight)
Cl-1 8 and Abamectin 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-2 8 and Acetamiprid 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-3 8 and Amitraz 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-4 8 and Avermectin 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-5 8 and Azadirachtin 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-6 8 and Bensultap 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-7 8 and Beta-cyfluthrin 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-8 8 and Bifenthrin 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-9 8 and Buprofezin 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-10 8 and Cartap 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-11 8 and Chlorantraniliprole 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-12 8 and Chlorfenapyr 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-13 8 and Chlorpyrifos 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-14 8 and Clothianidin 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-15 8 and Cyantraniliprole 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-16 8 and Cyfluthrin 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-17 8 and Cyhalothrin 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-18 8 and Cypermethrin 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-19 8 and Cyromazine 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-20 8 and Deltamethrin 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-21 8 and Dieldrin 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-22 8 and Dinotefuran 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-23 8 and Diofenolan 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-24 8 and Emamectin 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-25 8 and Endosulfan 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-26 8 and Esfenvalerate 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-27 8 and Ethiprole 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-28 8 and Fenothiocarb 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-29 8 and Fenoxycarb 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-30 8 and Fenvalerate 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-31 8 and Fipronil 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-32 8 and Flonicamid 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-33 8 and Flubendiamide 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-34 8 and Flufenoxuron 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-35 8 and Hexaflumuron 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-36 8 and Hydramethylnon 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
Cl-37 8 and Imidacloprid 100:1 10:1 5:1 2:1 1 1 1:2 1:5 1:10 1:100
102
Cl-38 8 and Indoxacarb 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-39 8 and Lambdacyhalothrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-40 8 and Lufenuron 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-41 8 and Metaflumizone 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-42 8 and Methomyl 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-43 8 and Methoprene 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-44 8 and Methoxyfenozide 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-45 8 and Nitenpyram 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-46 8 and Nithiazine 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-47 8 and Novaluron 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-48 8 and Oxamyl 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-49 8 and Phosmet 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-50 8 and Pymetrozine 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-51 8 and Pyrethrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-52 8 and Pyridaben 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-53 8 and Pyridalyl 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-54 8 and Pyriproxyfen 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-55 8 and Ryanodine 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-56 8 and Spinetoram 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-57 8 and Spinosad 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-58 8 and Spirodiclofen 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-59 8 and Spiromesifen 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-60 8 and Spirotetramat 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-61 8 and Sulfoxaflor 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-62 8 and Tebufenozide 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-63 8 and Tefluthrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-64 8 and Thiacloprid 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-65 8 and Thiamethoxam 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-66 8 and Thiodicarb 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-67 8 and Thiosultap-sodium 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-68 8 and Tolfenpyrad 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-69 8 and Tralomethrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-70 8 and Triazamate 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-71 8 and Triflumezopyrim 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-72 8 and Triflumuron 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-73 8 and Bacillus thuringiensis 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
103
Cl-74 Bacillus 8 and thwingiensis delta-endotoxin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Cl-75 NPV (e.g., 8 and Gemstar) 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100
Table C2
Table C2 is identical to Table Cl, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 14. For example, the first weight ratio entry of the first line of Table C2 specifically discloses the mixture of Compound 14 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.
Table C3
Table C3 is identical to Table Cl, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 19. For example, the first weight ratio entry of the first line of Table C3 specifically discloses the mixture of Compound 19 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.
Table C4
Table C4 is identical to Table Cl, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 78. For example, the first weight ratio entry of the first line of Table C4 specifically discloses the mixture of Compound 78 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.
Table C5
Table C5 is identical to Table Cl, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 3. For example, the first weight ratio entry of the first line of Table C5 specifically discloses the mixture of Compound 3 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.
Table C6
Table C6 is identical to Table Cl, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 86. For example, the first weight ratio entry of the first line of Table C6 specifically discloses the mixture of Compound 86 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.
104
Listed below in Tables DI to D6 are embodiments of spécifie compositions comprising a compound of Formula 1 (compound numbers (Cmpd. No.) refer to compounds in Index Table A) and an additional fungicide.
Table DI
Mixture No. Cmpd. No. and Fungicide Mixture No. Cmpd. No. and Fungicide
Dl-1 8 and Probenazole Dl-17 8 and Difenoconazole
Dl-2 8 and Tiadinil Dl-18 8 and Cyproconazole
Dl-3 8 and Isotianil Dl-19 8 and Propiconazole
Dl-4 8 and Pyroquilon Dl-20 8 and Fenoxanil
Dl-5 8 and Metominostrobin Dl-21 8 and Ferimzone
Dl-6 8 and Flutolanil Dl-22 8 and Fthalide
Dl-7 8 and Validamycin Dl-23 8 and Kasugamycin
Dl-8 8 and Furametpyr Dl-24 8 and Picoxystrobin
Dl-9 8 and Pencycuron Dl-25 8 and Penthiopyrad
Dl-10 8 and Simeconazole Dl-26 8 and Famoxadone
Dl-11 8 and Orysastrobin Dl-27 8 and Cymoxanil
Dl-12 8 and Trifloxystrobin Dl-28 8 and Proquinazid
Dl-13 8 and Isoprothiolane Dl-29 8 and Flusilazole
Dl-14 8 and Azoxystrobin Dl-30 8 and Mancozeb
Dl-15 8 and Tricyclazole Dl-31 8 and Copper hydroxide
Dl-16 8 and Hexaconazole Dl-32 8 and oxathiapiproiin
Table D2
Table D2 is identical to Table Dl, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 14. For example, the first mixture in Table D2 is designated D2-1 and is a mixture of compound 14 and the additional fungicide 10 probenazole.
Table D3
Table D3 is identical to Table Dl, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 19. For example, the first mixture in Table D3 is designated D3-1 and is a mixture of compound 19 and the additional fungicide 15 probenazole.
Table D4
Table D4 is identical to Table Dl, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 78. For example, the first mixture
105 in Table D4 is designated D4-1 and is a mixture of compound 78 and the additional fongicide probenazole.
Table D5
Table D5 is identical to Table Dl, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 3. For example, the first mixture in Table D5 is designated D5-1 and is a mixture of compound 3 and the additional fongicide probenazole.
Table D6
Table D6 is identical to Table Dl, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 86. For example, the first mixture in Table D6 is designated D6-1 and is a mixture of compound 86 and the additional fongicide probenazole.
Invertebrate pests are controlled in agronomie and nonagronomic applications by applying one or more compounds of this disclosure, typically in the form of a composition, in a biologically effective amount, to the environment of the pests, including the agronomie and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
Thus the présent disclosure comprises a method for controlling an invertebrate pest in agronomie and/or nonagronomic applications, comprising contacting the invertebrate pest or its environment with a biologically effective amount of one or more of the compounds of the disclosure, or with a composition comprising at least one such compound or a composition comprising at least one such compound and a biologically effective amount of at least one additional biologically active compound or agent. Examples of suitable compositions comprising a compound ôf the disclosure and a biologically effective amount of at least one additional biologically active compound or agent include granular compositions wherein the additional active compound is présent on the same granule as the compound of the disclosure or on granules separate from those of the compound of the disclosure.
To achieve contact with a compound or composition of the disclosure to protect a field crop from invertebrate pests, the compound or composition is typically applied to the seed of the crop before planting, to the foliage (e.g., leaves, stems, flowers, fruits) of crop plants, or to the soil or other growth medium before or after the crop is planted.
One embodiment of a method of contact is by spraying. Altematively, a granular composition comprising a compound of the disclosure can be applied to the plant foliage or the
106 soil. Compounds of this disclosure can also be effectively delivered through plant uptake by contacting the plant with a composition comprising a compound of this disclosure applied as a soil drench of a liquid formulation, a granular formulation to the soil, a nursery box treatment or a dip of transplants. Of note is a composition of the présent disclosure in the form of a soil drench liquid formulation. Also of note is a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of the présent disclosure or with a composition comprising a biologically effective amount of a compound of the présent disclosure. Of further note is this method wherein the environment is soil and the composition is applied to the soil as a soil drench formulation. Of further note is that compounds of this disclosure are also effective by localized application to the locus of infestation. Other methods of contact include application of a compound or a composition of the disclosure by direct and residual sprays, aerial sprays, gels, seed coatings, microencapsulations, systemic uptake, baits, ear tags, boluses, foggers, fumigants, aérosols, dusts and many others. One embodiment of a method of contact is a dimensionally stable fertilizer granule, stick or tablet comprising a compound or composition of the disclosure. The compounds of this disclosure can also be impregnated into materials for fabricating invertebrate control devices (e.g., insect netting).
Compounds of the disclosure are useful in treating ail plants, plant parts and seeds. Plant and seed varieties and cultivars can be obtained by conventional propagation and breeding methods or by genetic engineering methods. Genetically modified plants or seeds (transgenic plants or seeds) are those in which a heterologous gene (transgene) has been stably integrated into the plant's or seed’s genome. A transgene that is defmed by its particular location in the plant genome is called a transformation or transgenic event.
Genetically modified plant and seed cultivars which can be treated according to the disclosure include those that are résistant against one or more biotic stresses (pests such as nematodes, insects, mites, fringi, etc.) or abiotic stresses (drought, cold température, soil salinity, etc.), or that contain other désirable characteristics. Plants and seeds can be genetically modified to exhibit traits of, for example, herbicide tolérance, insect-resistance, modified oil profiles or drought tolérance. Useful genetically modified plants and seeds containing single gene transformation events or combinations of transformation events are listed in Table Z. Additional information for the genetic modifications listed in Table Z can be obtained from the following databases:
http://www2.oecd.org/biotech/byidentifier.aspx http://www.aphis.usda.go http://gmoinfo.jrc.ec. europa. eu
107
The following abbreviations are used in Table Z which follows: toi. is tolérance, res. is résistance, SU is sulfonylurea, ALS is acetolactate synthase, HPPD is 4-Hydroxyphenylpyruvate
Dioxygenase, NA is Not Available.
Table Z
Crop Event Name Event Code Trait(s) Gene(s)
Alfalfa J101 MON-00101-8 Glyphosate toi. cp4 epsps (aroA:CP4)
Alfalfa J163 MON-00163-7 Glyphosate toi. cp4 epsps (aroA:CP4)
Canola* 23-18-17 (Event 18) CGN-89465-2 High lauric acid oil te
Canola* 23-198 (Event 23) CGN-89465-2 High lauric acid oil te
Canola* 61061 DP-061061-7 Glyphosate toi. gat4621
Canola* 73496 DP-073496-4 Glyphosate toi. gat4621
Canola* GT200 (RT200) MON-89249-2 Glyphosate toi. cp4 epsps (aroA:CP4); goxv247
Canola* GT73 (RT73) MON-00073-7 Glyphosate toi. cp4 epsps (aroA:CP4); goxv247
Canola* HCN10 (Topas 19/2) NA Glufosinate toi. bar
Canola* HCN28 (T45) ACS-BN008-2 Glufosinate toi. pat (syn)
Canola* HCN92 (Topas 19/2) ACS-BN007-1 Glufosinate toi. bar
Canola* MON88302 MON-88302-9 Glyphosate toi. cp4 epsps (aroA:CP4)
Canola* MPS961 NA Phytate breakdown phyA
Canola* MPS962 NA Phytate breakdown phyA
Canola* MPS963 NA Phytate breakdown phyA
Canola* MPS964 NA Phytate breakdown phyA
Canola* MPS965 NA Phytate breakdown phyA
Canola* MSI (B91-4) ACS-BN004-7 Glufosinate toi. bar
Canola* MS8 ACS-BN005-8 Glufosinate toi. bar
Canola* OXY-235 ACS-BN011-5 Oxynil toi. bxn
Canola* PHY14 NA Glufosinate toi. bar
Canola* PHY23 NA Glufosinate toi. bar
Canola* PHY35 NA Glufosinate toi. bar
Canola* PHY36 NA Glufosinate toi. bar
Canola* RFI (B93-101) ACS-BN001-4 Glufosinate toi. bar
Canola* RF2 (B94-2) ACS-BN002-5 Glufosinate toi. bar
Canola* RF3 ACS-BN003-6 Glufosinate toi. bar
108
Bean EMBRAPA5.1 EMB-PV051-1 Disease res. acl (sense and antisense)
Brinjal EE-1 Insect res. crylAc
(Eggplant) Carnation 11 (7442) FLO-07442-4 SU toi..; modified flower surB; dfr; hfl (β'5'h)
Carnation 11363 (1363A) FLO-11363-1 color SU toi.; modified flower color surB; dfr; bp40 (β'5'h)
Carnation 1226A (11226) FLO-11226-8 SU toi.; modified flower color surB; dfr; bp40 (β'5'h)
Carnation 123.2.2 (40619) FLO-40619-7 SU toi.; modified flower color surB; dfr; hfl (β'5'h)
Carnation 123.2.38 (40644) FLO-40644-4 SU toi.; modified flower color surB; dfr; hfl (β'5'h)
Carnation 123.8.12 FLO-40689-6 SU toi.; modified flower color surB; dfr; bp40 (β'5'h)
Carnation 123.8.8 (40685) FLO-40685-1 SU toi.; modified flower color surB; dfr; bp40 (β'5'h)
Carnation 1351A(11351) FLO-11351-7 SU toi.; modified flower color surB; dfr; bp40 (β'5'h)
Carnation 1400A(11400) FLO-11400-2 SU toi.; modified flower color surB; dfr; bp40 (β'5'h)
Carnation 15 FLO-00015-2 SU toi.; modified flower color surB; dfr; hfl (β'5'h)
Carnation 16 FLO-00016-3 SU toi.; modified flower color surB; dfr; hfl (β'5'h)
Carnation 4 FLO-00004-9 SU toi.; modified flower color surB; dfr; hfl (β'5'h)
Carnation 66 FLO-00066-8 SU toi.; delayed senescence surB; acc
Carnation 959A(11959) FLO-11959-3 SU toi.; modified flower color surB; dfr; bp40 (β'5'h)
Carnation 988A(11988) FLO-11988-7 SU toi.; modified flower color surB; dfr; bp40 (β'5'h)
Carnation 26407 IFD-26497-2 SU toi.; modified flower color surB; dfr; bp40 (β'5'h)
Carnation 25958 IFD-25958-3 SU toi.; modified flower color surB; dfr; bp40 (β'5'h)
Chicory RM3-3 NA Glufosinate toi. bar
Chicory RM3-4 NA Glufosinate toi. bar
Chicory RM3-6 NA Glufosinate toi. bar
Cotton 19-51a DD-01951A-7 ALS herbicide toi. S4-HrA
Cotton 281-24-236 DAS-24236-5 Glufosinate toi.; insect res. pat (syn); crylF
Cotton 3006-210-23 DAS-21023-5 Glufosinate toi.; insect res. pat (syn); crylAc
Cotton 31707 NA Oxynil toi.; insect res. bxn; crylAc
Cotton 31803 NA Oxynil toi.; insect res. bxn; crylAc
Cotton 31807 NA Oxynil toi.; insect res. bxn; crylAc
Cotton 31808 NA Oxynil toi.; insect res. bxn; crylAc
Cotton 42317 NA Oxynil toi.; insect res. bxn; crylAc
Cotton BNLA-601 NA Insect res. crylAc
Cotton BXN10211 BXN10211-9 Oxynil toi. bxn; crylAc
Cotton BXN10215 BXN10215-4 Oxynil toi. bxn; crylAc
Cotton BXN10222 BXN10222-2 Oxynil toi. bxn; crylAc
Cotton BXN10224 BXN10224-4 Oxynil toi. bxn; crylAc
Cotton COT102 SYN-IR102-7 Insect res. vip3A(a)
Cotton COT67B SYN-IR67B-1 Insect res. crylAb
109
Cotton COT202 Insect res. vip3A
Cotton Event 1 NA Insect res. crylAc
Cotton GMF CrylA GTL-GMF311-7 Insect res. crylAb-Ac
Cotton GHB119 BCS-GH005-8 Insect res. cry2Ae
Cotton GHB614 BCS-GH002-5 Glyphosate toi. 2mepsps
Cotton GK12 NA Insect res. crylAb-Ac
Cotton LLCotton25 ACS-GH001-3 Glufosinate toi. bar
Cotton MLS 9124 NA Insect res. crylC
Cotton MON1076 MON-89924-2 Insect res. crylAc
Cotton MON1445 MON-01445-2 Glyphosate toi. cp4 epsps (aroA:CP4)
Cotton MON15985 MON-15985-7 Insect res. crylAc; cry2Ab2
Cotton MON1698 MON-89383-1 Glyphosate toi. cp4 epsps (aroA:CP4)
Cotton MON531 MON-00531-6 Insect res. crylAc
Cotton MON757 MON-00757-7 Insect res. crylAc
Cotton MON88913 MON-88913-8 Glyphosate toi. cp4 epsps (aroA:CP4)
Cotton Nqwe Chi 6 Bt NA Insect res. NA?
Cotton SKG321 NA Insect res. crylA; CpTI
Cotton T303-3 BCS-GH003-6 Insect res.; glufosinate toi. crylAb; bar
Cotton T304-40 BCS-GH004-7 Insect res.; glufosinate toi. crylAb; bar
Cotton CE43-67B Insect res. crylAb
Cotton CE46-02A Insect res. crylAb
Cotton CE44-69D Insect res. crylAb
Cotton 1143-14A Insect res. crylAb
Cotton 1143-51B Insect res. crylAb
Cotton T342-142 Insect res. crylAb
Cotton PV-GHGT07 Glyphosate toi. cp4 epsps (aroA:CP4)
(1445)
Cotton EE-GH3 Glyphosate toi. mepsps
Cotton EE-GH5 Insect res. crylAb
Cotton MON88701 MON-88701-3 Dicamba & glufosinate toi. Modified dmo; bar
Cotton OsCrll Anti-allergy Modified Cry j
Creeping ASR368 SMG-36800-2 Glyphosate toi. cp4 epsps (aroA:CP4)
Bentgrass
Eucalyptus 20-C Sait toi. codA
Eucalyptus 12-5C Sait toi. codA
Eucalyptus 12-5B Sait toi. codA
Eucalyptus 107-1 Sait toi. codA
Eucalyptus 1/9/2001 Sait toi. codA
Eucalyptus 2/1/2001 Sait toi. codA
Eucalyptus Cold toi. des9
110
Flax FP967 CDC-FL001-2 ALS herbicide toi. als
Lentil RH44 Imidazolinone toi. als
Maize 3272 SYN-E3272-5 Modified alpha-amylase amy797E
Maize 5307 SYN-05307-1 Insect res. ecry3.1Ab
Maize 59122 DAS-59122-7 Insectres.; glufosinate toi. cry34Abl; cry35Abl; pat
Maize 676 PH-000676-7 Glufosinate toi.; pollination control pat; dam
Maize 678 PH-000678-9 Glufosinate toi.; pollination control pat; dam
Maize 680 PH-000680-2 Glufosinate toi.; pollination control pat; dam
Maize 98140 DP-098140-6 Glyphosate toll; ALS herbicide toi. gat4621; zm-hra
Maize BtlO NA Insect res.; glufosinate toi. crylAb; pat
Maize Btl76 (176) SYN-EV176-9 Insect res.; glufosinate toi. crylAb; bar
Maize BVLA430101 NA Phytate breakdown phyA2
Maize CBH-351 ACS-ZM004-3 Insect res.; glufosinate toi. cry9C; bar
Maize DAS40278-9 DAS40278-9 2,4-D toi. aad-1
Maize DBT418 DKB-89614-9 Insect res.; glufosinate toi. crylAc; pinll; bar
Maize DLL25 (B 16) DKB-89790-5 Glufosinate toi. bar
Maize GA21 MON-00021-9 Glyphosate toi. mepsps
Maize GG25 Glyphosate toi. mepsps
Maize GUI Glyphosate toi. mepsps
Maize Fil 17 Glyphosate toi. mepsps
Maize GAT-ZM1 Glufosinate toi. pat
Maize LY038 REN-00038-3 Increased lysine cordapA
Maize MIR162 SYN-IR162-4 Insect res. vip3Aa20
Maize MIR604 SYN-IR604-5 Insect res. mcry3A
Maize MON801 (MON80100) MON801 Insect res.; glyphosate toi. crylAb; cp4 epsps (aroA:CP4); goxv247
Maize MON802 MON-80200-7 Insect res.; glyphosate toi. crylAb; cp4 epsps (aroA:CP4); goxv247
Maize MON809 PH-MON-809-2 InSect res.; glyphosate toi. crylAb; cp4 epsps (aroA:CP4); goxv247
Maize MON810 MON-00810-6 Insect res.; glyphosate toi. crylAb; cp4 epsps (aroA:CP4); goxv247
Maize MON832 NA Glyphosate toi. cp4 epsps (aroA:CP4); goxv247
Maize MON863 MON-00863-5 Insect res. cry3Bbl
Maize MON87427 MON-87427-7 Glyphosate toi. cp4 epsps (aroA:CP4)
Maize MON87460 MON-87460-4 Drought toi. cspB
Maize MON88017 MON-88017-3 Insect res.; glyphosate toi. cry3Bbl; cp4 epsps (aroA:CP4)
Maize MON89034 MON-89034-3 Insect res. cry2Ab2; crylA.105
Maize MS3 ACS-ZM001-9 Glufosinate toi.; pollination control bar; bamase
Maize MS6 ACS-ZM005-4 Glufosinate toi.; pollination control bar; bamase
Maize NK603 MON-00603-6 Glyphosate toi. cp4 epsps (aroA:CP4)
Maize T14 ACS-ZM002-1 Glufosinate toi. pat (syn)
Maize T25 ACS-ZM003-2 Glufosinate toi. pat (syn)
Maize TC1507 DAS-01507-1 Insect res.; glufosinate toi. crylFa2; pat
Maize Maize TC6275 VIP1034 DAS-06275-8 Insect res.; glufosinate toi. Insect res.; glufosinate toi. mocrylF; bar vip3A; pat
Maize 43A47 DP-043A47-3 Insect res.; glufosinate toi. crylF; cry34Abl; cry35Abl; pat
Maize 40416 DP-040416-8 Insect res.; glufosinate toi. crylF; cry34Abl; cry35Abl; pat
Maize 32316 DP-032316-8 Insect res.; glufosinate toi. crylF; cry34Abl; cry35Abl; pat
Maize 4114 DP-004114-3 Insect res.; glufosinate toi. crylF; cry34Abl; cry35Abl; pat
Melon Melon A NA Delayed ripening/senescence sam-k
Melon Melon B NA Delayed ripening/senescence sam-k
Papaya 55-1 CUH-CP551-8 Disease res. prsv cp
Papaya 63-1 CUH-CP631-7 Disease res. prsv cp
Papaya HuanongNo. 1 NA Disease res. prsv rep
Papaya X17-2 UFL-X17CP-6 Disease res. prsv cp
Pétunia Petunia-CHS NA Modifïed product quality CHS suppres.sion
Plum C-5 ARS-PLMC5-6 Disease res. ppv cp
Canola** ZSR500 NA Glyphosate toi. cp4 epsps (aroA:CP4); goxv247
Canola** ZSR502 NA Glyphosate toi. cp4 epsps (aroA:CP4); goxv247
Canola** ZSR503 NA Glyphosate toi. cp4 epsps (aroA:CP4); goxv247
Poplar Bt poplar NA Insect res. crylAc; API
Poplar Hybrid poplar clone 741 NA Insect res. crylAc; API
112
Poplar trg300-l High cellulose AaXEG2
Poplar trg300-2 High cellulose AaXEG2
Potato 1210 amk NA Insect res. cry3A
Potato 2904/1 kgs NA Insect res. cry3A
Canola** ZSR500 NA Glyphosate toi. cp4 epsps (aroA:CP4); goxv247
Canola** ZSR502 NA Glyphosate toi. cp4 epsps (aroA:CP4); goxv247
Potato ATBT04-27 NMK-89367-8 Insect res. cry3A
Potato ATBT04-30 NMK-89613-2 Insect res. cry3A
Potato ATBT04-31 NMK-89170-9 Insect res. cry3A
Potato ATBT04-36 NMK-89279-1 Insect res. cry3A
Potato ΑΤΒΊΌ4-6 NMK-89761-6 Insect res. cry3A
Potato BT06 NMK-89 812-3 Insect res. cry3A
Potato BT10 NMK-89175-5 Insect res. cry3A
Potato BT12 NMK-89601-8 Insect res. cry3A
Potato BT16 NMK-89167-6 Insect res. cry3A
Potato BT17 NMK-89593-9 Insect res. cry3A
Potato BT18 NMK-89906-7 Insect res. cry3A
Potato BT23 NMK-89675-1 Insect res. cry3A
Potato EH92-527-1 BPS-25271-9 Modified starch/carbohydrate gbss (antisense)
Potato HLMT15-15 NA Insect & disease res. cry3A; pvy cp
Potato HLMT15-3 NA Insect & disease res. cry3A; pvy cp
Potato HLMT15-46 NA Insect & disease res. cry3A; pvy cp
Potato RBMT15-101 NMK-89653-6 Insect & disease res. cry3A; pvy cp
Potato RBMT21-129 NMK-89684-1 Insect & disease res. cry3 A; plrv orfl ; plrv orf2
Potato RBMT21-152 NA Insect & disease res. cry3A; plrv orfl ; plrv orf2
Potato RBMT21-350 NMK-89185-6 Insect & disease res. cry3A; plrv orfl; plrv orf2
Potato RBMT22-082 NMK-89896-6 Insect & disease res.; Glyphosate toi. cry3A; plrv orfl ; plrv orf2; cp4 epsps (aroA:CP4)
Potato RBMT22-186 NA Insect & disease res.; Glyphosate toi. cry3A; plrv orfl ; plrv orf2; cp4 epsps (aroA:CP4)
Potato RBMT22-238 NA Insect & disease res.; Glyphosate toi. cry3A; plrv orfl; plrv orf2; cp4 epsps (aroA:CP4)
113
Potato RBMT22-262 NA Insect & disease res.; Glyphosate toi. cry3A; plrv orfl; plrv orf2; cp4 epsps (aroA:CP4)
Potato SEMT15-02 NMK-89935-9 Insect & disease res. cry3A; pvy cp
Potato SEMT15-07 NA Insect & disease res. cry3A; pvy cp
Potato SEMT15-15 NMK-89930-4 Insect & disease res. cry3A; pvy cp
Potato SPBT02-5 NMK-89576-1 Insect res. cry3A
Potato SPBT02-7 NMK-89724-5 Insect res. cry3A
Rice 7Crp#242-95-7 Anti-allergy 7crp
Rice 7Crp#10 NA Anti-allergy 7crp
Rice GM Shanyou 63 NA Insect res. crylAb; crylAc
Rice Huahui-1/TT51-1 NA Insect res. crylAb; crylAc
Rice LLRICE06 ACS-OSOOl-4 Glufosinate toi. bar
Rice LLRICE601 BCS-OS003-7 Glufosinate toi. bar
Rice LLRICE62 ACS-OS002-5 Glufosinate toi. bar
Rice Tarom molaii + crylAb NA Insect res. crylAb (truncated)
Rice GAT-OS2 Glufosinate toi. bar
Rice GAT-OS3 Glufosinate toi. bar
Rice PE-7 Insect res. CrylAc
Rice 7Crp#10 NA Anti-allergy 7 erp
Rice KPD627-8 High tryptophan OASA1D
Rice KPD722-4 High tryptophan OASA1D
Rice KA317 High tryptophan OASA1D
Rice HW5 High tryptophan OASA1D
Rice HW1 High tryptophan OASA1D
Rice B-4-1-18 Erect leaves semidwarf Δ OsBRIl
Rice G-3-3-22 Semidwarf OSGA2oxl
Rice AD77 Disease res. DEF
Rice AD51 Disease res. DEF
Rice AD48 Disease res. DEF
Rice AD41 Disease res. DEF
Rice 13pNasNaatAprtl Low iron toi. HvNASl; HvNAAT-A; APRT
Rice 13pAprtl Low iron toi. APRT
Rice gHvNASl- gHvNAAT-1 Low iron toi. HvNASl; HvNAAT-A; HvNAAT-B
Rice gHvIDS3-l Low iron toi. HvIDS3
Rice gHvNAATl Low iron toi. HvNAAT-A; HvNAAT- B
114
Rice gHvNASl-1 Low iron toi. HvNASl
Rice NIA-QS006-4 Disease res. WRKY45
Rice NIA-OS005-3 Disease res. WRKY45
Rice NIA-OS004-2 Disease res. WRKY45
Rice NIA-OS003-1 Disease res. WRKY45
Rice NIA-OS002-9 Disease res. WRKY45
Rice NIA-OSOOl-8 Disease res. WRKY45
Rice OsCrll Anti-allergy Modified Cry j
Rice 17053 Glyphosate toi. cp4 epsps (aroA:CP4)
Rice 17314 Glyphosate toi. cp4 epsps (aroA:CP4)
Rose WKS82/ 130-4-1 IFD-52401-4 Modified flower color 5AT; bp40 (β'5'h)
Rose WKS92 / 130-9-1 IFD-52901-9 Modified flower color 5AT; bp40 (β'5'h)
Soybean 260-05 (G94-1, G94-19, G168) NA Modified oil/fatty acid gm-fad2-l (silencing locus)
Soybean A2704-12 ACS-GM005-3 Glufosinate toi. pat
Soybean A2704-21 ACS-GM004-2 Glufosinate toi. pat
Soybean A5547-127 ACS-GM006-4 Glufosinate toi. pat
Soybean A5547-35 ACS-GM008-6 Glufosinate toi. pat
Soybean CV127 BPS-CV127-9 Imidazolinone toi. csrl-2
Soybean DAS68416-4 DAS68416-4 Glufosinate toi. pat
Soybean DP305423 DP-305423-1 Modified oil/fatty acid; ALS herbicide toi. gm-fad2-l (silencing locus); gm-hra
Soybean DP356043 DP-356043-5 Modified oil/fatty acid; glyphosate toi. gm-fad2-l (silencing locus); gat4601
Soybean FG72 MST-FG072-3 Glyphosate & HPPD toi. 2mepsps; hppdPF W336
Soybean GTS 40-3-2 (40-3- 2) MON-04032-6 Glyphosate toi. cp4 epsps (aroA:CP4)
Soybean GU262 ACS-GM003-1 Glufosinate toi. pat
Soybean MON87701 MON-87701-2 Insect res. crylAc
Soybean MON87705 MON-87705-6 Modified oil/fatty acid; glyphosate toi. fatbl-A (sense & antisense); fad2-lA (sense & antisense); cp4 epsps (aroA:CP4)
Soybean MON87708 MON-87708-9 Dicamba & glyphosate toi. dmo; cp4 epsps (aroA:CP4)
Soybean MON87769 MON-87769-7 Modified oil/fatty acid; glyphosate toi. Pj.D6D; Nc.Fad3; cp4 epsps (aroA:CP4)
Soybean MON89788 MON-89788-1 Glyphosate toi. cp4 epsps (aroA:CP4)
Soybean W62 ACS-GM002-9 Glufosinate toi. bar
Soybean W98 ACS-GM001-8 Glufosinate toi. bar
115
Soybean MON87754 MON-87754-1 High oil dgat2A
Soybean DAS21606 DAS-21606 Aryloxyalkanoate & glufosinate toi. Modified aad-12; pat
Soybean DAS44406 DAS-44406-6 Aryloxyalkanoate, glyphosate & glufosinate toi. Modified aad-12; 2mepsps; pat
Soybean SYHT04R SYN-0004R-8 Mesotrione toi. Modified avhppd
Soybean 9582.814.19.1 Insect res. & glufosinate toi. crylAc, crylF, PAT
Squash CZW3 SEM-0CZW3-2 Disease res. cmv cp, zymv cp, wmv cp
Squash ZW20 SEM-0ZW20-7 Disease res. zymv cp, wmv cp
Sugar Beet GTSB77 (T9100152) SY-GTSB77-8 Glyphosate toi. cp4 epsps (aroA:CP4); goxv247
Sugar Beet H7-1 KM-000H71-4 Glyphosate toi. cp4 epsps (aroA:CP4)
Sugar Beet T120-7 ACS-BV001-3 Glufosinate toi. pat
Sugar Beet T227-1 Glyphosate toi. cp4 epsps (aroA:CP4)
Sugarcane NXI-1T Drought toi. EcbetA
Sunflower X81359 Imidazolinone toi. als
Sweet Pepper PK-SP01 NA Disease res. cmv cp
Tobacco C/F/93/08-02 NA Oxynil toi. bxn
Tobacco Vector 21-41 NA Reduced nicotine NtQPTl (antisense)
Tomato 1345-4 NA Delayed ripening/senescense acc (truncated)
Tomato 35-1-N NA Delayed ripening/senescense sam-k
Tomato 5345 NA Insect res. crylAc
Tomato 8338 CGN-89322-3 Delayed ripening/senescense accd
Tomato B SYN-0000B-6 Delayed ripening/senescense pg (sense or antisense)
Tomato Da SYN-0000DA-9 Delayed ripening/senescense pg (sense or antisense)
Sunflower X81359 Imidazolinone toi. als
Tomato Da Dong No 9 NA Modified product NA
Tomato F (1401F, h38F, 11013F,7913F) SYN-0000F-1 Delayed ripening/senescense pg (sense or antisense)
Tomato FLAVR SAVR™ CGN-89564-2 Delayed ripening/senescense pg (sense or antisense)
Tomato HuafanNo 1 NA Delayed ripening/senescense anti-efe
Tomato PK-TM8805R (8805R) NA Disease res. cmv cp
Wheat MON71800 MON-71800-3 Glyphosate toi. cp4 epsps (aroA:CP4)
* Argentine, ** Polish, # Eggplant
116
Treatment of genetically modified plants and seeds with compounds of the disclosure may resuit in enhanced effects. For example, réduction in application rates, broadening of the activity spectrum, increased tolérance to biotic/abiotic stresses or enhanced storage stabilitymay be greater than expected from just simple additive effects of the application of compounds of the disclosure on genetically modified plants and seeds.
Compounds of this disclosure are also usefiil in seed treatments for protecting seeds from invertebrate pests. In the context of the présent disclosure and daims, treating a seed means contacting the seed with a biologically effective amount of a compound of this disclosure, which is typically formulated as a composition of the disclosure. This seed treatment protects the seed from invertebrate soil pests and generally can also protect roots and other plant parts in contact with the soil of the seedling developing from the germinating seed. The seed treatment may also provide protection of foliage by translocation of the compound of this disclosure or a second active ingrédient within the developing plant. Seed treatments can be applied to ail types of seeds, including those from which plants genetically transformed to express specialized traits will germinate. Représentative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis toxin or those expressing herbicide résistance such as glyphosate acetyltransferase, which provides résistance to glyphosate. Seed treatments with compounds of this disclosure can also increase vigor of plants growing from the treated seed.
One method of seed treatment is by spraying or dusting the seed with a compound of the disclosure (i.e. as a formulated composition) before sowing the seeds. Compositions formulated for seed treatment generally comprise a film former or adhesive agent. Therefore typically a seed coating composition of the présent disclosure comprises a biologically effective amount of a compound of Formula 1, an TV-oxide or sait thereof, and a film former or adhesive agent. Seed can be coated by spraying a flowable suspension concentrate directly into a tumbling bed of seeds and then drying the seeds. Altematively, other formulation types such as wetted powders, solutions, suspoemulsions, emulsifiable concentrâtes and émulsions in water can be sprayed on the seed. This process is particularly usefùl for applying film coatings on seeds. Varions coating machines and processes are available to one skilled in the art. Suitable processes include those listed in P. Kosters et al., Seed Treatment: Progress and Prospects, 1994 BCPC Mongraph No. 57, and references listed therein.
Compounds of Formula 1 and their compositions, both alone and in combination with other insecticides and fungicides, are particularly useful in seed treatment for crops including, but not limited to, maize or corn, soybeans, cotton, cereal (e.g., wheat, oats, barley, rye and rice), potatoes, vegetables and oilseed râpe.
117
Other insecticides with which compounds of Formula 1 can be formulated to provide mixtures useful in seed treatment include abamectin, acetamiprid, acrinathrin, amitraz, avermectin, azadirachtin, bensultap, bifenthrin, buprofezin, carbaryl, carbofuran, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flonicamid, flubendiamide, fhifenoxuron, fluvalinate, formetanate, fosthiazate, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, metaflumizone, methiocarb, methomyl, methoprene, methoxyfenozide, nitenpyram, nithiazine, novaluron, oxamyl, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide, tetramethrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate, triflumuron, Bacillus thuringiensis deltaendotoxins, ail strains of Bacillus thuringiensis and ail strains of nuclear polyhedrosis viruses.
Fungicides with which compounds of Formula 1 can be formulated to provide mixtures useful in seed treatment include amisulbrom, azoxystrobin, boscalid, carbendazim, carboxin, cymoxanil, cyproconazole, difenoconazole, dimethomorph, fluazinam, fludioxonil, fluquinconazole, fluopicolide, fluoxastrobin, flutriafol, fluxapyroxad, ipconazole, iprodione, metalaxyl, mefenoxam, metconazole, myclobutanil, paclobutrazole, penflufen, picoxystrobin, prothioconazole, pyraclostrobin, sedaxane, silthiofam, tebuconazole, thiabendazole, thiophanatemethyl, thiram, trifloxystrobin and triticonazole.
Compositions comprising compounds of Formula 1 useful for seed treatment can further comprise bacteria such as Bacillus pumilus (e.g., strain GB34) and Bacillus firmus (e.g., isolate 1582), rhizobia inoculants/extenders, isoflavonoids and lipo-chitooligosaccharides.
The treated seed typically comprises a compound of the présent disclosure in an amount from about 0.1 g to 1 kg per 100 kg of seed (i.e. from about 0.0001 to 1% by weight of the seed before treatment). A flowable suspension formulated for seed treatment typically comprises from about 0.5 to about 70% of the active ingrédient, from about 0.5 to about 30% of a film-forming adhesive, from about 0.5 to about 20% of a dispersing agent, from 0 to about 5% of a thickener, from 0 to about 5% of a pigment and/or dye, from 0 to about 2% of an antifoaming agent, from 0 to about 1% of a preservative, and from 0 to about 75% of a volatile liquid diluent.
The compounds of this disclosure can be incorporated into a bait composition that is consumed by an invertebrate pest or used within a device such as a trap, bait station, and the like. Such a bait composition can be in the form of granules which comprise (a) active ingrédients,
118 namely a biologically effective amount of a compound of Formula 1, an 7V-oxide, or sait thereof; (b) one or more food materials; optionally (c) an attractant, and optionally (d) one or more humectants. Of note are granules or bait compositions which comprise between about 0.001-5% active ingrédients, about 40-99% food material and/or attractant; and optionally about 0.05-10% humectants, which are effective in controlling soil invertebrate pests at very low application rates, particularly at doses of active ingrédient that are léthal by ingestion rather than by direct contact. Some food materials can function both as a food source and an attractant. Food materials include carbohydrates, proteins and lipids. Examples of food materials are vegetable flour, sugar, starches, animal fat, vegetable oil, yeast extracts and milk solids. Examples of attractants are odorants and flavorants, such as fruit or plant extracts, perfume, or other animal or plant component, pheromones or other agents known to attract a target invertebrate pest. Examples of humectants, i.e. moisture retaining agents, are glycols and other polyols, glycérine and sorbitol. Of note is a bait composition (and a method utilizing such a bait composition) used to control at least one invertebrate pest selected from the group consisting of ants, termites and cockroaches. A device for controlling an invertebrate pest can comprise the présent bait composition and a housing adapted to receive the bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to the bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest.
The compounds of this disclosure can be applied without other adjuvants, but most often application will be of a formulation comprising one or more active ingrédients with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. One method of application involves spraying a water dispersion or refined oil solution of a compound of the présent disclosure. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and piperonyl butoxide often enhance compound efficacy. For nonagronomic uses such sprays can be applied from spray containers such as a can, a bottle or other container, either by means of a pump or by releasing it from a pressurized container, e.g., a pressurized aérosol spray can. Such spray compositions can take varions forms, for example, sprays, mists, foams, fumes or fog. Such spray compositions thus can further comprise propellants, foaming agents, etc. as the case may be. Of note is a spray composition comprising a biologically effective amount of a compound or a composition of the présent disclosure and a carrier. One embodiment of such a spray composition comprises a biologically effective amount of a compound or a composition of the présent disclosure and a propellant. Représentative propellants include, but are not limited to, methane, ethane, propane,
119 butane, isobutane, butene, pentane, isopentane, neopentane, pentene, hydrofluorocarbons, chlorofluorocarbons, dimethyl ether, and mixtures of the foregoing. Of note is a spray composition (and a method utilizing such a spray composition dispensed from a spray container) used to control at least one invertebrate pest seleçted from the group consisting of mosquitoes, black flies, stable flies, deer Aies, horse flies, wasps, yellow jackets, homets, ticks, spiders, ants, gnats, and the like, including individually or in combinations.
One embodiment of the présent disclosure relates to a method for controlling invertebrate pests, comprising diluting the pesticidal composition of the présent disclosure (a compound of Formula 1 formulated with surfactants, solid diluents and liquid diluents or a formulated mixture of a compound of Formula 1 and at least one other pesticide) with water, and optionally adding an adjuvant to form a diluted composition, and contacting the invertebrate pest or its environment with an effective amount of said diluted composition.
Although a spray composition formed by diluting with water a sufficient concentration of the présent pesticidal composition can provide sufficient efficacy for controlling invertebrate pests, separately formulated adjuvant products can also be added to spray tank mixtures. These additional adjuvants are commonly known as “spray adjuvants” or “tank-mix adjuvants”, and include any substance mixed in a spray tank to improve the performance of a pesticide or alter the physical properties of the spray mixture. Adjuvants can be surfactants, emulsifying agents, petroleum-based crop oils, crop-derived seed oils, acidifiers, buffers, thickeners or defoaming agents. Adjuvants are used to enhancing efficacy (e.g., biological availability, adhesion, pénétration, uniformity of coverage and durability of protection), or minimizing or eliminating spray application problems associated with incompatibility, foaming, drift, évaporation, volatilization and dégradation. To obtain optimal performance, adjuvants are seleçted with regard to the properties of the active ingrédient, formulation and target (e.g., crops, insect pests).
Among the spray adjuvants, oils including crop oils, crop oil concentrâtes, vegetable oil concentrâtes and methylated seed oil concentrâtes are most commonly used to improve the efficacy of pesticides, possibly by means of promoting more even and uniform spray deposits. In situations where phytotoxicity potentially caused by oils or other water-immiscible liquids are of concem, spray compositions prepared from the composition of the présent disclosure will generally not contain oil-based spray adjuvants. However, in situations where phytotoxicity caused by oil-based spray adjuvants is commercially insignificant, spray compositions prepared from the composition of the présent composition can also contain oil-based spray adjuvants, which can potentially further increase control of invertebrate pests, as well as rainfastness.
120
Products identified as “crop oil” typically contain 95 to 98% paraffin or naphtha-based petroleum oil and 1 to 2% of one or more surfactants functioning as emulsifiers. Products identified as “crop oil concentrâtes” typically consist of 80 to 85% of emulsifiable petroleumbased oil and 15 to 20% of nonionic surfactants. Products correctly identified as “vegetable oil concentrâtes” typically consist of 80 to 85% of vegetable oil (i.e. seed or fruit oil, most commonly from cotton, linseed, soybean or sunflower) and 15 to 20% of nonionic surfactants. Adjuvant performance can be improved by replacing the vegetable oil with methyl esters of fatty acids that are typically derived from vegetable oils. Examples of methylated seed oil concentrâtes include MSO® Concentrate (UAP-Loveland Products, Inc.) and Premium MSO Methylated Spray Oil (Helena Chemical Company).
The amount of adjuvants added to spray mixtures generally does not exceed about 2.5% by volume, and more typically the amount is from about 0.1 to about 1% by volume. The application rates of adjuvants added to spray mixtures are typically between about 1 to 5 L per hectare. Représentative examples of spray adjuvants include: Adigor® (Syngenta) 47% methylated rapeseed oil in liquid hydrocarbons, Silwet® (Helena Chemical Company) polyalkyleneoxide modified heptamethyltrisiloxane and Assist® (BASF) 17% surfactant blend in 83% paraffin based minerai oil.
Nonagronomic applications include protecting an animal, particularly a vertebrate, more particularly a homéothermie vertebrate (e.g., mammal or bird) and most particularly a mammal, from an invertebrate parasitic pest by administering a parasiticidally effective (i.e. biologically effective) amount of a compound of the disclosure, typically in the form of a composition formulated for veterinary use, to the animal to be protected. Therefore of note is a method for protecting an animal comprising administering to the animal a parasiticidally effective amount of a compound of the disclosure. As referred to in the présent disclosure and daims, the ternis “parasiticidal” and “parasiticidally” refers to observable effects on an invertebrate parasite pest to provide protection of an animal from the pest. Parasiticidal effects typically relate to diminishing the occurrence or activity of the target invertebrate parasitic pest. Such effects on the pest include necrosis, death, retarded growth, diminished mobility or lessened ability to remain on or in the host animal, reduced feeding and inhibition of reproduction. These effects on invertebrate parasite pests provide control (including prévention, réduction or élimination) of parasitic infestation or infection of the animal. Examples of invertebrate parasitic pests controlled by administering a parasiticidally effective amount of a compound of the disclosure to an animal to be protected include ectoparasites (arthropods, acarines, etc) and endoparasites (helminths, e.g., nematodes, trematodes, cestodes, acanthocephalans, etc.). In particular, the compounds of this disclosure are
121 effective against ectoparasites including: flies such as Haematobia (Lyperosia) irritons (hom fly), Stomoxys calcitrans (stable fly), Simulium spp. (blackfly), Glossina spp. (tsetse flies), Hydrotaea irritons (head fly), Musca autumnalis (face fly), Musca domestica (house fly), Morellia simplex (sweat fly), Tabanus spp. (horse fly), Hypoderma bovis, Hypoderma lineatum, Lucilia sericata, Lucilia cuprina (greenblowfly), Calliphora spp. (blowfly), Protophormia spp., Oestrus ovis (nasal botfly), Culicoides spp. (midges), Hippobosca equine, Gastrophilus instestinalis, Gastrophilus haemorrhoidalis and Gastrophilus naslis', lice such as Bovicola (Damalinia) bovis, Bovicola equi, Haematopinus asini, Felicola subrostratus, Heterodoxus spiniger, Lignonathus setosus and Trichodectes canis; keds such as Melophagus ovinus; mites such as Psoroptes spp., Sarcoptes scabei, Chorioptes bovis, Demodex equi, Cheyletiella spp., Notoedres cati, Trombicula spp. and Otodectes cyanotis (ear mites); ticks such as Ixodes spp., Boophilus spp., Rhipicephalus spp., Amblyomma spp., Dermacentor spp., Hyalomma spp. and Haemaphysalis spp.; and fleas such as Ctenocephalides felis (cat flea) and Ctenocephalides canis (dog flea).
Nonagronomic applications in the veterinary sector are by conventional means such as by enterai administration in the form of, for example, tablets, capsules, drinks, drenching préparations, granulates, pastes, boli, feed-through procedures, or suppositories; or by parentéral administration, such as by injection (including intramuscular, subcutaneous, intravenous, intraperitoneal) or implants; by nasal administration; by topical administration, for example, in the form of immersion or dipping, spraying, washing, coating with powder, or application to a small area of the animal, and through articles such as neck collars, ear tags, tail bands, limb bands or halters which comprise compounds or compositions of the présent disclosure.
Typically a parasiticidal composition according to the présent disclosure comprises a mixture of a compound of Formula 1, an TV-oxide or a sait thereof, with one or more pharmaceutically or veterinarily acceptable carriers comprising excipients and auxiliaries selected with regard to the intended route of administration (e.g., oral, topical or parentéral administration such as injection) and in accordance with standard practice. In addition, a suitable carrier is selected on the basis of compatibility with the one or more active ingrédients in the composition, including such considérations as stability relative to pH and moisture content. Therefore of note is a composition for protecting an animal from an invertebrate parasitic pest comprising a parasitically effective amount of a compound of the disclosure and at least one carrier.
For parentéral administration including intravenous, intramuscular and subcutaneous injection, a compound of the présent disclosure can be formulated in suspension, solution or émulsion in oily or aqueous vehicles, and may contain adjuncts such as suspending, stabilizing and/or dispersing agents. Pharmaceutical compositions for injection include aqueous solutions of
122 water-soluble forms of active ingrédients (e.g., a sait of an active compound), preferably in physiologically compatible buffers containing other excipients or auxiliaries as are known in the art of pharmaceutical formulation.
For oral administration in the form of solutions (the most readily available form for absorption), émulsions, suspensions, pastes, gels, capsules, tablets, boluses powders, granules, rumen-retention and feed/water/lick blocks, a compound of the present disclosure can be formulated with binders/fillers known in the art to be suitable for oral administration compositions, such as sugars (e.g., lactose, sucrose, mannitol, sorbitol), starch (e.g., maize starch, wheat starch, rice starch, potato starch), cellulose and dérivatives (e.g., methylcellulose, carboxymethylcellulose, ethylhydroxycellulose), protein dérivatives (e.g., zein, gelatin), and synthetic polymers (e.g., polyvinyl alcohol, polyvinylpyrrolidone). If desired, lubricants (e.g., magnésium stéarate), disintegrating agents (e.g., cross-linked polyvinylpyrrolidinone, agar, alginic acid) and dyes or pigments canbe added. Pastes and gels often also contain adhesives (e.g., acacia, alginic acid, bentonite, cellulose, xanthan gum, colloïdal magnésium aluminum silicate) to aid in keeping the composition in contact with the oral cavity and not being easily ejected.
If the parasiticidal compositions are in the form of feed concentrâtes, the carrier is typically selected from high-performance feed, feed cereals or protein concentrâtes. Such feed concentratecontaining compositions can, in addition to the parasiticidal active ingrédients, comprise additives promoting animal health or growth, improving quality of méat from animais for slaughter or otherwise useful to animal husbandry. These additives can include, for example, vitamins, antibiotics, chemotherapeutics, bacteriostats, fungistats, coccidiostats and hormones.
Compounds of the present disclosure hâve been discovered to hâve favorable pharmacokinetic and pharmacodynamie properties providing systemic availability from oral administration and ingestion. Therefore after ingestion by the animal to be protected, parasiticidally effective concentrations of compounds of the disclosure in the bloodstream protect the treated animal from blood-sucking pests such as fleas, ticks and lice. Therefore of note is a composition for protecting an animal from an invertebrate parasite pest in a form for oral administration (i.e. comprising, in addition to a parasiticidally effective amount of a compound of the disclosure, one or more carriers selected from binders and fillers suitable for oral administration and feed concentrate carriers).
Formulations for topical administration are typically in the form of a powder, cream, suspension, spray, émulsion, foam, paste, aérosol, ointment, salve or gel. More typically a topical formulation is a water-soluble solution, which can be in the form of a concentrate that is diluted before use. Parasiticidal compositions suitable for topical administration typically comprise a
123 compound of the présent disclosure and one or more topically suitable carriers. In applications of a parasiticidal composition topically to the exterior of an animal as a line or spot (i.e. “spot-on” treatment), the active ingrédient migrâtes over the surface of the animal to cover most or ail of its extemal surface area. As a resuit, the treated animal is particularly protected from invertebrate pests that feed off the epidermis of the animal such as ticks, fleas and lice. Therefore formulations for topical localized administration often comprise at least one organic solvent to facilitate transport of the active ingrédient over the skin and/or pénétration into the epidermis of the animal. Solvents commonly used as carriers in such formulations include propylene glycol, parafions, aromatics, esters such as isopropyl myristate, glycol ethers, and alcohols such as éthanol and npropanol.
The rate of application required for effective control (i.e. “biologically effective amount”) will dépend on such factors as the species of invertebrate to be controlled, the pest’s life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, température, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingrédients per hectare are sufficient to control pests in agronomie ecosystems, but as little as 0.0001 kg/hectare may be sufficient or as much as 8 kg/hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required. One skilled in the art can easily détermine the biologically effective amount necessary for the desired level of invertebrate pest control.
In general for veterinary use, a compound of Formula 1, an TV-oxide or a sait thereof, is administered in a parasiticidally effective amount to an animal to be protected from invertebrate parasite pests. A parasiticidally effective amount is the amount of active ingrédient needed to achieve an observable effect diminishing the occurrence or activity of the target invertebrate parasite pest. One skilled in the art will appreciate that the parasitically effective dose can vary for the varions compounds and compositions of the présent disclosure, the desired parasitical effect and duration, the target invertebrate pest species, the animal to be protected, the mode of application and the like, and the amount needed to achieve a particular resuit can be determined through simple expérimentation.
For oral administration to homéothermie animais, the daily dosage of a compound of the présent disclosure typically ranges from about 0.01 mg/kg to about 100 mg/kg, more typically from about 0.5 mg/kg to about 100 mg/kg, of animal body weight. For topical (e.g., dermal) administration, dips and sprays typically contain from about 0.5 ppm to about 5000 ppm, more typically from about 1 ppm to about 3000 ppm, of a compound of the présent disclosure.
124
Spécifie compounds of Formula 1 prepared by the methods and variations as described in preceding Schemes 1-11 and Synthesis Examples 1-2, are shown in the Index Tables A and B below. See Index Table C for *H NMR data. For mass spectral (MS) data, the numerical value reported is the molecular weight of the highest isotopic abundance parent ion (M+l) formed by 5 addition of H+ (molecular weight of 1) to the molécule, observed by mass spectrometry using atmospheric pressure Chemical ionization (AP+). The following abbreviations are used in the Index Tables which follow: Cmpd means Compound, t is tertiary, c is cyclo, Me is methyl, Et is ethyl, Pr is propyl, z-Pr is isopropyl, Bu is butyl, c-Pr is cyclopropyl, c-Pn is cyclopentyl, c-Hx is cyclohexyl, /-Bu is Zerriary-butyl, Ph is phenyl, OMe is methoxy, SMe is methylthio, and 10 SO2Me means methylsulfonyl. A wavy line in a structure fragment dénotés the attachment point of the fragment to the remainder of the molécule. The abbreviation “Ex.” stands for “Example” and is followed by a number indicating in which Synthesis Example the compound is prepared.
INDEX TABLE A
Cmpd. No. R3 R4 RW MS data
1 F pyrazol-l-yl -SCF3 372
2 F 1//-1,2,4-triazol-1 -yl -scf3 373
3 F 2//-l,2,3-triazol-2-yl -scf3 373
4 F 3-(trifluoromethyl)-\Hpyrazol-l-yl -scf3 440
5 F 3 -methyl- 1/7-pyrazol-1 -yl -scf3 386
6 F 4-methyl- l//-pyrazol-1 -yl -scf3 386
7 F 1/7-1,2,4-triazol-1 -yl -scf3 357
8 F 2/7-l,2,3-triazol-2-yl -ocf3 357
9 H 2//-1,2,3-triazol-2-yl -ocf3 339
10 H IH-1,2,3-triazol-l-yl -ocf3 339
11 H pyrazol-l-yl -ocf3 338
125
12 H 1H-1,2,4-triazol-1 -yl -OCF3 339
13 H 27/-1,2,3-triazol-2-yl -ocf2chf2 389
14 Cl ΊΗ-1,2,3-triazol-2-yl -OCF3 373
15 Cl 1 H-1,2,4-triazol-1 -yl -OCF3 373
17 Br 2H-1,2,3-triazol-2-yl -OCF3 417
18 F 17/-1,2,4-triazol-l-yl -cf3 341
19 F 27/-1,2,3-triazol-2-yl -OCF3 369
20 F 27/-l,2,3-triazol-2-yl -CF3 341
21 F pyrazol-l-yl -CF3 340
22 F furan-2-yl -OCF3 356
23 F furan-3-yl -OCF3 356
24 Cl 2X2-tetrazol-5-yl -OCF3 374
25 F 1 -methyl- 17/-imidazol-2-yl -OCF3 370
26 F l//-pyrrol-2-yl -OCF3 355
27 Br //° EtOC ,-- FV N N JL -OCF3 517
28 Br //° EtOC N N JL -OCF3 489
29 Br 4,5-dibromo-27/-l,2,3triazol-2-yl -OCF3 *
30 F 1,3,4-oxadiazol-2-yl -OCF3 358
31 F 5-methyl-1,3,4-oxadiazol2-yl -OCF3 372
32 F oxazol-2-yl -OCF3 357
33 F thiazol-2-yl -OCF3 373
34 F oxazol-5-yl -OCF3 357
35 -OMe oxazol-5-yl -OCF3 369
36 F thiazol-2-yl -OCF3 *
38 Me 27/-1,2,3-triazol-2-yl -OCF3 353
126
39 F 3-methyl-l,2,4-oxadiazol- 5-yl -ocf3 *
40 F 177-1,2,4-triazol-3 -yl -ocf3 357
41 F isoxazol-5-yl -ocf3 357
42 F 177-pyrazol-5-yl -ocf3 357
43 F 277-1,2,3-triazol-2-yl C(OMe)(CF3) 2 453
44 F 1-ethyl- 177-pyrazol-4-yl -OCF3 384
45 F thiophen-2-yl -ocf3 372
46 F thiophen-3-yl -ocf3 372
47 Me 177-1,2,3-triazol-l-yl -ocf3 353
48 CN 277-1,2,3-triazol-2-yl -ocf3 *
49 F thiazol-4-yl -ocf3 373
50 Cl thiazol-2-yl -ocf3 389
51 Cl oxazol-2-yl -ocf3 373
53 c-propyl 277-1,2,3-triazol-2-yl -ocf3 379
54 F 277-l,2,3-triazol-2-yl -so2cf3 405
55 F 1 -ethyl- 177-pyrazol-5-yl -ocf3 384
56 F 1 -isopropyl- 177-pyrazol-4yi -ocf3 398
57 F 1 -ethyl- 177-pyrazol-3-yl -ocf3 384
58 F 1 -(2,2,2-trifluoroethyl)-177pyrazol-4-yl -ocf3 438
59 F l-methyl-177-pyrazol-3-yl -ocf3 370
60 Cl oxazol-5-yl -ocf3 373
61 F 477-1,2,4-triazol-4-yl -scf3 372
62 F 1 -z-propyl-177-pyrazol-3 -yl -ocf3 398
63 F 1 -(2,2,2-trifluoroethyl)-177pyrazol-3-yl -ocf3 438
64 Br 277-l,2,3-triazol-2-yl -so2cf3 465
67 F 277-l,2,3-triazol-2-yl -socf3 389
68 H 177-1,2,3-triazol-l-yl -scf3 355
127
69 H 2/7-1,2,3-triazol-2-yl -scf3 355
73 F pyrazol-l-yl -socf3 388
77 F thiazol-2-yl -scf3 389
78 F oxazol-2-yl -scf3 373
85 Br pyrazol-l-yl -scf3 432
86 Br 2/7-l,2,3-triazol-2-yl -scf3 433
87 Br l//-l,2,3-triazol-l-yl -scf3 433
88 Cl pyrazol-l-yl -OCF3 372
89 Cl 2/7-1,2,3-triazol-2-yl -SCF3 389
90 Cl 2/7-1,2,3-triazol-2-yl -SOCF3 405
91 Cl 2/7-1,2,3-triazol-2-yl -SO2CF3 421
92 F 2/7-1,2,3-triazol-2-yl Br 351
93 F 3-methyl-l ,2,4-oxadiazol5-yl SCF3 388
94 F 3 -methyl-1,2,4-oxadiazol5-yl SOCF3 404
95 I 2/7-1,2,3-triazol-2-yl SCF3 481
96 F O^O T SCF3 378
97 I 2/7-1,2,3-triazol-2-yl SOCF3 497
98 F .... SCF3 392
99 I 2/7-l,2,3-triazol-2-yl CF2H 431
100 F oxazol-5-yl SCF3 373
101 F oxazol-5-yl SOCF3 389
102 Cl pyrazol-l-yl SCF3 388
103 Cl 3 -methyl-1,2,4-oxadiazol5-yl SCF3 404
104 Cl 3-methyl-l ,2,4-oxadiazol5-yl SOCF3 420
105 Cl oxazol-5-yl SCF3 389
128
106 Cl 1,2,4-oxadiazol-5-yl SCF3 390
107 Cl oxazol-5-yl SOCF3 405
108 Br 2H-1,2,3-triazol-2-yl t-Bu 389
109 Cl 277-1,2,3-triazol-2-yl Br 367
110 Cl 277-l,2,3-triazol-2-yl t-Bu 345
111 F Thiophene-2-yl SCF3 388
112 F Thiophene-2-yl SCF3 388
113 F 2-methyl- thiophene-3-yl SCF3 402
114 F 3-methyl- thiophene-4-yl SCF3 402
115 F 4-methyl-277-1,2,3-triazol2-yl SCF3 387
116 F 4-methyl- 1H-1,2,3-triazol- 1-yl SCF3 387
INDEX TABLE B
R3 OMe
Cmpd. No. R3 R4 RW MS data
16 Cl 277-l,2,3-triazol-2-yl -ocf3 385
37 F pyrazol-l-yl -ocf3 368
52 Cl pyrazol-l-yl -ocf3 384
65 Br 277-l,2,3-triazol-2-yl -ocf3 429
66 Br pyrazol-l-yl -ocf3 428
70 F pyrazol-l-yl -scf3 384
71 F 177-1,2,4-triazol-1 -yl -scf3 385
72 F pyrazol-l-yl -socf3 400
74 F 177-1,2,4-triazol-1 -yl -socf3 401
75 F thiazol-2-yl -scf3 401
129
76 F oxazol-2-yl -scf3 385
79 F 5-methyl-1,2,4-oxadiazol3-yl -scf3 400
80 F 2,5-dihydro-5-oxo-l ,2,4oxadiazol-3-yl -scf3 402
81 F 5-trifluoromethyl-1,2,4oxadiazol-3-yl -scf3 454
82 F 3-methyl-5-isoxazolyl -scf3 399
83 F 1,2,4-oxadiazol-3-yl -scf3 386
84 F 2,5-dihydro-5-thioxo-1,2, 4-oxadiazol-3-yl -scf3 418
117 F 277-1,2,3-triazol-2-yl Br 363
118 F 277-1,2,3-triazol-2-yl SCF2H 367
119 I pyrazol-l-yl SCF3 492
120 I 2H-1,2,3 -triazol-2-yl SCF3 493
121 F 3-nitrile- pyrazol-l-yl SCF3 409
122 F JO7O SCF3 442
123 F 277-l,2,3-triazol-2-yl SCF3 385
124 F 277-1,2,3-triazol-2-yl OCF3 369/S-enantiomer* *
125 F 277-1,2,3-triazol-2-yl OCF3 3 69/R-enantiomer
126 Cl 177-1,2,3-triazol-1-yl OCF3 385
127 Cl 2H-1,2,3 -triazol-2-yl SCF3 401
128 Cl 177-1,2,3-triazol-l-yl SCF3 401
129 I 277-l,2,3-triazol-2-yl OCF3 477
130 Cl 277-l,2,3-triazol-2-yl SCF3 401 /R-enantiomer
131 Cl 277-1,2,3-triazol-2-yl SCF3 401/S-enantiomer
130
132 F 0 H2N-Y N 1 1 SCF3
133 Br 1H-1,2,3 -triazol-2-yl SCF3 445
134 Br 1/7-1,2,3-triazol-1 -yl SCF3 445
135 F 3-methyl-1,2,4-oxadiazol5-yl SCF3 400
136 F LX N NH2 1 __ î SCF3 399
137 F 3-methyl-1,2,4-oxadiazol5-yl OCF3 384
138 F 1,2,4-oxadiazol-5-yl OCF3 370
139 F 1,2,4-oxadiazol-5-yl t-Bu 342
140 F I // \\ n K N NH2 î SCF3 525
141 F 2tt-l,2,3-triazol-2-yl OCH3 315
142 Cl 3 -methyl-1,2,4-oxadiazol5-yl OCF3 400
143 F 4-methyl-2/7-1,2,3triazol-2-yl SCF3 399
144 Cl 0 0— / \ N·^/0 ____ OCF3 458
145 H 2H-1,2,3-triazol-2-yl OCF3 351
146 Cl 3-methyl-l ,2,4-oxadiazol5-yl SCF3 416
**[α]25= +153.54'
[C=0.30%, ΜΕΟΗ]
Cmpd. No. A R4 RI Q MS data
147 C-Br 2/7-l,2,3-triazol-2-yl F cY' o P 414
148 C-Br 127-1,2,3-triazol-l-yl F T £ X YY F 414
149 C-Cl 1/7-1,2,3-triazol-l-yl F Yx/ f T £ X 369
150 C-Cl 2//-1,2,3-triazol-2-yl F XIX 369
151 C-F pyrazol-l-yl F xix 352
152 C-F 2//-1,2,3-triazol-2-yl F ' Y £ X 353
153 C-Cl pyrazol-l-yl F qY o P 367
154 C-F pyrazol-l-yl OEt P-C6H4OCF3 *
132
155 C-F pyrazol-l-yl OMe F *
156 C-F pyrazol-l-yl F H^<F \ F F 341
157 C-F pyrazol-l-yl OMe \ F F 353
158 C-F 2H-1,2,3-triazol-2-yl OMe %^XF \ F F 354
159 C-F 277-l,2,3-triazol-2-yl OMe xna<f \ F F 342
160 C-F pyrazol-l-yl OMe V F 354
161 C-F 227-l,2,3-triazol-2-yl OMe V F 355
162 C-F pyrazol-l-yl F z=< P 342
163 C-F 2H-Ï ,2,3-triazol-2-yl F V F 343
164 C-F pyrazol-l-yl OMe 363
165 C-F pyrazol-l-yl F ^VV^Br 351
166 C-F 2tt-l,2,3-triazol-2-yl F '^VY^Br 352
167 C-F 2H-1,2,3-triazol-2-yl OMe ^ΗΥ^Βγ 364
168 C-Cl 2H-1,2,3 -triazol-2-yl F 346
133
169 C-Cl 2H-1,2,3-triazol-2-yl F XX W^Br 368
170 C-Cl 2H-l,2,3-triazol-2-yl F Γ 347
171 C-F pyrazol-l-yl F XX_F P 341
172 C-F 2ZM,2,3-triazol-2-yl F OXf P 342
173 C-F pyrazol-l-yl OMe XL· F P 353
174 C-F 2/7-1,2,3 -triazol-2-yl OMe Χφ P 354
175 N 2/7-l,2,3-triazol-2-yl OMe P-C6H4OCF3 352
176 N pyrazol-l-yl OMe P-C6H4OCF3 353
177 N pyrazol-l-yl OMe P-C6H4CF3 335
* See Index Table D for L· NMR data.
INDEX TABLE D
Cmpd. No. IR NMR Data (CDCI3 solution unless indicated otherwise)a
29 δ 8.62 (s, 1H), 8.45 (s, 1H), 7.49 (d, 2H), 7.25 (d, 2H), 6.95 (d, 1H).
36 δ 8.80 (s, br. 1H), 8.55 (s, br. 1H), 8.01 (d, 1H), 7.63 (d, 2H), 7.56 (d, 1H), 7.55 (d, 1H), 7.22 (d, 1H).
39 δ 9.13 (s, 1H), 8.68 (s, 1H), 7.71 (d, 1H), 7.56 (d, 1H), 7.23 (d, 1H), 2.52 (s, 3H).
48 δ 9.29 (s, 1H), 8.99 (s, 1H), 7.96 (s, 2H), 7.44 (d, 2H), 7.40 (d, 1H), 7.23 (d, 1H).
154 δ 8.50 (s, 1H), 8.47 (s, 1H), 7.78 (s, 1H), 7.68 (s, 1H), 7.44 (d, 2H), 7.14 (d, 2H), 6.51 (s, 1H), 5.69 (s, 1H), 3.47 (q, 2H), 1.19 (t, 3H).
155 δ ppm 3.32 (s, 3 H), 5.55 (s, 1 H), 6.55 (s, 1 H), 6.97 (d, J=8.35 Hz, 1 H), 7.10 (d, J=8.05 Hz, 1H), 7.25 - 7.28 (m, 1 H), 7.70 (d, 1=2.57 Hz, 1 H), 7.82 (s, 1 H), 8.47 (s, 1 H), 8.51 (s, 1 H).
134 a NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (m)-multiplet, (dd)-doublet of doublets, (dt)-doublet of triplets, (br s)-broad singlet, (br t)-broad triplet.
The following Tests demonstrate the control effïcacy of compounds of this disclosure on spécifie pests. “Control efficacy” represents inhibition of invertebrate pest development (including mortality) that causes significantly reduced feeding. The pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A and B for compound descriptions.
BIOLOGICAL EXAMPLES
Formulation and Spray Methodology for Tests A-H
Test compounds were formulated using a solution containing 10% acetone, 90% water and 300 ppm Activator 90® non-ionic surfactant (Loveland Products, Loveland, Colorado, USA). The formulated compounds were applied in 1 mL of liquid through an atomizer nozzle positioned 1.27 cm (0.5 inches) above the top of each test unit. Test compounds were sprayed at the rates indicated, and each test was replicated three times.
Test A
For evaluating control of diamondback moth (Plutella xylostella (L.)) the test unit consisted of a small open container with a 12-14-day-old mustard plant inside. This was pre-infested with ~50 neonate larvae that were dispensed into the test unit via corn cob grits using an inoculator. The larvae moved onto the test plant after being dispensed into the test unit.
Test compounds were formulated and sprayed at 250 ppm. After spraying of the formulated test compound, each test unit was allowed to dry for 1 hour and then a black, screened cap was placed on top. The test units were held for 6 days in a growth chamber at 25 °C and 70% relative humidity. Plant feeding damage was then visually assessed based on foliage consumed, and larvae were assessed for mortality.
Of the compounds of Formula 1 tested at 250 ppm, the following provided very good to excellent levels of control efficacy (40% or less feeding damage and/or 100% mortality): 1,3, 18, 19, 20, 21, 22, 23, 29, 30, 32, 33, 34, 36, 39, 45 ,48 ,50 ,51, 53, 55, 59, 60, 78, 89, 92, 100, 103, 104, 105, 118, 120, 123, 125, 130, 133, 147, 155, 162, 166, 171, 172, 175.
Test B
For evaluating control of corn planthopper (Peregrinus maidis (Ashmead)) through contact and/or systemic means, the test unit consisted of a small open container with a 3^1-day-old corn
135 (maize) plant inside. White sand was added to the top of the soil prior to application of the test compound.
Test compounds were formulated and sprayed at 250 and/or 50 ppm and/or lOppm. After spraying of the formulated test compound, the test units were allowed to dry for 1 h before they were post-infested with -15-20 nymphs (18-to-21 -day-old). A black, screened cap was placed on the top of each test unit, and the test units were held for 6 days in a growth chamber at 22-24 °C and 50-70% relative humidity. Each test unit was then visually assessed for insect mortality.
Of the compounds of Formula 1 tested at 250 ppm, the following resulted in at least 80% mortality: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 21, 22, 23, 25, 26, 30, 31, 32, 33, 34,36, 37, 38, 39, 49, 67, 69, 70, 75, 76, 77, 78, 79, 81, 82, 83, 85, 86, 88, 89, 90, 92, 93, 94, 95, 96, 98, 103, 104, 105, 106, 108, 109, 110, 111, 112, 113, 114, 120, 123, 125, 127, 130, 138, 139, 147, 156, 157, 158, 159, 161, 163, 166, 168, 169, 170, 172, 173, 174, 175.
Of the compounds of Formula 1 tested at 50 ppm, the following resulted in at least 80% mortality: 1, 2, 3, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 25, 26, 29, 30, 31, 32, 33, 34,36, 37, 38, 39, 40, 41, 43, 45, 46, 48, 49, 50, 51, 55, 56, 57, 62, 63, 64, 65, 67, 69, 70, 76, 77, 78, 79, 83, 85, 86, 88, 89, 90, 92, 93, 94, 95, 96, 98, 103, 104, 105, 106, 108, 109, 110, 111, 112, 113, 114, 120, 123, 125, 127, 130, 138, 139, 147, 156, 157, 158, 159, 161, 163, 166, 168, 169, 170, 172, 173, 174, 175.
Of the compounds of Formula 1 tested at 10 ppm, the following resulted in at least 80% mortality: 22, 30, 32, 33, 38, 41, 43, 45, 46, 48, 49, 50, 51, 62, 69, 70, 78. 89, 92, 93, 94, 95, 96, 98, 103, 106, 109, 110, 111, 112, 113, 114, 123, 125, 127, 130, 147, 156, 159, 163, 169, 172, 173, 174.
Teste
For evaluating control of potato leafhopper (Empoasca fabae (Harris)) through contact and/or systemic means, the test unit consisted of a small open container with a 5-6-day-old Soleil bean plant (primary leaves emerged) inside. White sand was added to the top of the soil, and one of the primary leaves was excised prior to application of the test compound.
Test compounds were formulated and sprayed at 250 ppm. After spraying of the formulated test compound, the test units were allowed to dry for 1 hour before they were post-infested with 5 potato leafhoppers (18-to-21-day-old adults). A black, screened cap was placed on the top of the test unit, and the test units were held for 6 days in a growth chamber at 20 °C and 70% relative humidity. Each test unit was then visually assessed for insect mortality.
Of the compounds of Formula 1 tested at 250 ppm, the following resulted in at least 80% mortality: 4, 8, 9, 11, 14, 21, 32, 33, 36, 37, 69.
136
Test D
For evaluating control of green peach aphid (Myzus persicae (Sulzer)) through contact and/or systemic means, the test unit consisted of a small open container with a 12-15-day-old radish plant inside. This was pre-infested by placing on a leaf of the test plant 3 0-40 aphids on a piece of leaf excised from a culture plant (cut-leaf method). The aphids moved onto the test plant as the leaf piece desiccated. After pre-infestation, the soil of the test unit was covered with a layer of sand.
Test compounds were formulated and sprayed at 250 and/or 50 ppm. After spraying of the formulated test compound, each test unit was allowed to dry for 1 hour and then a black, screened cap was placed on top. The test units were held for 6 days in a growth chamber at 19-21 °C and 50-70% relative humidity. Each test unit was then visually assessed for insect mortality.
Of the compounds of Formula 1 tested at 250 ppm, the following resulted in at least 80% mortality: 1, 2, 3, 5, 7, 8, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 25, 29, 30, 34, 36, 37, 38, 39, 48, 54, 67, 68, 69, 70, 71, 72, 74, 77, 78, 79, 81, 83, 86, 87. 1, 2, 3, 5, 7, 8, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 25, 29, 30, 34, 36, 37, 38, 39, 48, 54, 67, 68, 69, 70, 71, 72, 74, 77, 78, 79, 81, 83, 86, 87, 88, 89, 90, 91, 93, 94, 95, 96, 97, 103, 104, 118, 123, 125, 127, 130, 147, 159, 163.
Of the compounds of Formula 1 tested at 50 ppm, the following resulted in at least 80% mortality: 2, 3, 7, 8,13,14,15,16, 17,18, 19, 20, 21, 29, 34, 39, 48, 54, 67, 69, 71, 74, 78, 86, 89, 90, 91, 93, 94, 95, 103, 104, 118, 123, 125, 127, 130, 147, 159.
Test E
For evaluating control of cotton melon aphid (Aphis gossypii (Glover)) through contact and/or systemic means, the test unit consisted of a small open container with a 5-day-old okra plant inside. This was pre-infested with 30-40 insects on a piece of leaf according to the cut-leaf method, and the soil of the test unit was covered with a layer of sand.
Test compounds were formulated and sprayed at 250 and/or 50 ppm. After spraying, the test units were maintained in a growth chamber for 6 days at 19 °C and 70% relative humidity. Each test unit was then visually assessed for insect mortality.
Of the compounds of Formula 1 tested at 250 ppm, the following resulted in at least 80% mortality: 1, 2, 3, 7, 8, 9, 11, 12, 14, 16, 17, 19, 20, 21, 22, 29, 32, 33, 34, 36, 37, 38, 39, 41, 45, 49, 50, 51, 52, 54, 56, 57, 59, 60, 62, 64, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 83, 84, 85, 86, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 100, 102, 103, 104, 105, 106, 109, 111, 112, 113,
137
118, 123, 125, 127, 130, 133, 147, 148, 154, 156, 157, 158, 159, 160, 161, 163, 166, 169, 171, 172, 174, 175, 176.
Of the compounds of Formula 1 tested at 50 ppm, the following resulted in at least 80% mortality: 1,3,8,9, 11, 12, 14, 16, 17, 19, 20,21,22, 29,32,33,34,36,37,38,39, 45, 50,51,54, 67, 68, 69, 70, 71, 73, 74, 76, 78, 83, 85, 86, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 100, 102, 103, 104, 105, 106, 109, 111, 112, 113, 118, 123, 125, 127, 130, 133, 147, 148, 154, 156, 157, 158, 159, 160, 161, 163, 166, 169, 171, 172, 174, 175, 176.
Test F
For evaluating control of the sweetpotato whitefly (Bemisia tabaci (Gennadius)) through contact and/or systemic means, the test unit consisted of a small open container with a 12-14-dayold cotton plant inside. Prior to the spray application, both cotylédons were removed from the plant, leaving one true leaf for the assay. Adult whiteflies were allowed to lay eggs on the plant and then were removed from the test unit. Cotton plants infested with at least 15 eggs were submitted to the test for spraying.
Test compounds were formulated and sprayed at 250 and/or 50 ppm. After spraying, the test units were allowed to dry for 1 hour. The cylinders were then removed, and the units were taken to a growth chamber and held for 13 days at 28 °C and 50-70% relative humidity. Each test unit was then visually assessed for insect mortality.
Of the compounds of Formula 1 tested at 250 ppm, the following resulted in at least 70% mortality: 1, 3, 12, 13, 14, 15, 17, 19, 29, 36, 37, 39, 67, 69, 71, 78, 88, 89, 90, 91, 92, 93, 94, 95, 108, 109, 117, 118, 120, 123, 125, 127, 133, 134, 147, 155, 156, 168, 172.
Of the compounds of Formula 1 tested at 50 ppm, the following resulted in at least 70% mortality: 1, 13, 14, 19, 69, 71, 78, 88, 89, 90, 91, 92, 93, 94, 95, 108, 109, 117, 118, 120, 123, 125, 127, 133, 134, 147, 155, 156, 168, 172.
Test G
For evaluating control of the Western Flower Thrips (Frankliniellla occidentalis (Pergande)) through contact and/or systemic means, the test unit consisted of a small open container with a 57-day-old Soleil bean plant inside.
Test compounds were formulated and sprayed at 250 ppm. After spraying, the test units were allowed to dry for 1 hour, and then about 60 thrips (adults and nymphs) were added to each unit. A black, screened cap was placed on top, and the test units were held for 6 days at 25 °C and
138
45-55% relative humidity. Each test unit was then visually assessed for plant damage and insect mortality.
Of the compounds of Formula 1 tested at 250 ppm, the following provided very good to excellent levels of control efficacy (30% or less plant damage and/or 100% mortality): 1, 19, 29, 32,33,36,41,50.
ADDITIONAL EXAMPLE
Control Efficacy and Vapor Pressure
The values of control efficacy and vapor pressure for compounds 8 and A are shown in Additional Table 1.
Additional Table 1
Compound 8 A
Structure N N N p ôc F F F U F
Control Efficacy CMA GPA CPH PLH CMA GPA CPH PLH
250ppm 80 100 100 93 72 L 92 L
50 ppm 96 100 100 0 67 L 100 L
10 ppm 88 94 95 53
2 ppm 79 100 89 4
Vapor Pressure 6.04E-06 1.45E-03
CMA represents cotton melon aphid; GPA represents green peach aphid; CPH represents corn planthopper; PLH represents potato leafhopper.
The testing protocols for the control efficacy of both compounds are as described in the Biological Examples section.
The procedures to obtain the vapor pressure values for both compounds are as follows:
A solution of the test compound was prepared in acetonitrile at a concentration of 50 pg/mL and was then analyzed by gas chromatography/mass spectrometry (GC/MS). A linear corrélation of rétention times vs. known vapor pressure values of standard compounds is used to obtain an estimate of the vapor pressure of the test compounds by using interpolation. Détection and rétention time of the subject compounds are confirmed by interprétation of the mass spectrum.
139
Surprisingly, the results show that compound 8 of this disclosure demonstrates significantly higher control efficacy than compound A on species of CMA, GPA and CPH down to 2 ppm and PLH at 250 ppm. The results also show that the vapor pressure of compound 8 is significantly lower than that of compound A, almost 1000 times lower. It is noted that the only structure 5 différence between compounds 8 and A is that compound 8 of Formula 1 has R4 as a 5-membered heterocyclic ring triazol-l-yl while compound A has R4 as F which excludes compound A from the scope of this disclosure. While not being bound to this theory, it is contemplated that R4 as a heterocyclic ring, making the compound less volatile, may at least partially account for the higher control efficacy.

Claims (10)

1) when R1 is F, R2 is H, A is CR3 wherein R3 is F, R4 is 1-pyrazole and R5 is H, Q is other than 4-OCF3-phenyl; and
1. A compound selected from Formula 1, an TV-oxides or sait thereof,
R1
R5 wherein
R1 is F, OR6 or S(O)nR6;
A is N or CR3;
R2 is H, halogen, CN, C^-C^ alkyl, Cj-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, Cj-C4 alkoxy or Cj-C4 haloalkoxy;
R3 is H, halogen, CN, CrC4 alkyl, Cj-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, Cj-C4 alkoxy or Cj-C4 haloalkoxy;
R4 is a 5- to 6-membered heterocyclic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(=O), C(=S), S(=O) and S(=O)2, each ring optionally substituted with up to 5 substituents independently selected from Rv, and r is the number of the substituents.
each Rv is independently H, cyano, halogen, CpCg alkyl, Cj-Cg alkoxy, Cj-Cg haloalkoxy, CpCg haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 cyanoalkyl, CrC6 hydroxyalkyl, C4-C10 alkylcycloalkyl, C4-C10 cycloalkylalkyl, C3-C6 cycloalkenyl, C3-C6 halocycloalkenyl, C2-C6 alkoxyalkyl, C4-C10 cycloalkoxyalkyl, C3-C10
141 alkoxyalkoxyalkyl, C2-Cg alkylthioalkyl, C2-Cg alkylsulfinylalkyl, C3-Cg cycloalkoxy, C3-Cg halocycloalkoxy, C4-C10 cycloalkylalkoxy, C2-Cg alkenyloxy, C2-Cg haloalkenyloxy, C2-C6 alkoxyalkoxy, C2-Cg alkylcarbonyloxy, CpCg alkylthio, Cj-Cg haloalkylthio, C3-Cg cycloalkylthio, Cj-Cg alkylsulfinyl, CpCg haloalkylsulfmyl, Cj-Cg alkylsulfonyl, CpCg haloalkylsulfonyl, C3-Cg cycloalkylsulfonyl, Q-Cg alkylamino, C2-Cg dialkylamino, Cj-Cg haloalkylamino, C2-Cg halodialkylamino or C3-C6 cycloalkylamino;
r is 1, 2, 3, 4 or 5;
R5 is H, halogen, CN, C4-C4 alkyl, Cj-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, Cj-C4 alkoxy or Cj-C4 haloalkoxy;
R6 is C|-C4 alkyl, Cj-C4 haloalkyl, C3-C4 cycloalkyl or C3-C4 halocycloalkyl;
Q is a six membered aromatic ring containing ring members selected from carbon atoms and up to 2 nitrogen atoms, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from one or more Rw; and s is the number of the substituents;
Rwis independently H, cyano, halogen, C^-Cg alkyl, Cj-Cg haloalkyl, Cj-Cg alkoxy, CjCg haloalkoxy, C2-Cg alkenyl, C2-Cg haloalkenyl, C2-Cg alkynyl, C2-Cg haloalkynyl, C3-C6 cycloalkyl, C3-Cg halocycloalkyl, C2-C6 cyanoalkyl, CrCg hydroxyalkyl, C4C10 alkylcycloalkyl, C4-C10 cycloalkylalkyl, C3-Cg cycloalkenyl, C3-C6 halocycloalkenyl, C2-Cg alkoxyalkyl, C4-C10 cycloalkoxyalkyl, C3-C10 alkoxyalkoxyalkyl, C2-Cg alkylthioalkyl, C2-Cg alkylsulfinylalkyl, CrCg alkoxy, CjCg haloalkoxy, C3-Cg cycloalkoxy, C3-Cg halocycloalkoxy, C4-Cjq cycloalkylalkoxy, C2-Cg alkenyloxy, C2-Cg haloalkenyloxy, C2-Cg alkoxyalkoxy, C2-Cg alkylcarbonyloxy, Cj-Cg alkylthio, Cj-Cg haloalkylthio, C3-Cg cycloalkylthio, Cj-Cg alkylsulfinyl, Cj-Cg haloalkylsulfmyl, C3-Cg cycloalkylsulfinyl, Cj-Cg alkylsulfonyl, CpCg haloalkylsulfonyl, C3-Cg cycloalkylsulfonyl, Cj-Cg alkylamino, C2-Cg dialkylamino, Cj-Cg haloalkylamino, C2-Cg halodialkylamino or C3-C6 cycloalkylamino; or two Rw on adjacent carbon atoms together can form a -OCF2O-, -OCH2O-, -OCF2S-, -OCH2CH2)-, OCF2CF2O- cyclic ether ring;
142 s is 1, 2, 3, 4 or 5;
n is 0, 1 or 2;
with the proviso that
2. The compound of Claim 1 wherein:
A compound of Formula 1 wherein
R1 is F;
Ais CR3;
R2 is H, halogen, CN, C1-C4 alkyl, Cj-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, Cj-C4 alkoxy or Cj-C4 haloalkoxy;
R3 is H, halogen, CN, CpC4 alkyl, Cj-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, Cj-C4 alkoxy or Cj-C4 haloalkoxy;
R4 is a 5- to 6-membered heterocyclic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(=O), C(=S), S(=O) and S(=O)2, each ring or ring System optionally substituted with up to 5 substituents independently selected from Rv, and r is the number of the substituents.
each Rv is independently H, halogen, Cj-Cg alkyl, Cj-C6 haloalkyl, Cj-Cg alkoxy or C^C$ haloalkoxy;
ris 1, 2, 3, 4 or 5;
R5 is H, halogen, CN, Cj-C4 alkyl, Cj-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, Cj-C4 alkoxy or Cj-C4 haloalkoxy;
Q is a six membered aromatic ring with 0 to 2 N on the ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw;
143
Rwis independently cyano, halogen, CpC6 alkyl, C;-C6 alkoxy, Cj-C6 haloalkoxy, CpCg haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, Cp C6 alkylthio, CpC6 haloalkylthio, CpCg alkylsulfinyl, CpC$ haloalkylsulfinyl, Cp C6 alkylsulfonyl or CpC^ haloalkylsulfonyl;
s is 1, 2, 3, 4 or 5;
n is 0, 1 or 2.
2) R4 is other than pyridinyl.
3 -Bromo-4-[fluoro [4- [(trifluoromethyl)thio]phenyl]methyl] -5-(277-1,2,3 -triazol-2yl)pyridine.
14. A composition comprising a compound of claim 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents,
149 said composition optionally further comprising at least one additional biologically active compound or agent.
15. The composition of Claim 14 wherein the at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acephate, acequinocyl, acetamiprid, acrinathrin, afidopyropen, amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, benfuracarb, bensultap, bifenthrin, bifenazate, bistrifluron, borate, bromantraniliprole, buprofezin, carbaryl, carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cycloxaprid, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalodiamide, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dichlorantraniliprole, dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide, flucythrinate, flufenerim, flufenoxuron, flufenoxystrobin, fluensulfone, fluopyram, flupyradifurone, fluvalinate, tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide, heptafluthrin, hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidal soaps, isofenphos, lufenuron, malathion, meperfluthrin, metaflumizone, metaldehyde, methamidophos, methidathion, methiocarb, methomyl, methoprene, methoxychlor, methoxyfenozide, metofluthrin, monocrotophos, monofluorothrin, nicotine, M[l,l-dimethyl-2-(methylthio)ethyl]-7-fluoro-2-(3-pyridinyl)-2/findazole-4-carboxamide, 7V-[l,l-dimethyl-2-(methylsulfmyl)ethyl]-7-fluoro-2-(3-pyridinyl)-277indazole-4-carboxamide, 7V-[ 1,1 -dimethyl-2-(methylsulfonyl)ethyl] -7-fluoro-2-(3 -pyridinyl)-277indazole-4-carboxamide, N-(l-methylcyclopropyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide, 7V-[l-(difluoromethyl)cyclopropyl]-2-(3-pyridinyl)-277-indazole-4-carboxamide, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, propargite, protrifenbute, pyflubumide, pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl, pyrifluquinazon, pyriminostrobin, pyriprole, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulprofos, sulfoxaflor, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, tetrachlorantraniliprole, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tioxazafen,
150 tolfenpyrad, tralomethrin, triazamate, trichlorfon, triflumezopyrim, triflumuron, Bacillus thuringiensis delta-endotoxins, entomopathogenic bacteria, entomopathogenic viruses and entomopathogenic fungi.
16. A composition for protecting an animal from an invertebrate parasitic pest
3-Fluoro-4-[fluoro [4-[(trifluoromethyl)thio]phenyl]methyl]-5-(277-1,2,3-triazol-2yl)pyridine;
3-Fluoro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2-oxazolyl)pyridine;
3-Fluoro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(277-l,2,3-triazol-2yl)pyridine;
3 -Chloro-4-[fluoro [4- [(trifluoromethyl)thio]phenyl]methyl]-5-(2/7-1,2,3 -triazol-2yl)pyridine;
3-Chloro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(277-l,2,3-triazol-2-yl)pyridine;
3-Fluoro-4-[fluoro[4-(trifhioromethoxy)phenyl]methyl]-5-(277-l,2,3-triazol-2-yl)pyridine;
3-Fluoro-4-[methoxy[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(l,2,4-oxadiazol-3yl)pyridine.
13. The compound of Claim 12 wherein the compound is selected from the group consisting of:
3-Bromo-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2/7-l,2,3-triazol-2yl)pyridine; and
3-Chloro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(277-l,2,3-triazol-2yl)pyridine;
3-Fluoro-4-[methoxy[4-(trifiuoromethoxy)phenyl]methyl]-5-(277-l,2,3-triazol-2yl)pyridine;
3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(3-methyl-l,2,4-oxadiazol-5yl)pyridine;
3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(5-oxazolyl)pyridine;
3-Fluoro-4-[fluoro[4-[(trifluoromethyl)sulfinyl]phenyl]methyl]-5-(277-l,2,3-triazol-2yl)pyridine;
3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2-oxazolyl)pyridine;
3-Fhioro-4-[fhioro[4-(trifluoromethyl)phenyl]methyl]-5-(277-l,2,3-triazol-2-yl)pyridine;
3-Chloro-4-[fluoro [4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2Zf-1,2,3-triazol-2yl)pyridine;
3-Fluoro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2//-l,2,3-triazol-2yl)pyridine;
148
3-Fluoro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2-oxazolyl)pyridine;
3-Fluoro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(2//-l,2,3-triazol-2yl)pyridine;
3 -Chloro-4- [fluoro [4-(trifluoromethoxy)phenyl]methyl]-5-(2//-1,2,3 -triazol-2-yl)pyridine;
3-Fhioro-4-[fhioro[4-(trifhioromethoxy)phenyl]methyl]-5-(2Z/-l,2,3-triazol-2-yl)pyridine;
3. The compound of Claim 2 wherein:
R2 is H, halogen or CpC4 alkyl;
R3 is H, halogen, CpC4 alkyl, CpC4 haloalkyl, Cj-C4 alkoxy or Cp-C4 haloalkoxy;
R4 is selected from U-2 to U-49 or U52 to U61 as shown in Exhibit 1 ;
r is 1 or 2;
R5 is H, halogen, CpC4 alkyl, CpC4 haloalkyl, Cj-C4 alkoxy or Cj-C4 haloalkoxy;
Rwis Cj-C6 haloalkoxy, CpCg haloalkyl, C2-C$ haloalkenyl, C2-C6 haloalkynyl, CpCg haloalkylthio, CpCg haloalkylsulfinyl, CpC6 haloalkylsulfonyl.
s is 1 or 2.
4. The compound of Claim 3 wherein:
R2 is H;
R3 is H or halogen;
R4 is selected from U-2 to U-49;
Rv is H;
R5 is H or halogen;
Q is a phenyl, pyridinyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw;
Rwis OCF3, SCF3, CF3, CF2CF3j SOCF3 or SO2CF3.
5 comprising a parasiticidally effective amount of a compound of claim 1 and at least one carrier.
17. A method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of claim 1.
18. The method of Claim 17 wherein invertebrate pest comprises stink bugs from the family Pentatomidae.
5. The compound of Claim 3 wherein:
R2 is CpC4 alkyl;
R3 is H or halogen;
144
R4 is selected from U-2 to U-49;
Rv is H;
r is 2;
R5 is H;
Q is a phenyl, pyridinyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw;
Rwis OCF3, SCF3, CF3, CF2CF3 SOCF3 or SO2CF3.
6. The compound of claim 1 wherein:
R1 is OR6;
Ais CR3;
R2 is H, halogen, CN, Cj-C4 alkyl, ΟρΟ4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, Cj-C4 alkoxy or Cj-C4 haloalkoxy;
R3 is H, halogen, CN, Cj-C4 alkyl, Cj-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, Q-C4 alkoxy or C1-C4 haloalkoxy;
R4 is a 5- to 6-membered heterocyclic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(=O), C(=S), S(=O) and S(=O)2, each ring or ring System optionally substituted with up to 5 substituents independently selected from Rv, and r is the number of the substituents.
each Rv is independently H, halogen, Cj-Cg alkyl, Cj-C^ haloalkyl, Cj-Cg alkoxy or CjCg haloalkoxy;
r is 1, 2, 3, 4 or 5;
R5 is H, halogen, CN, CrC4 alkyl, CrC4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, Cj-C4 alkoxy or Cj-C4 haloalkoxy;
R6 is CpC4 alkyl;
Q is a six membered aromatic ring with 0 to 2 N on the ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw;
145
Rwis independently cyano, halogen, Cj-Cg alkyl, Cj-Cg alkoxy, Cj-Cg haloalkoxy, C^-Cg haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, Cr C6 alkylthio, CrCg haloalkylthio, Cj-Cg alkylsulfmyl, CrCg haloalkylsulfinyl, Cr C6 alkylsulfonyl or CpCg haloalkylsulfonyl;
s is 1, 2, 3, 4 or 5; n is 0, 1 or 2.
7. The compound of Claim 6 wherein:
R2 is H, halogen or C4-C4 alkyl;
R3 is H, halogen, C^-C4 alkyl, C4-C4 haloalkyl, C4-C4 alkoxy or Cj-C4 haloalkoxy;
R4 is selected from U-2 to U-49 or U52 to U61 as shown in Exhibit 1 ;
r is 1 or 2;
R5 is H, halogen, C4-C4 alkyl, C4-C4 haloalkyl, C4-C4 alkoxy or C4-C4 haloalkoxy;
R6 is Me;
Rwis Cj-Cg haloalkoxy, CrC6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, CrC6 haloalkylthio, Cj-Cg haloalkylsulfinyl, Cj-Cg haloalkylsulfonyl.
s is 1 or 2.
8. The compound of Claim 7 wherein:
R2 is H;
R3 is H or halogen;
R4 is selected from U-2 to U-49;
Rv is H;
r is 2;
R5 is H or halogen;
Q is a phenyl, pyridinyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw;
Rwis OCF3, SCF3, CF3, CF2CF3 SOCF3 or SO2CF3.
9. The compound of claim 1 wherein:
146
R1 is SR6;
A is CR3;
R2 is H, halogen, CN, CpC4 alkyl, CpC4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, Cj-C4 alkoxy or Cj-C4 haloalkoxy;
R3 is H, halogen, CN, CpC4 alkyl, CpC4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, Cj-C4 alkoxy or C]-C4 haloalkoxy;
R4 is a 5- to 6-membered heterocyclic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(=O), C(=S), S(=O) and S(=O)2, each ring or ring System optionally substituted with up to 5 substituents independently selected from Rv, and r is the number of the substituents.
each Rv is independently H, halogen, Cj-Cg alkyl, C]-C6 haloalkyl, C]-Cg alkoxy or C}C6 haloalkoxy;
r is 1, 2, 3, 4 or 5;
R5 is H, halogen, CN, CpC4 alkyl, CpC4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, Cj-C4 alkoxy or Cj-C4 haloalkoxy;
R6 is CpC4 alkyl;
Q is a six membered aromatic ring with 0 to 2 N on the ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw;
Rwis independently cyano, halogen, CpC6 alkyl, Cj-C6 alkoxy, Ci-Cg haloalkoxy, CpC6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, Cp C6 alkylthio, CpCg haloalkylthio, CpC6 alkylsulfinyl, CpC6 haloalkylsulfmyl, Cp Cg alkylsulfonyl or CpCg haloalkylsulfonyl;
s is 1, 2, 3, 4 or 5; n is 0, 1 or 2.
10. The compound of Claim 9 wherein: R2 is H, halogen or CpC4 alkyl;
147
R3 is H, halogen, Cj-C4 alkyl, C/-C4 haloalkyl, C]-C4 alkoxy or Cj-C4 haloalkoxy;
R4 is selected from U-2 to U-49 or U52 to U61 as shown in Exhibit 1;
Rv is H, halogen, Cj-Cg alkyl, C]-C6 alkoxy, Q-Cg haloalkoxy or Cy-C^ haloalkyl, r is 1 or 2;
R5 is H, halogen, CpC4 alkyl, CpC4 haloalkyl, C1-C4 alkoxy or Cj-C4 haloalkoxy;
R6 is Me;
Rwis Cj-C/ haloalkoxy, CpC6 haloalkyl, C2-C6 haloalkenyl, C2-Cg haloalkynyl, Cj-C6 haloalkylthio, Cj-Cg haloalkylsulfînyl, Cj-Cg haloalkylsulfonyl.
s is 1 or 2.
11. The compound of Claim 10 wherein:
R2 is H;
R3 is H or halogen;
R4 is selected from U-2 to U-49;
Rv is H;
r is 2;
R5 is H;
Q is a phenyl, pyridinyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on carbon atom ring members with up to 5 substituents independently selected from Rw;
Rwis OCF3, SCF3, CF3, CF2CF3; SOCF3 or SO2CF3.
12. The compound of claim 1 wherein the compound is selected from the group consisting of:
10 19. A treated seed comprising a compound of claim 1 in an amount of from about 0.0001 to 1 % by weight of the seed before treatment.
OA1202200290 2020-01-30 2021-01-29 Pyridine compounds for controlling invertebrate pests. OA21278A (en)

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