NZ717749B2 - Heterocycle-substituted bicyclic azole pesticides - Google Patents

Abstract

Disclosed are compounds of Formula 1, including all geometric and stereoisomers, N-oxides, and salts thereof, and A, R1, m, X1, X2, X3, X4, Y1, Y2 and Y3 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 invention. e pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound or a composition of the invention.

Description

(12) Granted patent specificaon (19) NZ (11) 717749 (13) B2 (47) Publicaon date: 2021.12.24 (54) CYCLE-SUBSTITUTED BICYCLIC AZOLE PESTICIDES (51) Internaonal Patent Classificaon(s): C07D 401/14 C07D 405/14 C07D 413/14 A01N 43/56 A01N 43/78 C07D 401/04 C07D 403/04 C07D 407/14 C07D 409/14 C07D 413/04 C07D 417/04 C07D 417/14 C07D 471/04 C07D 513/04 A01P 7/00 A01P 7/04 A01P 5/00 (22) Filing date: (73) Owner(s): 2014.09.09 FMC CORPORATION (23) Complete caon filing date: (74) Contact: 2014.09.09 HOULIHAN2 PTY LTD (30) Internaonal Priority Data: (72) Inventor(s): US 61/877,329 2013.09.13 CLARK, David, Alan FRAGA, Breena, Gloriana (86) Internaonal Applicaon No.: ZHANG, Wenming (87) Internaonal Publicaon number: WO/2015/038503 (57) Abstract: Disclosed are nds of Formula 1, including all ric and stereoisomers, N-oxides, and salts thereof, and A, R1, m, X1, X2, X3, X4, Y1, Y2 and Y3 are as defined in the sure. Also disclosed are composions containing the compounds of Formula 1 and methods for controlling an invertebrate pest comprising contacng the invertebrate pest or its environment with a biologically effecve amount of a compound or a composion of the invenon.

NZ 717749 B2 WO 38503 TITLE HETEROCYCLE-SUBSTITUTED BICYCLIC AZOLE PESTICIDES FIELD OF THE INVENTION This invention relates to certain substituted bicyclic azoles, their N—oxides, salts and compositions suitable for agronomic and nonagronomic uses, and methods of their use for controlling invertebrate pests such as arthropods in both agronomic and nonagronomic environments.

BACKGROUND OF THE INVENTION The control of invertebrate pests is extremely important in achieving high crop efficiency. Damage by invertebrate pests to growing and stored agronomic crops can cause significant ion in productivity and y result 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 , less toxic, nmentally safer or have different sites of .

SUMMARY OF THE INVENTION This invention is directed to compounds of Formula 1 (including all geometric and stereoisomers), N—oxides, and salts thereof, and compositions containing them and their use for controlling invertebrate pests: wherein W0 2015f038503 X1 1 X1 2 ch Y X2 , }\ I I I ’ ’ , / E— 3 X3\ X \ \ /N—§' \X4 N \X4 N Q-l Q-2 2’X1\ Y3 ’Xl a“ “y; / — 01‘ >6” 3 ~ X \ g / §— X’\ ,N \X4 N \X4 \N Q-S Q-4 A is CH, CR1 or N; each R1 is independently n, cyano, nitro, C1—C4 alkyl, C1—C4 haloalkyl, C1—C4 alkoxy, C1—C4 haloalkoxy, C1—C4 alkylthio or C1—C4 haloalkylthio; misO,1,2or3; X1, X2, X3 and X4 are each independently CR2, CR3 or N, provided that (i) one of X1, X2, X3 and X4 is CR2, and (ii) no more than one of X1, X2, X3 and X4 is N; R2 is C(=Z)NR6R7, N(R8)C(=Z)R9, C(=NR10)R11 or Qa; each Z is independently O or S; each R3 is independently H, halogen, cyano, nitro, C1—C4 alkyl, C1—C4 haloalkyl, C1— C4 alkoxy or C1—C4 haloalkoxy; Y1 is O, S or NR4; Y2 is N or CRsa; Y3 is N or CRSb; R4 is H or C1—C4 alkyl, R5a is H, halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1— C4 alkoxy or C1—C4 haloalkoxy; R5b is H, halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 kyl, C1— C4 alkoxy or C1—C4 haloalkoxy; R6 is H, NR15R16, 0R”, C(=NR10)R11, C(O)OR21, C(O)NR15R16, C(O)R22, 51(0),,R23 or Qb; or C1—C6 alkyl, C3—C6 cycloalkyl, C2—C6 alkenyl or C2—C6 alkynyl, each unsubstituted or substituted with at least one RX; R7 is H or Qb; or C1—C6 alkyl, C3—C5 cycloalkyl, C2—C6 alkenyl or C2—C6 alkynyl, each unsubstituted or substituted with at least one RX; or R6 and R7 are taken together with the nitrogen atom to Which they are attached to form a 3— to lO-membered ring containing ring s selected from carbon atoms and up to 2 atoms independently ed from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring W0 2015f038503 members are independently selected from C(=O) and C(=S) and the sulfur atom ring member is ed from S, 8(0) or S(O)2, said ring being unsubstituted or substituted with up to 4 RX; or R6 and R7 are taken er as =S(O)pR18R19 or =S(=NR20)R18 19; each Rx is independently halogen, cyano, nitro, hydroxy, C1—C6 alkyl, C1—C6 haloalkyl, C3—C6 cycloalkyl, C1—C6 alkoxy, C1—C6 haloalkoxy, C3—C6 cycloalkoxy, C(=NR10)R11, C(O)OR21, C(O)NR15R16, OC(O)R22, NR25R26, NR24C(O)R22, C(O)R22, 5(0),,R23, Si(R28)3, osrafg)3 or Qb; R8 is H, C(O)OR21, C(O)NR15R16, C(O)R22, 5(0),,R23 or Qb; or cl—c6 alkyl, c3—c6 cycloalkyl, C2—C6 alkenyl or C2—C6 alkynyl, each unsubstituted or substituted with at least one RX; R9 is H, C(=NR10)R11, OR21 or NR15R16; or C1—C6 alkyl, C3—C6 cycloalkyl, C2—C6 alkenyl or C2—C6 alkynyl, each unsubstituted or substituted with at least one RX; or phenyl, phenoxy or a 5- or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 koxy; or a 3- to 6- membered heterocyclic non-aromatic ring, each ring containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 1 carbon atom ring member is independently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, 8(0) or S(O)2, each ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 koxy; each R10 is independently OR12, S(O)nR13 or NHR14; each R11 is independently H; or C1—C6 alkyl, C3—C6 cycloalkyl, C2—C6 alkenyl or C2— C6 alkynyl, each unsubstituted or tuted with at least one RX; or C1—C6 alkoxy, cl—c6 haloalkoxy, c3—c6 cycloalkoxy, C(O)OR21, C(O)NR15R16, 1x11125186, NR24C(O)R22, C(0)R22 or Qb; each R12 is ndently C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 kyl, C(O)R22, 3(0)an3 or Qb; each R13 is ndently C1—C4 alkyl or C1—C4 haloalkyl, R14 is cl—c4 alkyl, c3—c6 cycloalkyl, cl—c4 haloalkyl, C(0)R22 or C(O)OR21; or , unsubstituted or substituted with at least one substituent independently selected from the group consisting of n, cyano, nitro, C1—C4 alkyl, C3—C6 lkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 haloalkoxy; W0 2015f038503 each R15 is independently H, C1—C6 alkyl, C1—C4 haloalkyl, C(O)R27 or S(O)2R27; or phenyl or a 5- or 6-membered heterocyclic aromatic ring, each tituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 haloalkoxy; each R16 is independently H, C1—C6 alkyl or C1—C4 haloalkyl; or R15 and R16 are taken together with the nitrogen atom to which they are attached to form a 3- to 7-membered ring containing ring members ed from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are ndently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, 8(0) or S(O)2, said ring being tituted or substituted with at least one substituent independently selected from the group consisting of n, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 haloalkoxy; R1? is C1—C4 alkyl, C3—C6 lkyl or C1—C4 haloalkyl; or , unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 haloalkoxy; each R18 is independently C1—C4 alkyl or C1—C4 haloalkyl, or phenyl, unsubstituted or substituted with at least one tuent independently selected from the group consisting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 haloalkoxy; each R19 is independently C1—C4 alkyl or C1—C4 haloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently ed from the group consisting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 lkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 haloalkoxy; or R18 and R19 are taken together with the sulfur atom to which they are attached to form a ring; R20 is H, cyano, C1—C4 alkyl, C1—C4 haloalkyl or C(O)R22; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of n, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 haloalkoxy; each R21 is independently C1—C4 alkyl, C1—C4 haloalkyl, C3—C6 cycloalkyl or C3—C6 halocycloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 haloalkoxy; W0 2015f038503 each R22 is independently C1—C4 alkyl, C1—C4 haloalkyl, C3—C6 cycloalkyl or C3—C6 halocycloalkyl; or phenyl, tituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 haloalkoxy; each R23 is independently C1—C4 alkyl, C1—C4 haloalkyl, C3—C6 cycloalkyl, C3—C6 cloalkyl, C3—C6 cycloalkylalkyl or C3—C6 halocycloalkylalkyl; or phenyl, unsubstituted or substituted with at least one tuent independently selected from the group consisting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 haloalkoxy; each R24 is independently C1—C4 alkyl; each R25 is independently H, C1—C4 alkyl or C1—C4 haloalkyl; or phenyl, unsubstituted or tuted with at least one substituent independently ed from the group consisting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 kyl, C1—C4 alkoxy and C1—C4 haloalkoxy; each R26 is independently C1—C4 alkyl or C1—C4 haloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 haloalkoxy; or R25 and R26 are independently taken together with the nitrogen atom to which they are attached to form a 3- to 7-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, 8(0) or S(O)2, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 lkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 haloalkoxy; each R27 is independently C1—C6 alkyl, C1—C6 haloalkyl, C1—C6 alkoxy, C1—C6 haloalkoxy or 0; or phenyl or a 5- or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent ndently selected from the group consisting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 haloalkoxy; each R28 is independently C1—C6 alkyl, C3—C6 cycloalkyl or phenyl; each R29 is ndently H or Qb; or C1—C6 alkyl, C3—C6 cycloalkyl, C2—C6 alkenyl or C2—C6 alkynyl, each unsubstituted or substituted with at least one substituent ndently selected from the group consisting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 haloalkoxy; W0 2015f038503 each R30 is independently H or Qb; or C1—C5 alkyl, C3—C6 cycloalkyl, C2—C6 alkenyl or C2—C6 alkynyl, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 haloalkoxy; R29 and R30 are taken together with the nitrogen atom to which they are attached to form a 3- to lO-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are ndently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, S(O) or S(O)2, said ring being unsubstituted or substituted with up to 4 substituents independently selected from the group ting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 koxy; Q21 is a 5— to lO-membered aromatic ring or ring system, each ring or ring system containing ring members selected from carbon atoms and up to 3 heteroatoms ndently selected from one oxygen atom, one sulfur atom, and up to 3 nitrogen atoms, wherein up to 2 carbon atom ring s are independently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, 8(0) or S(O)2, each ring or ring system being unsubstituted or substituted with at least one RX; or a 3- to 6-membered partially saturated ring, each ring containing ring members ed from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently ed from C(=O) and C(=S) and the sulfur atom ring member is selected from S, S(O) or S(O)2, each ring unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 haloalkoxy; each Qb is ndently phenyl, a 5- or 6-membered heterocyclic aromatic ring or a 3— to 6—membered heterocyclic non-aromatic ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are ndently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, 8(0) or S(O)2, each ring tituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1—C4 alkyl, C3—C6 cycloalkyl, C1—C4 haloalkyl, C1—C4 alkoxy and C1—C4 haloalkoxy; each n is independently 0, l or 2; and pislor2.

This invention also provides a composition comprising a compound of Formula 1, an N—oxide or a salt thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. In one embodiment, this ion also provides a ition for controlling an ebrate pest comprising a compound of Formula 1, an N—oxide or a salt f, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally r comprising at least one additional biologically active compound or agent.

This invention further provides a spray composition for controlling an invertebrate pest comprising a compound of Formula 1, an e or a salt f, or the compositions described above, and a propellant. This invention also provides a bait composition for controlling an invertebrate pest comprising a compound of Formula 1, an N—oxide or a salt f, or the compositions described in the embodiments above, one or more food materials, optionally an attractant, and optionally a humectant.

This invention further provides a trap 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.

This ion 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 e or a salt f, (e.g., as a composition described herein). This invention also relates to such method wherein the invertebrate pest or its environment is contacted with a composition sing a biologically effective amount of a nd of a 1, an N—oxide or a salt thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition ally further comprising a biologically effective amount of at least one additional biologically active compound or agent.

This invention also provides a method for protecting a seed from an invertebrate pest comprising contacting the seed with a biologically effective amount of a compound of Formula 1, an e or a salt thereof, (e.g., as a ition described herein). This invention also relates to the treated seed. This invention further provides a method for protecting an animal from an invertebrate parasitic pest comprising administering to the animal a ticidally effective amount of a compound of Formula 1, an N—oxide or a salt W0 2015f038503 f, (e.g., as a composition described herein). This invention also provides for the use of a compound of Formula 1, an N—oxide or a salt thereof, (e.g., as a composition described herein) in ting an animal from an invertebrate pest.

This invention also provides a method for increasing vigor of a crop plant comprising contacting the crop plant, the seed from which the crop plant is grown or the locus (e.g., growth medium) of the crop plant with a biologically ive amount of a compound of Formula 1 (e.g., as a composition described herein).

DETAILS OF THE INVENTION As used herein, the terms “comprises, 3, CCcomprising, ,3 udes,77 ‘6'including,” “has,” “having, 7, ‘5contains)3 ‘6 “characterized by” or any other variation thereof, , containing,3, are intended to cover a clusive ion, subject to any limitation explicitly indicated.

For e, a composition, e, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.

The tional phrase “consisting of” excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of” appears in a clause of the body of a claim, rather than immediately ing the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define a composition or method that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional als, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term “consisting essentially of” es a middle ground between “comprising” and “consisting of”.

Where applicants have defined an invention or a n thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the terms sting essentially of” or “consisting of.” Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

Also, the indefinite articles “a” and “an” preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the t or component. Therefore “ 77 a or “an” should be read to include W0 2015f038503 one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.

As referred to in this disclosure, the term “invertebrate pest” includes arthropods, gastropods, nematodes and helminths of economic importance as pests. The term “arthropod” es insects, mites, s, scorpions, centipedes, millipedes, pill bugs and symphylans. The term “gastropod” includes snails, slugs and other Stylommatophora. The term “nematode” includes s of the phylum Nematoda, such as phytophagous nematodes and helminth nematodes parasitizing animals. The term “helminth” includes all of the parasitic worms, such as roundworms (phylum Nematoda), heartworms (phylum Nematoda, class Secernentea), fiukes (phylum Platyhelminthes, class Tematoda), acanthocephalans m Acanthocephala), and tapeworms (phylum Platyhelminthes, class Cestoda).

In the context of this disclosure “invertebrate pest control” means inhibition of invertebrate pest development ding mortality, feeding reduction, and/or mating disruption), and related sions are defined analogously.

The term “agronomic” refers to the tion 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., s and cherries) and other specialty crops (e.g., canola, sunflower and ).

The term “nonagronomic” refers to other than field crops, such as horticultural crops (e. g., greenhouse, nursery or ornamental plants not grown in a field), residential, agricultural, commercial and industrial structures, turf (e.g., sod farm, pasture, golf , lawn, sports field, etc.), wood products, stored product, agro-forestry and vegetation ment, public health (i.e. human) and animal health (e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife) applications.

The term “crop vigor” refers to rate of growth or biomass accumulation of a crop plant.

An ase in vigor” refers to an increase in growth or biomass accumulation in a crop plant relative to an ted control crop plant. The term “crop yield” refers to the return on crop material, in terms of both quantity and quality, obtained after harvesting a crop plant.

An “increase in crop yield” refers to an se in crop yield ve 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 ebrate 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).

The position of the variable R1 in the ure of Formula 1 is described by the numbering system shown below.

Q{?(R)m 1 A wavy line in a structure fragment denotes the attachment point of the fragment to the remainder of the molecule. For example, when the variable Q in Formula 1 is defined as Q-l, the wavy line bisecting the bond in Q-l means that Q-l is attached to the remainder of the structure of a 1 at said on, as shown below.

In structures Q-l, Q-Z, Q-3 and Q-4, the variables X1, X2, X3 and X4 are defined as each being independently CR2, CR3 or N, provided that (i) one of X1, X2, X3 and X4 is CR2, and (ii) no more than one of X1, X2, X3 and X4 is N. This ion of X1, X2, X3 and X4 describes sixteen possible combinations of X1, X2, X3 and X4, shown in the table below.

W0 2015f038503 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, i—propyl, or the different butyl, pentyl or hexyl isomers. “Alkenyl” includes straight-chain or branched alkenes such as l, l-propenyl, enyl, and the different butenyl, pentenyl and hexenyl isomers. “Alkenyl” also includes polyenes such as l,2-propadienyl and 2,4-hexadienyl. “Alkynyl” includes straight-chain or branched alkynes such as ethynyl, l-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.

“Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. “Alkylthio” includes ed or straight-chain alkylthio moieties such as thio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio s.

“Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

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, e or iodine. Further, when used in nd words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” said alkyl may be partially or fillly substituted with n atoms which may be the same or different. Examples of “haloalkyl” or “alkyl tuted with halogen” e F3C-, ClCH2-, CF3CH2- and CF3CClz-. The terms “halocycloalkyl”, “haloalkoxy”, “haloalkylthio”, “haloalkenyl”, “haloalkynyl”, and the like, are defined analogously to the term “haloalkyl”. Examples of “haloalkoxy” e CF3O-, CCl3CH20-, HCFZCHZCHZO- and CF3CH20—. Examples of lkylthio” include CCl3S-, CF3S-, CCl3CHZS- and ClCHZCHZCH28-.

The chemical abbreviations 8(0) and S(=O) as used herein represent a sulfmyl moiety.

The chemical abbreviations SOZ, S(O)2 and S(=O)2 as used herein represent a sulfonyl moiety. The chemical iations C(0) and C(=O) as used herein represent a carbonyl moiety. The chemical abbreviations C02, C(O)O and C(=O)O as used herein represent an oxycarbonyl moiety. “CHO” means formyl.

The total number of carbon atoms in a substituent group is indicated by the “Ci—Cj” prefix where i and j are numbers from 1 to 6. For example, C1—C4 ulfonyl designates methylsulfonyl through butylsulfonyl; C2 alkyl designates CH3OCH2-; C3 W0 2015f038503 2014/054671 alkoxyalkyl designates, for example, CH3CH(OCH3)-, CH3OCH2CH2- or CH3CH20CH2-g and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH20CH2- and CH3CH20CH2CH2-.

When a compound is substituted with a substituent bearing a subscript that indicates the number of said tuents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents, e.g., (R1)m, m is 0, l, 2 or 3.

Further, when the subscript tes a range, e.g. (R)i,j, then the number of substituents may be ed from the integers between i and j inclusive. When a group contains a substituent which can be hydrogen, for example R3 or R4, then when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being tituted. When a variable group is shown to be optionally attached to a position, for example (R1)m wherein m may be 0, then hydrogen may be at the position even if not recited in the variable group definition. 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” or “ring system” as a component of Formula 1 (e.g., substituent Qa) is yclic or cyclic. The term “ring system” denotes two or more fused rings. The terms “bicyclic ring system” and “fused bicyclic ring system” denote a ring system consisting of two fused rings, which can be “ortho-fused”, “bridged bicyclic” or “spirobicyclic”. An -fused bicyclic ring system” denotes a ring system wherein the two constituent rings have two adjacent atoms in common. A “bridged bicyclic ring system” is formed by g a segment of one or more atoms to nonadjacent ring members of a ring. A “spirobicyclic ring system” is formed by bonding a t of two or more atoms to the same ring member of a ring. The term “fused heterobicyclic ring system” denotes a fused bicyclic ring system in which at least one ring atom is not carbon. The term “ring member” refers to an atom or other moiety (e.g., C(=O), C(=S), 8(0) or S(O)2) forming the backbone of a ring or ring system.

The terms “carbocyclic ring”, “carbocycle” or “carbocyclic ring system” denote a ring or ring system wherein the atoms forming the ring backbone are selected only from carbon.

The terms ocyclic ring”, “heterocycle” or “heterocyclic ring system” denote a ring or ring system in which at least one atom forming the ring backbone is not carbon, e.g., nitrogen, oxygen or sulfiir. Typically a heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. Unless ise 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 ise specified, the remaining atom es are occupied by hydrogen atoms.

Unless otherwise stated, an “unsaturated ring” may be lly unsaturated or fully unsaturated. The expression “fiilly unsaturated ring” means a ring of atoms in which the W0 2015f038503 2014/054671 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” denotes a ring comprising at least one ring member bonded to an adjacent ring member through a double bond and which conceptually potentially accommodates 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 t (i.e. in its partially unsaturated form).

Unless otherwise indicated, heterocyclic rings and ring systems can be attached h any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.

“Aromatic” indicates that each of the ring atoms is ially in the same plane and has a p-orbital perpendicular to the ring plane, and in which (4n + 2) 7r electrons, where n is a positive r, are associated with the ring to comply with Hiickel’s rule. The term “aromatic ring ” denotes a carbocyclic or heterocyclic ring system in which at least one ring of the ring system is aromatic. When a fully unsaturated carbocyclic ring satisfies Hiickel’s rule, then said ring is also called an “aromatic ring” or “aromatic carbocyclic ring”.

The term “aromatic yclic ring system” denotes a carbocyclic ring system in which at least one ring of the ring system is aromatic. When a fully unsaturated heterocyclic ring satisfies Huckel’s rule, then said ring is also called a “heteroaromatic ring”, “aromatic cyclic ring” or “heterocyclic aromatic ring”. The term “aromatic heterocyclic ring system” denotes a heterocyclic ring system in which at least one ring of the ring system is ic. The term “nonaromatic ring system” denotes a carbocyclic or heterocyclic ring system that may be fully saturated, as well as partially or fully unsaturated, provided that none of the rings in the ring system are aromatic. The term “nonaromatic carbocyclic ring system” denotes a carbocyclic ring in which no ring in the ring system is aromatic. The term “nonaromatic heterocyclic ring ” denotes a heterocyclic ring system in which no ring in the ring system is aromatic.

The term “optionally substituted” in tion with the heterocyclic rings refers to groups which are unsubstituted or have at least one non-hydrogen substituent that does not uish the biological activity possessed by the unsubstituted analog. As used herein, the following definitions shall apply unless otherwise ted. 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 have a substituent at each substitutable position of the group, and each substitution is independent of the other.

When a substituent 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 WO 38503 atom, unless otherwise described. As noted above, Q3 can be (among ) phenyl optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of Invention. An e of phenyl optionally substituted with one to five substituents is the ring illustrated as U-1 in t 1, wherein RV is Rx as defined in the Summary of the Invention for Qa and r is an integer from 0 to 5.

As noted above, Qb can be (among others) a 5- or 6-membered heterocyclic aromatic ring, optionally substituted with one or more substituents selected from a group of tuents as defined in the Summary of Invention. 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 of the Invention for Qb and r is an integer from 0 to 4, limited by the number of ble positions on each U group. As U-29, U-30, U-36, U-37, U-38, U-39, U—40, U-41, U-42 and U-43 have only one available position, for these U groups r is limited to the integers 0 or 1, and r being 0 means that the U group is unsubstituted and a hydrogen is present at the position indicated by (RV)r.

Exhibit 1 3 (RV)r 4 (RV)r 3 (RV)r (Rv)r 4 (RV)r 4| r074 {7 fl \ s O {55 2 S 5 2 0 U-1 U-2 U-3 U-4 U-5 <va (RV)r (RV)r <th (Rm \N/y7 // \/\ N N J 7 / / 4 /\ 2 9 a \ a XJ , K7 9 N N o 5 5 o U-6 U-7 U-8 U-9 U-10 4 (RV)r <th (Rm 4 (RV)r (RV)r KW“ N N O_//2 9 Y77“ 9 \4C‘72 9 RA“ 9 ‘N\ 9 _V7“ S 5 5 S 8J2 U-11 U-12 U-13 U 14 U 15 (Rv)r (Rv)r (Rv)r 4 (Rv)r 3 (RV)r N. N. 4'w g<\// 5K; KQ \z” WO 38503 PCT/USZOl4/054671 4/(RV)r 4 (RV)r V// 3 \v \- \o U—21 \(74/(RV)r\\ 5 \- u u U-26 (Rv)r \N \AN EN/ n u u U-31 N”NM u u (Rv)r U-36 \- u \- u u v u \- u \- \- 1qu /\(Rv)r4 U—6l As noted above, Q81 can be (among others) an 8-, 9- or lO—membered fused bicyclic ring system optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of Invention. Examples of 8-, 9- or 10- ed ortho-fused bicyclic ring system optionally substituted with from one or more substituents include the rings U-81 through U-123 illustrated in Exhibit 3 wherein RV is any substituent as defined in the Summary of the ion for Qa, and r is typically an integer from 0 to 4.

Exhibit 3 90 goN goO (RV>r ’ '\(RV)r ’ \(RV)r ’ CE}N(RV)r \- U-82 U 83 52>N\V(R>r / ’ “3%N ’ 90 ’ 9Q(RV)r \- (R >r fig” U—85 U-86 U-87 U-88 \ \ 0 \ (/1 \? X \/\ X @ X \/\ @ fl \/2 ng;Af< _\:gg/x/z \ /z \ <X 7: X O\/E< X 3M25< §§/:/:C7% u \fg \ /\/O \ \<:’A/73 X E< X JV“5< u U-9? U-98 U-99 3::dz; U- 100 XN \(Rv)r \ V zX u ~ @H X 0\ ’73 av / \(RV>r U—lOl U-102 U-103 U-104 U-121 U-122 U-123 Although RV groups are shown in the structures U—l through U-123, it is noted that they do not need to be present since they are optional substituents. Note that when RV is H when attached to an atom, this is the same as if said atom is unsubstituted. The nitrogen atoms that require substitution to fill their valence are substituted with H or RV. Note that when the attachment point between (RV)r and the U group is illustrated as floating, (RV)I can be attached to any available carbon atom or nitrogen atom of the U group. Note that when the attachment point on the U group is illustrated as g, 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 groups can only be substituted with less than 4 RV groups (e. g., U-2 h U-5, U-7 through U-48, and U-52 through U-61).

A wide variety of synthetic methods are known in the art to enable preparation of aromatic and matic heterocyclic rings and ring s; for extensive reviews see the eight volume set of Comprehensive Heterocyclic Chemistry, A. R. zky and C. W. Rees editors-in-chief, Pergamon Press, Oxford, 1984 and the twelve volume set of Comprehensive cyclz’c Chemistry II, A. R. Katritzky, C. W. Rees and E. F. V. Scriven editors-in-chief, Pergamon Press, Oxford, 1996.

Compounds of this invention 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, ans isomers (also known as geometric isomers) W0 2015f038503 and atropisomers. Atropisomers result from restricted rotation about single bonds where the rotational barrier is high enough to permit isolation of the ic species. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit ial effects when enriched relative to the other isomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. For a comprehensive discussion of all aspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

This ion comprises all stereoisomers, conformational s and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.

One d in the art will iate that not all en-containing heterocycles can form N—oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form N—oxides. One skilled in the art will also recognize that tertiary amines can form N—oxides.

Synthetic methods for the preparation of N—oxides of cycles 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 t—butyl hydroperoxide, sodium perborate, and dioxiranes such as yldioxirane. These methods for the preparation of es have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive c Synthesis, vol. 7, pp 748—750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic try, vol. 3, pp 18—20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149—161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285—291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390—392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.

One skilled in the art recognizes that because in the environment and under physiological conditions salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms. Thus a wide variety of salts of the compounds of Formula 1 are useful for control of invertebrate pests. The salts of the compounds of a 1 include acid-addition salts with inorganic or organic acids such as hydrobromic, hloric, nitric, phosphoric, ic, acetic, butyric, fumaric, , 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 phenol, 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, m, calcium, magnesium or barium. Accordingly, the present invention comprises compounds selected from Formula 1, N-oxides and suitable salts Compounds ed from Formula 1, stereoisomers, tautomers, N—oxides, and salts thereof, typically exist in more than one form, and Formula 1 thus includes all crystalline and non—crystalline forms of the compounds that Formula 1 ents. 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 e embodiments which represent ially a single crystal type and embodiments which represent a mixture of rphs (i.e. different crystalline types). The term “polymorph” refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due to the presence or e of co- crystallized water or other molecules, which can be weakly or strongly bound in the lattice.

Polymorphs can differ in such chemical, physical and ical ties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, ution rate and biological availability. One skilled in the art will appreciate that a polymorph of a compound represented by Formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another rph or a mixture of polymorphs of the same compound represented by Formula 1. ation 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, llization using selected solvents and temperatures. Compounds of this invention may exist as one or more crystalline polymorphs. This ion comprises both individual polymorphs and mixtures of polymorphs, including mixtures enriched in one polymorph relative to others. For a comprehensive discussion of rphism see R.

Hilfiker, Ed., Polymorphism In the Pharmaceutical Industry, VCH, Weinheim, 2006.

Embodiments of the present invention as described in the Summary of the Invention include those described below. In the following Embodiments, reference to “a compound of Formula 1” includes the definitions of tuents specified in the Summary of the Invention unless further defined in the Embodiments.

Embodiment l. A compound of Formula 1 wherein Q is Q-l, Q-2 or Q-3.

Embodiment 2. A compound of Formula 1 wherein Q is Q-l, Q-2 or Q-3, and Y3 is CR5b.

Embodiment 3. A compound of Formula 1 n Q is Q-l or Q—2.

Embodiment 4. A compound of Formula 1 wherein Q is Q-l.

Embodiment 5. A compound of Formula 1 wherein Q is Q-l, and Y1 is O or S. ment 6. A compound of Formula 1 wherein Q is Q-l, and Y1 is S.

Embodiment 7. A compound of a 1 wherein Q is Q-l, and Y1 is O.

Embodiment 8. A compound of Formula 1 wherein Q is Q-2. ment 9. A compound of Formula 1 wherein Q is Q—2, and Y2 is CR5a.

Embodiment 10. A compound of Formula 1 or any of Embodiments 1—9 wherein A is CH, CR1 or N, and R1 is halogen.

Embodiment 11. A compound of Embodiment 10 wherein A is CH, CF or N.

Embodiment 11a. A compound of Embodiment 10 wherein A is CF or N.

Embodiment 12. A compound of Embodiment 10 wherein A is CH or CF. ment 13. A compound of Embodiment 10 wherein A is CH.

Embodiment 14. A compound of Embodiment 10 wherein A is N. ment 15. A compound of Formula 1 or any of Embodiments 1—9 wherein m is 1, and R1 is C1—C4 alkyl, C1—C4 haloalkyl, C1—C4 alkoxy or halogen.

Embodiment 16. A compound of Embodiment 15 wherein R1 is CF3, OMe, Me, or F.

Embodiment 17. A compound of Embodiment 16 wherein R1 is CF3, OMe, Me, or F, and is in the 4-position.

Embodiment 18. A compound of Embodiment 17 wherein R1 is CF3, and is in the 4- position.

Embodiment 19. A compound of Formula 1 or any of Embodiments 1—9 n m is 0.

Embodiment 20. A compound of Formula 1 or any of Embodiments 1—19 wherein X1 is CR2, and X2, X3 and X4 are each independently CR3; or X2 is CR2, and X1, X3 and X4 are each independently CR3.

Embodiment 21. A compound of Embodiment 20 wherein X1 is CR2, and X2, X3 and X4 are each independently CR3.

Embodiment 22. A compound of Embodiment 20 wherein X2 is CR2, and X1, X3 and X4 are each independently CR3. ment 23. A compound of Formula 1 or any of ments 1—22 wherein each R3 is independently H or halogen.

Embodiment 24. A nd of Embodiment 23 wherein each R3 is independently H or F. ment 25. A compound of Embodiment 24 wherein each R3 is H.

Embodiment 26. A compound of Formula 1 or any of Embodiments 1—25 wherein R2 is C(=Z)NR6R7, C(=NR“’)R11 or Qa.

Embodiment 27. A compound of Formula 1 or any of ments 1—25 n R2 is C(=NR10)R11.

Embodiment 28. A compound of Formula 1 or any of Embodiments 1—25 wherein R2 is C(=NR10)R11; R10 is C1—C4 alkoxy; and R11 is C1—C4 alkyl substituted with S(O)nR23.

Embodiment 29. A compound of Formula 1 or any of Embodiments 1—25 wherein R2 is R6R7 or Q3.

Embodiment 30. A compound of Formula 1 or any of Embodiments 1—25 wherein R2 is C(=Z)NR6R7.

Embodiment 31. A compound of Formula 1 or any of Embodiments 1—25 n R2 is C(=O)NR6R7.

Embodiment 32. A compound of Formula 1 or any of Embodiments 1—25 wherein R2 is C(=S)NR6R7.

Embodiment 33. A nd of Formula 1 or any of Embodiments 1—25 wherein R2 is C(=O)NR6R7; and R6 is H, C(O)OR21, C(0)R22 or c1—c6 alkyl.

Embodiment 35. A compound of Formula 1 or any of Embodiments 1—25 wherein R2 is C(=O)NR6R7; and R6 is H, C(O)OMe, C(O)Me or methyl. ment 36. A compound of a 1 or any of Embodiments 1—25 wherein R2 is C(=O)NR6R7; and R6 is H.

Embodiment 36a. A compound of Formula 1 or any of Embodiments 1—25 wherein R2 is C(=O)NR6R7; and R6 is C(O)OMe.

Embodiment 36b. A compound of Formula 1 or any of Embodiments 1—25 wherein R2 is R6R7; and R6 is C(O)Me.

Embodiment 360. A compound of Formula 1 or any of Embodiments 1—25 wherein R2 is C(=0)NR6R7; and R6 is methyl.

Embodiment 37. A compound of Formula 1 or any of Embodiments 1—25 wherein R2 is ment 38. A compound of Formula 1 or any of ments 1—25 wherein R2 is Qa; and Qa is a 5- or 6-membered aromatic ring, each ring containing ring members selected from carbon atoms and up to 3 heteroatoms independently ed from one oxygen atom, one sulfur atom, and up to 3 nitrogen atoms, each ring being unsubstituted or substituted with at least one RX.

Embodiment 39. A compound of Formula 1 or any of Embodiments 1—25 wherein R2 is Qa; and Qa is a 5- or 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 3 en atoms, each ring being unsubstituted or substituted with at least one RX. ment 40. A compound of Embodiment 39 wherein the heteroaromatic ring is a -membered heteroaromatic ring.

Embodiment 41. A compound of Embodiment 40 wherein the aromatic ring is a —membered heteroaromatic ring having a nitrogen atom at the 2—position.

Embodiment 42. A compound of Embodiment 39 wherein the heteroaromatic ring is a 6—membered heteroaromatic ring.

W0 38503 Embodiment 43. A compound of Embodiment 42 wherein the heteroaromatic ring is a 6-membered heteroaromatic ring having a nitrogen atom at the 2-position.

Embodiment 44. A compound of Embodiment 43 n the heteroaromatic ring is a 6—membered heteroaromatic ring having a nitrogen atom at the 2—position and substituted with C1—C4 haloalkyl.

Embodiment 45. A compound of Embodiment 44 wherein the aromatic ring is a 6—membered heteroaromatic ring having a nitrogen atom at the 2—position and substituted with CF3.

Embodiments of this invention, including Embodiments l—45 above as well as any other embodiments described , can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula 1 but also to the starting compounds and intermediate compounds useful for preparing the nds of Formula 1. In on, embodiments of this invention, including Embodiments l—45 above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present ion.

Combinations of Embodiments 1—45 are rated by: Embodiment A. A compound of Formula 1 wherein X1 is CR2, and X2, X3 and X4 are each independently CR3; or X2 is CR2, and X1, X3 and X4 are each independently CR3.

Embodiment B. A compound of Embodiment A wherein Q is Q—l or Q—2.

Embodiment C. A compound of Embodiment B wherein Q is Q—l; and Y1 is 0 or s.

Embodiment D. A compound of Embodiment C wherein Q is Q-2; and Y2 is CR5? Embodiment E. A compound of any of Embodiments A—D wherein A is CH or CF; and rn is 0. ment F. A compound of Formula 1 wherein A is CH or CF; m is 0; Q is Q-2; Y2 is CR5a; X1 is CR2 and X2, X3 and X4 are each CH; or X2 is CR2 and X1, X3 and X4 are CH; R2 is C(:Z)NR6R7 or Qa.

Embodiment G. A compound of Formula 1 wherein W0 38503 PCT/U82014/054671 A is CH or CF; m is 0; Q is Q-2; Y2 is CR5a; X1 is CR2 and X2, X3 and X4 are each CH; R2 is C(:Z)NR6R7 or Qa.

Embodiment H. A compound of Formula 1 wherein A is CH or CF; m is 0; Q is Q-2; Y2 is CR5a; X2 is CR2 and X1, X3 and X4 are CH; R2 is C(=Z)NR6R7 or Qa.

Embodiment I. A nd of Formula 1 wherein A is CH; m is 0; Q is Q-2; Y2 is CR5a; R5a is H; X1 is CR2 and X2, X3 and X4 are each CH; or X2 is CR2 and X1, X3 and X4 are CH; R2 is C(O)NR6R7; and R6 is H.

Embodiment J. A compound of Formula 1 wherein A is CH; m is 0; Q is Q-2; Y2 is CR5a; R5a is H; X1 is CR2 and X2, X3 and X4 are each CH; R2 is C(O)NR6R7; and R6 is H.

Embodiment K. A compound of Formula 1 wherein A is CH; m is 0; Q is Q-2; Y2 is CR5a; R5a is H; X2 is CR2 and X1, X3 and X4 are CH; R2 is C(O)NR6R7; and R6 is H.

Specific embodiments include compounds of Formula 1 selected from the group ting of (compound numbers refer to Index Tables A-N): ethylethyl)—2-(3 -pyridinyl)-2H—indazolecarboxamide und 8); N—cyclopropyl—2—(3-pyridinyl)—2H—indazolecarboxamide (compound 14); N—cyclohexyl—Z—(3—pyridinyl)-2H—indazolecarboxamide (compound 16); 2-(3-pyridinyl)—N—(2,2,2-trifluoroethyl)-2H-indazolecarboxamide (compound 19); 2-(3 -pyridinyl)—N—[(tetrahydrofuranyl)methyl]-2H-indazolecarboxamide (compound 41); methyl 2-[[2-(3—pyridinyl)—2H—indazolyl]carbonyl]hydrazinecarboxylate (compound 42); N—[(2,2-difluorocyclopropyl)methyl](3-pyridinyl)-2H—indazole-S-carboxamide (compound 51); N—(2,2-difluoropropyl)—2-(3-pyridinyl)-2H—indazolecarboxamide (compound 54); 2—(3-pyridinyl)-N—(2-pyrimidinylmethyl)-2H—indazolecarboxamide (compound 55); and N—[(5-methylpyrazinyl)methyl](3-pyridinyl)-2H—indazole-S-carboxamide (compound 76).

Of note is that compounds of this invention are characterized by favorable metabolic and/or soil residual patterns and exhibit activity lling a spectrum of agronomic and nonagronomic invertebrate pests.

Of particular note, for reasons of invertebrate pest control spectrum and economic ance, protection of agronomic crops from damage or injury caused by invertebrate pests by controlling ebrate pests are embodiments of the invention. Compounds of this invention because of their favorable translocation properties or systemicity in plants also t foliar or other plant parts which are not directly contacted with a compound of Formula 1 or a composition comprising the compound.

Also noteworthy as embodiments of the present invention are compositions comprising a compound of any of the ing 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 fithher comprising at least one additional biologically active nd or agent.

Further noteworthy as embodiments of the present invention are compositions for controlling an ebrate pest comprising a compound of any of the preceding Embodiments, as well as any other ments described herein, and any combinations thereof, and at least one additional ent 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 invention further include methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its nment with a biologically effective amount of a compound of any of the preceding Embodiments (e.g., as a ition bed herein).

Embodiments of the invention also include a composition comprising a compound of any of the preceding Embodiments, in the form of a soil drench liquid formulation.

Embodiments of the invention further include methods for controlling an ebrate pest comprising contacting the soil with a liquid composition as a soil drench comprising a ically effective amount of a compound of any of the preceding ments.

Embodiments of the invention also include a spray ition 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 invention 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 ant. Embodiments of the invention also include a device for controlling an invertebrate pest comprising said bait composition and a housing adapted to receive said bait composition, wherein the g 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 on outside the housing, and wherein the housing is fiirther adapted to be placed in or near a locus of potential or known activity for the invertebrate pest.

Embodiments of the invention also include methods for ting a seed from an invertebrate pest comprising contacting the seed with a biologically ive amount of a compound of any of the preceding Embodiments.

Embodiments of the invention 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. ments of the invention also include methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of a 1, an e or a salt f, (e.g., as a composition described herein), provided that the methods are not methods of medical treatment of a human or animal body by therapy.

This invention also relates to such methods wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of Formula 1, an N—oxide or a salt f, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said ition optionally further sing 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—13 can be used to e the compounds of Formula 1. The ions of substituents in the compounds of Formulae 1—23 below are as defined above in the Summary of the Invention unless otherwise noted. Compounds of ae la—lg are various subsets of the compounds of Formula 1, and all substituents for ae la—lg are as defined above for Formula 1. The following abbreviations are used: THF is tetrahydrofuran, DMF is N,N— dimethylformamide, NMP is N—methylpyrrolidinone, Ac is e, MS is mesylate, Tf is triflate, and Nf is nonaflate.

Compounds of a 1a (Formula 1 wherein Q is Q-l, Q-3 or Q—4) can be prepared as shown in Scheme 1 by the ng of a cyclic compound of Formula 2 (wherein LG is a suitable g group such as Cl, Br, I, Tf or Nf) with a heterocyclic compound of a 3 (wherein M is a suitable metal or metalloid such as a Mg, Zn or B species) in the presence of a catalyst and appropriate ligand. sts can be generated from transition metals such as Pd (for example Pd(OAc)2 or Pd2(dba)3 and mono- or bi-dentate s such as PPh3, PCy3, Pt—Bu3, , xantphos, s-phos, and dppf. Typical bases used include carbonates such as sodium carbonate or cesium carbonate, phosphates such as potassium sphate, amines such as ethyldiisopropylamine, or alkoxides such as sodium tert- butoxide. Typical solvents include THF, dioxane, toluene, ethanol, DMF, water or mixtures thereof. Typical reaction temperatures range from ambient temperature to the boiling point of the solvent.

Scheme 1 1 1 —A\/(R )1“ catalyst, ligand —A‘/(R )m Q_LG + M \ /) —> Q \ /) N N 2 3 la wherein Q is Q-l, Q-3 or Q-4 Compounds of Formula 121 (Formula 1 wherein Q is Q-l, Q-3 or Q—4) can also be ed as shown in Scheme 2 by the coupling of a compound of Formula 4 with a compound of Formula 5 (wherein LG is a suitable g group such as Cl, Br, I, Tf or Nf) in the presence of a catalyst and an appropriate ligand. A variety of catalysts can be used in the method of Scheme 2, and these can be generated from a transition metal species such as copper or Pd (for example complexes such as Pd(OAc)2 or Pd2(dba)3) and a ligand. Typical ligands may be mono- or bi-dentate, and include PPh3, PCy3, Pt-Bu3, x—phos, xantphos, s- phos, and dppf. l bases used include carbonates such as sodium carbonate or cesium carbonate, phosphates such as potassium triphosphate, amines such as ethyldiisopropylamine or alkoxides such as sodium tert-butoxide. Additives such as molecular sieves, Bu4N+Br' or copper or silver salts (e.g., AgOAc) can be beneficial. Typical reaction solvents include THF, dioxane, toluene, ethanol, DMF, water, or mixtures thereof. Typical reaction temperatures range from ambient temperature to the boiling point of the solvent. For W0 2015f038503 2014/054671 examples, see Chemical Communications 2011, 47(17), pages 5043-5045; Journal of the American Chemical Society 2010, 132(11), pages 3674-3675; Heterocycles 2011, 83(6), pages 1371-1376; US. Patent Application Publication 20090076266; Bulletin of the Chemical Society n 1998, 71(2), pages 467-473; Tetrahedron Letters 2008, , pages 1598—1600; and Tetrahedron Letters 2010, 51 (42), pages 5624—5627.

S—cheme2 —A‘/(R1 )1“ catalyst ligand \—A//(Rl )m 4 5 1a wherein Q Is Q-l, Q-3 or Q-4. . nds of Formula 2 wherein LG is halogen can be prepared from the corresponding amines by ent with a source of ON+ such as l nitrite or t-butyl nitrite or nitrous acid in the presence of a halogen source such as CuBr2 or BnNEt3+Br'.

Preferred reaction conditions include aqueous or organic solvents such as THF or acetonitrile, and reaction temperatures ranging from 0 °C to the boiling point of the solvent.

Compounds of Formula 2 wherein LG is C1 or Br can also be ed from the corresponding hydroxy compounds by treatment with a halogenating agent such as POC13, PC15, PBr3 or SOCIZ. Compounds of Formula 2 n LG is OMS or OTf can also be prepared from the corresponding hydroxy compounds by treatment with MsCl or ngO.

Compounds of a 4 can be prepared from the corresponding amine compounds by treatment with a source of ON+ such as isoamyl nitrite or t-butyl nitrite. Preferred reaction conditions e ethereal solvents such as THF at temperatures g from ambient temperature to the boiling point of the solvent.

Compounds of Formula 6 can be prepared by electrophilic halogenation of the corresponding compounds of Formula 7 by treatment with a halogenating agent such as N- uccinimide in a suitable solvent such as DMF, NMP or acetic acid at temperatures ranging from ambient temperature up to the boiling point of the solvent (Scheme 3).

Scheme 3 X2X$\NJ;:\3>—H XZX’e\N —> J;§—Nhalogen 2-Aminobenzothiazoles of Formula 8 can be prepared from ortho-unsubstituted anilines of Formula 9 and a thiocyanate anion (wherein M is K+, Na+ or Bu4N+) as shown in Scheme 4. The reaction can be conducted in a single step in acetic acid for example, or through the intermediacy of a thio-urea followed by ion. Suitable oxidants include bromine.

Scheme 4 Z’X] l NHZ MSCN, bromine acetic acid X 2¢ N X X or MSCN, sulfuric acid, then bromine I I I \ 3 l NHz x3\ x§ \X4 X4 3 M is Kl, Na+ or Bu4NJr 9 8 Compounds of Formula 1b can be prepared from compounds of a 10 by the method shown in Scheme 5, in which a compound of Formula 10 is treated with an azide reagent (for example, sodium azide or tetrabutylammonium azide). l reaction conditions include DMF or NMP as solvent, and reaction temperatures ranging from 80 °C to the boiling point of the t.

Scheme 5 IQ4<i/(12)m azide reagent XZI’:jrf:{/(R1)m _> | LG is a leaving group such 1b as F or N02 Compounds of Formula 1b can also be prepared from compounds of Formula 1021 by the method shown in Scheme 5a, in which a nd of a 10a is treated with triethyl phosphite.

X29 —/(R )mA l a R1 (EtO)3P XZ'X )m I, | N _. xi, \ /) \—A//( X LG N 103 LG is N02 1b Compounds of Formulae 10 and 1021 are Schiff bases and can be prepared by methods known in the art (see, for e, March, J Advanced Organic Chemistry, Wiley, 1992, pages 896—898.

W0 2015f038503 Compounds of Formula 1c can be prepared from nds of Formula 11 by the method shown in Scheme 6 via ion of a nd of Formula 11 with lar oxygen or a peroxide such as t-butyl hydroperoxide in the presence of a copper (II) catalyst such as Cu(OAc)2 or CuBrz. Typical on conditions ed alcoholic solvents such as t-amyl alcohol, DMF, NMP or aqueous ammonia, and reaction temperatures from 60 °C to the boiling point of the solvent.

Scheme 6 X2¢XX1 \\ \A//—(R)m Cu(II) oxidant X2’X —A/(R )m 13I}: w? 11 1c 2-Aminoazo compounds of Formula 11 can be prepared by reaction of an aniline of a 9 with a diazonium salt of Formula 12 by methods known in the art (see, for example, March, 1, Advanced Organic Chemistry, Wiley, 1992, pages 525-526).

Compounds of Formula 11 can also be prepared by reaction of an aryl nitroso compound of Formula 13 with a diamine of Formula 14 in a solvent such as acetic acid. These two methods are shown in Scheme 7.

Scheme7 XXX NH2 —A/(R1)m )2, | + New \ 2 _» §x4 H X" N x 1 2¢ N X —A, 9 12 \\ /(R)m l: N \ /) \x4 N112 N ,x NH X2' 2 0\\ —A/(R)m1 11 l3 l + N \ /) —> \x4 NH2 N 14 13 Compounds of Formula 1d can be prepared by condensation of a compound of Formula 14 (wherein Lg is a suitable leaving group such as C1 or Br) with an aminopyridine or aminodiazine of Formula 16 as shown in Scheme 8. l reaction conditions include an alcoholic solvent such as ethanol or toluene, and a reaction temperature range from t temperature to the boiling point of the solvent. The pyridine nitrogen can optionally be protected as a BH3 , an N-oxide, or a 2- or 6-halopyridine derivative.

Scheme 8 ,X NH 1 l )|(2 , T 2 0 —A/<R )m chX N \ —A/<R1>m 3 / ' X§X4IN \ —> 3 LG N X§X4J§N \ N/) LG 15 a leavmg group. . 14 1d such as C1 or Br Compounds of Formula 1e can be prepared as shown in Scheme 9 by the cycloaddition of 2-aminopyridines of Formula 15 with arylnitriles of Formula 16 (see, for example, l of the American Chemical Society 2009, 131(42), pages 15080-15081, and WO 2013041472.

Scheme 9 ,X NH 1 1 X2’ \r 2 —A/(R )m /N —A/(R])m >l<3\ |N + NC \ / —’ '3 k \ \ /) \X4’ N XNX4 N N 16 1e Compounds of a 1e can also be prepared by rearrangement of compounds of Formula 17 by treatment with base as shown in Scheme 10 (see, for example, J. Het Chem 1970, 7 page 1019). Compounds of Formula 17 can be prepared by methods described in WO 2008006540 and J. Org. Chem, 1966, page 251. ¥2¢X\N/N\ —A/(Rl)m ’ X3§X4J§N \ N) W0 2015I038503 PCT/U82014/054671 ediates of Formula 18 can be prepared by the method shown in Scheme 11 by treatment of a 2-aminopyridine of Formula 15 with an nate followed by hydroxylamine and a suitable base such as triethylamine.

Scheme 11 x1 NH ,Xl Xz” 2 1. EtOC(O)NCS XZ’ \N/N\ I | —> | NH2 x3 N X3 \ §X4’ 2. NHZOH-HCI, §X4 N base 18 Compounds of Formula 1 wherein Q is Q-4 can also be prepared by the method described in Synthesis Example 6.

Compounds of Formula 1f can be ed as shown in Scheme 12 by oxidatiVe lO cyclization of an aryl aldehyde of Formula 20 with an aniline of Formula 19 bearing an ortho-halogen, preferably iodine, in the presence of sulfur which acts as both a source of sulfur and as an oxidizing agent. The reaction is carried out in the presence of a base such as K2C03 in a suitable solvent such as water or DMF, and is catalyzed by the addition of copper salts (for example, CuI or CuClz) and ably a suitable ligand such as 1,10- phenanthroline. Typical reaction temperatures range from 70 °C to the boiling point of the solvent.

Scheme 12 l I + OHC X3§ \ / —> X4 halogen N 19 20 halogen 2’IX S —A, (R1)m 1‘ S I / zcxl _A (R1)m x; \ /) r —» | /) / 4 X3\ \ X E N \X4 N N 21 1f ,X 1 r” 15%“ a_ 3 \ r X§X4 E N Compounds of Formula 1f can also be prepared by cyclization of 2-halothioamides of Formula 21 as shown in the second reaction of Scheme 12 with a base such as KOtBu, NaH, DBU or C82CO3 in a suitable solvent such as toluene or DMF, optionally with the addition of copper salts such as CuI, and preferably a suitable ligand such as 1,10-phenanthroline.

This reaction can also be catalyzed by Pd species such as that prepared from Pd2(dba)3 and (t-Bu)2P-o-bipheny1, a base such as C82CO3 in a suitable solvent, such as 1,2- dimethoxyethane or dioxane. Typical reaction temperatures range from 80 °C to the boiling point of the solvent. For - and Pd-catalyzed reactions, the halogen substituent on the compound of Formula 21 is preferably Br or I. For example, see Journal of Organic Chemistry 2006, 71(5), pages 808; Tetrahedron Letters 2003, 44(32), pages 6073- 6077; tic Communications 1991, 21(5), pages ; and Eur. Pat. Appl. No. 450420.

Compounds of Formula 1f can also be prepared by the oxidative cyclization of thioamides of Formula 22 as shown in the third reaction of Scheme 12. Oxidants lly used in this method include bromine or iodine, DDQ and N)6. For example, see edron 2007, 63(41), pages 10276-10281; Synthesis 2007, (6), 819-823; and US. Pat.

Appl. Publ., 20120215154.

W0 2015f038503 The three methods described in Scheme 12 can be used to prepare compounds wherein Xl-X4 are carbon atoms, or wherein one of Xl-X4 is a nitrogen (for example, see J.

Heterocyclz’c Chem. 2009, 46, page 1125 and references cited therein).

Compounds of Formula 1, and intermediates used in the preparation of compounds of Formula 1, wherein Z is S can be prepared by thionation of the corresponding compounds wherein Z is O with, for e, Lawesson’s reagent (CAS No. 19172—47—5), Belleau’s reagent (CAS No. 888168) or P2S5. The thionation reactions are typically conducted in solvents such as toluene, s or dioxane, and at elevated temperature from 80 0C to the boiling point of the solvent.

Compounds of Formula 1 n R2 is C(O)NR6R7 can be prepared by carbonylation of the corresponding compounds wherein R2 is halogen (preferably Br or I), or wherein R2 is a sulfonate (for example, triflate or te). The reaction is performed in the presence of a source of carbon monoxide such as carbon de gas or Mo(CO)6 at pressures between atmospheric pressure and 25 bar, optionally with microwave g, and generally at ed temperatures in the range of 80 to 160 0C. Typical reaction solvents include DMF, NMP, toluene or ethereal solvents such as THF or dioxane. nds of Formula 1 wherein R2 is Qa can be prepared as shown in Scheme 13.

The method of Scheme 13 is similar to the method described in Scheme 1; M is a suitable metal or metalloid such as a Mg, Zn or B species, and R2 corresponds to LG in Scheme 1 and is a suitable leaving group such as Cl, Br, I, Tf or Nf.

Ri —A\/(R1 )111 catalyst, ligand —A\/(R1 )m Qa_M + Q Qa\Q \ N) \ N) 23 1 1g Compounds of Formula 1 wherein R2 is Qa and Qa is bonded to Q via a nitrogen atom in Qa can be prepared by a method similar to that of Scheme 13. In this method, M in the compound of Formula 23 is hydrogen. Coupling ts include copper(I) salts such as CuI, and a suitable ligand such as trans-bis(N,N-dimethyl-l,2-cyclohexanediamine. Typical reaction conditions include a solvent such as toluene or dioxane, and an ed on temperature ranging from 80 0C to the boiling point of the solvent.

Examples of intermediates useful in the preparation of nds of this invention are shown in Tables I-l through I-l6. The following abbreviations are used in the Tables which : Me means methyl, Et means ethyl, Ph means phenyl, C(O) means carbonyl and CH0 means formyl.

TABLE I-l ifHN\ / {A\ /> N N Ais CH -COOH -C(O)OMe 'C(O)OEt cyano -C(O)C1 -C(O)OPh (4-nitr0phenyl) -C(O)Me -CHO Cl Br I 2CF3 NH2 mm — Ais CF 3 __ -COOH —C(O)OMe -C(O)0Et -C(O)C1 -C(O)OPh —C(O)O(4-nitr0phenyl) -C(O)Me -CHo -0s<o>2CF3 mm) — AisN 3 —_ -COOH -C(O)OMe -C(O)C1 -C(O)OPh -C(O)O(4-nitr0pheny1) -C(O)Me -CH0 -OS(O)2CF3 ZIN zAzV> Ais CH -COOH -C(O)OMe -C(O)OEt cyano -C(O)C1 Ph —C(O)O(4-nitr0phenyl) -C(O)Me -CHO Q Br >—4 -OS(O)2CF3 2mN nitro Ais CF -COOH -C(O)OMe -C(O)OEt cyano -C(O)C1 -C(O)OPh -C(O)O(4-nitr0phenyl) -C(O)Me -CHO Q Br fi—1 -0S(O)2CF3 2IN nitro -C(O)0Et -C(O)C1 Ph —C(O)O(4-nitr0phenyl) -C(O)Me W0 2015I038503 -OS(O)2CF3 NH2 nitro TABLE 1-3 N {:9 A is CH -COOH -C(O)OMe -C(O)OEt cyano -C(O)C1 -C(O)OPh —C(O)O(4-nitr0phenyl) -C(O)Me —CHO C1 Br I 2CF3 ZIN nitro A is CF -COOH -C(O)OMe -C(O)OEt cyano -C(O)C1 -C(O)OPh -C(O)O(4-nitr0phenyl) -C(O)Me -CHO O,_.

-OS(O)2CF3 ZIN nitro AisN -COOH -C(O)OMe W0 2015/‘038503 PCT/U82014/054671 —C(O)O(4—nitropheny1) 2CF3 NH2 nitro TABLE 1-4 R _A \N/ \ N/> A is CH -COOH -C(O)OMe -C(O)OEt cyano -C(O)C1 -C(O)OPh -C(O)O(4-nitropheny1) -C(O)Me -CHo Br I -os<o>2CF3 nitro — A is CF 3 —_ -COOH -c<o>0Et -c<o>c1 -c<o>o<4-nmopheny1> -<:Ho -os<o>2cF3 nitro — A is N -COOH -c<o>0Et -c<o>c1 <4-nmopheny1> -CHo 2CF3 nitro — TABLE 1-5 / —A Table 1-5 is identical to Table 1-1, except that the structure shown under the heading "Table 1-1" is replaced by the structure shown above.

TABLE 1-6 \ \N \ N/> Table 1—6 is identical to Table 1-1, except that the structure shown under the heading "Table 1-1" is replaced by the structure shown above.

TABLE 1-7 / _A Table 1-7 is identical to Table 1-1, except that the structure shown under the heading "Table 1-1" is replaced by the structure shown above.

PCT/USZOl4/054671 TABLE 1-8 / _A Table 1—8 is cal to Table 1-1, except that the structure shown under the heading "Table 1-1" is replaced by the structure shown above.

TABLE 1-9 Table 1—9 is identical to Table 1-1, except that the structure shown under the heading "Table 1-1" is replaced by the structure shown above.

TABLE 1-10 7:1M_A\ /> N N Table 1—10 is identical to Table 1-1, except that the structure shown under the g "Table 1-1" is replaced by the structure shown above.

TABLE 1-1 1 SIM? Table 1—4 is identical to Table 1-1, except that the structure shown under the heading "Table 1-1" is replaced by the structure shown above.

TABLE 1-12 (EH? PCT/USZOl4/054671 Table 1-4 is cal to Table 1-1, except that the structure shown under the heading "Table 1-1" is replaced by the structure shown above.

TABLE 1-13 R H / i r U.

N02 Table 1-13 is identical to Table 1-1, except that the structure shown under the g "Table 1-1" is replaced by the structure shown above.

TABLE 1-14 R@N \\ N N02 Table 1—14 is identical to Table 1-1, except that the structure shown under the heading "Table 1-1" is replaced by the structure shown above.

TABLE 1-15 dgR H / F Table 1-15 is identical to Table 1-1, except that the structure shown under the heading "Table 1-1" is replaced by the structure shown above.

TABLE 1-16 H / Rag@N F Table 1-16 is identical to Table 1-1, except that the structure shown under the heading "Table 1-1" is replaced by the structure shown above.

It is recognized that some reagents and reaction conditions bed above for ing compounds of Formula 1 may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group onversions 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 introduction of the reagents depicted in the individual schemes, onal routine synthetic steps not described in detail may be needed to complete the synthesis of compounds of Formula 1. One skilled in the art will also recognize that it may be necessary to m a combination of the steps rated in the above schemes in an order other than that d by the particular sequence presented to prepare the compounds of Formula 1.

One skilled in the art will also recognize that compounds of Formulal and the ediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction ons to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the art using the preceding description can e the present invention to its fullest extent. The following Synthesis Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Steps in the following Synthesis Examples illustrate a procedure for each step in an overall synthetic transformation, and the starting material for each step may not have necessarily been prepared by a ular preparative run whose procedure is described in other Examples or Steps. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. 1H NMR spectra are reported in ppm ld from tetramethylsilane; (C ,3 s means singlet, “d” means doublet, “t” means triplet, “q” means quartet, “m” means multiplet, “dd” means doublet of doublets, “dt” means t of triplets, “br s” means broad singlet. DMF means N,N— dimethylformamide. nd numbers refer to Index Tables A-N.

SYNTHESIS EXAMPLE 1 Preparation ofN-[2-(methylthio)ethyl](3-pyridinyl)—7-benzothiazolecarboxamide (compound 84) Step A: Preparation of 3-[(aminothioxomethyl)amino]benzoic acid ethyl ester Ethyl 3-aminobenzoate (35.25 g, 213.6 mmol) was dissolved in chlorobenzene (250 mL) and cooled to -10 °C. Concentrated sulfiaric acid (5.93 mL) was added followed by KSCN (21.76 g) and 18-crown-6 (600 mg), and the reaction mixture was heated at 100 0C for 14 hours. Hexanes was added to the cooled mixture, and the precipitated solid was isolated by filtration. The solid was slurried in a e of water and hexanes, and the slurry was stirred for 1 hour. The solid was isolated by filtration and dried in vacuo overnight to give the title nd as a gray solid (40.7 g). 1H NMR (DMSO-d6) 5: 10.10 + 9.87 (two 5, 1H), 8.08 + 8.05 (two s, 1H), 7.66-7.80 (m, 2H), 7.43-7.51 (m, 1H), 8.0-7.0 (br s, 2H), 4.28-4.35 (m, 2H), 1.29-1.35 (m, 3H).

Step B: Preparation of 2-aminobenzothiazolecarboxylic acid ethyl ester The t of Step A was taken up in chloroform (300 mL) and acetic acid (200 mL) and bromine (21 mL) in chloroform (100 mL) was added dropwise over 1.5 hours. The reaction mixture was then heated at 70 °C for 4 hours, cooled, filtered, and the ed solid was washed with 50 mL of 1:1 acetone/chloroform. The solid was added to a solution of Na2C03 (25 g) in water (400 mL) and stirred for 20 minutes. The suspension was d, and the ed solid was washed with water, and dried in vacuo overnight to give the title nd (6.73 g) as a white solid. The c filtrate was concentrated and re-slurried in 100 mL of 1:1 chloroform/acetone, and processed as described above to give an additional 8.1 g of white solid (90% purity, the remaining 10% being the regioisomeric benzothiazole). 1H NMR d6) 8: 7.66 (dd, J=7.7, 0.9 Hz, 1H), 7.60 (s, 1H), 7.57 (dd, 1H), 7.35 (t, J=7.8 Hz, 1H), 4.37 (q, J=7.1 Hz, 2H), 1.36 (t, J=7.1 Hz, 3H).

Step C: Preparation of 2-chlorobenzothiazolecarboxylic acid ethyl ester The product of Step B (7.97 g, 9:1 e of regioisomers, 35.9 mmol) was added portionwise over 45 minutes to a mixture of tert—butylnitrite (7.1 mL) and CuC12 (5.31 g) in acetonitrile (360 mL) at 65 °C. After stirring for an additional 15 minutes, the cooled mixture was extracted 6 times with hexanes. The combined extracts were concentrated to give the title compound (5.85 g) as a yellow solid. The acetonitrile layer was diluted with water (200 mL), extracted with hexanes, and the hexane fraction was filtered through a pad of silica gel eluting with butyl chloride to yield an additional 0.55 g of product upon concentration. 1H NMR (CDC13) 8: 8.14 (d, 2H), 7.58 (t, 1H), 4.49 (q, J=7.1 Hz, 2H), 1.47 (t, J=7.2 Hz, 3H).

Step D: ation of 2-(3-pyridinyl)benzothiazolecarboxylic acid The product of Step C (6.2 g, 9:1 mixture of regioisomers) was combined with 3- nylboronic acid (3.79 g), PPh3 (1.35 g) and Na2C03 (5.44 g) in toluene (100 mL), water (25 mL) and ethanol (15 mL), and the reaction mixture was sparged with en for minutes. szdba3 (588 mg) was added, and the on mixture was heated at reflux for 4 hours. The cooled reaction mixture was diluted with water, extracted twice with dichloromethane, and the combined organic extracts were dried over MgSO4 and concentrated. The residue was purified by column chromatography (silica gel eluted with % to 50% ethyl acetate in hexanes) to give an orange solid (6.7 g) Recrystallization from ethanol (25 mL) yielded the ethyl ester of the title compound (5.65 g) as the single desired regioisomer. 1H NMR(CDC13) 8: 9.38 (br s, 1H), 8.75 (br s, 1H), 8.44 (dt, J=8.0, 1.9 Hz, 1H), 8.30 (dd, J=8.2, 1.1 Hz, 1H), 8.19 (dd, J=7.6, 1.1 Hz, 1H), 7.62 (t, 1H), 7.47 (dd, J=8.4, 4.4 Hz, 1H), 4.53 (q, J=7.2 Hz, 2H), 1.50 (t, J=7.2 Hz, 3H).

The product obtained above was dissolved in ethanol (100 mL) and treated with a 1N solution ofNaOH (24.8 mL). The reaction mixture was heated at reflux for 1.5 hours before being cooled, neutralized with concentrated HCl (2.0 mL), and trated. The residue was dried in vacuo to give a mixture of the title compound and NaCl, which was used without further ation in the next step.

Step B: Preparation ofN—[2-(methylthio)ethyl](3 -pyridinyl) benzothiazolecarboxamide Thionyl chloride (40 mL) was added to the product of Step D (0.55 g), and the reaction mixture was heated at reflux for 3 hour. The reaction mixture was then cooled and trated. The resulting residue was suspended in toluene and concentrated to yield the crude acid de, which was used without further purification.

The crude acid chloride (containing 120 mol% NaCl, 114 mg, 0.3 mmol) was treated with dichloromethane (5 mL), MeSCHZCHZNHZ (33 ML) and triethylamine (125 uL), and the reaction mixture was then stirred at ambient temperature for 14 hours. The reaction mixture was diluted with a saturated aqueous solution of NaHCO3, extracted twice with dichloromethane, and dried over MgSO4. The combined organic layers were trated, and the residue was purified by column chromatography (silica gel eluted with 30% ethyl acetate in hexanes to 100% ethyl acetate) to give 65 mg of the title compound, a nd ofthis invention. 1H NMR (CDCl3) 8: 9.39 (d, J=1.7 Hz, 1H), 8.74 (d, J=3.3 Hz, 1H), 8.40- 8.47 (dt, 1H), 8.26 (dd, J=8.0, 0.9 Hz, 1H), 7.71 (dd, J=7.6, 0.9 Hz, 1H), 7.58—7.64 (t, 1H), WO 38503 7.47 (dd, J=7.2, 5.0 Hz, 1H), 6.94 (br t, 1H), .82 (q, 2H), 2.80-2.88 (t, 2H), 2.18 (s, 3H).

SYNTHESIS EXAMPLE 2 Preparation of 2—(5—fluoropyridinyl)-N—(2,2,2-trifluoroethyl)—6—benzothiazolecarboxamide (compound 127) Step A: Preparation of 2-(5-fluoropyridinyl)benzothiazolecarboxylic acid Methyl 4-aminoiodobenzoate (1.93 g, 6.96 mmol) was combined with K2C03 (1.92 g), S8 (668 mg), CuC12-2H20 (119 mg), 1,10-phenanthroline (125 mg) and 5-fluoro pyridinecarboxaldehyde (957 mg) in H20 (30 mL), and the reaction e was heated at reflux 16 hours. The cooled reaction mixture was filtered, and the filtrate was treated with NH4Cl (1.49 g). The reaction e was stirred at ambient temperature for 10 minutes, filtered, and the solid was dried in vacuo to yield a gray solid. The solid was suspended in dioxane, the suspension was heated to reflux, cooled, and filtered to isolate a solid. The solid was rinsed with ethyl ether to give the title compound (0.66 g). 1H NMR (DMSO-d6) 8: 9.15 (s, 1H), 8.80 (d, J=2.7 Hz, 1H), 8.65 (s, 1H), 8.39 (dt, J=9.5, 2.2 Hz, 1H), 8.10 (d, 1H), 8.05 (d, 1H), 8.0—6.5 (br s).

Step B: Preparation of 2-(5-fluoropyridinyl)-N—(2,2,2—trifluoroethyl)—6— benzothiazolecarboxamide Thionyl chloride (5 mL) was added to the product of Step A (0.66 g), and the mixture was heated at reflux for 16 hours. The reaction e was then cooled and trated.

The resulting residue was suspended in toluene and concentrated to provide the crude acid chloride, which was used without further purification.

The crude acid chloride (103 mg, 0.31 mmol) was treated with dichloromethane (5 mL), triethylamine (131 uL) and CF3CH2NH2 (29 uL), and the reaction mixture was stirred at ambient temperature for 3 days. The reaction mixture was diluted with a ted aqueous on ofNaHCOg, extracted twice with dichloromethane, and dried over MgSO4.

The combined organic layers were concentrated, and the residue was purified by column chromatography (silica gel eluted with 20% to 40% ethyl acetate in s) to give the title compound, a compound of this invention, as a white solid (52 mg). 1H NMR (CDCl3) 8: 9.32 (br s, 1H), 8.77 (d, J=4.3 Hz, 1H), 8.48 (d, J=l.4 Hz, 1H), 8.40 (dt, J=7.9, 2.0 Hz, 1H), 8.16 (d, J=8.5 Hz, 1H), 7.90 (dd, J=8.5, 1.7 Hz, 1H), 7.48 (dd, J=7.8, 4.7 Hz, 1H), 6.48 (br t, 1H), 4.20 (qd, J=9.0 Hz, 1H).

SYNTHESIS EXAMPLE 3 Preparation ofN-(l-methylethy1)(3-pyridinyl)—2H—indazolecarboxamide (compound 8) Step A: Preparation ofN-[(2-bromofluorophenyl)methylene]—3—pyridinamine A on of 2-bromofluorobenzaldehyde (5 g, 24.6 mmol) and 3—aminopyridine (2.7 g, 29.5 mmol) in EtOH (4 mL) was heated to reflux overnight. The reaction mixture was concentrated and the resulting solid was purified by column chromatography (silica gel eluted with 0—40% ethyl acetate in hexanes) to afford the title compound (4.5 g) as an orange solid. 1H NMR (CDC13) 8: 8.66-8.70 (s, 1H), 8.48-8.53 (m, 2H), 7.52-7.58 (m, 1H), 7.41- 7.48 (m, 1H), 7.31-7.37 (m, 1H), 6.95-7.06 (m, 2H).

Step B: ation of o(3-pyridinyl)-2H—indazole A solution of the product of Step A (4.5 g, 16.1. mmol) and NaN3 (1.2 g, 19.3 mmol) in DMF (20 mL) was heated to 90 0C for 24 hours. The cooled mixture was diluted with water and extracted 3 times with dichloromethane. The combined c layers were dried (MgSO4), filtered, concentrated, and the residue was purified by column chromatography a gel eluted with 0-30% ethyl acetate in hexanes) to give the title compound (4.0 g) as a yellow solid. 1H NMR (CDC13) 8: 9.21 (d, J=2.4 Hz, 1H), 8.69 (dd, J=4.8, 1.3 Hz, 1H), 8.46-8.49 (d, 1H), 8.28 (ddd, J=8.3, 2.7, 1.5 Hz, 1H), 7.73 (d, J=8.7 Hz, 1H), 7.50 (ddd, J=8.2, 4.8, 0.7 Hz, 1H), 7.31 (d, 1H), 7.21 (dd, J=8.7, 7.3 Hz, 1H).

Step C: ation ofN—(1 -methylethyl)(3-pyridinyl)-2H-indazole—4—carboxamide The product of Step B (200 mg, 0.727 mmol), isopropylamine (183 uL, 2.18 mmol), trans-bis(acetato)bis[o-(di-o-tolylphosphino)benzyl]dipalladium(II) (17 mg, 0.018 mmol), tri-tert—butylphosphonium tetrafluoroborate (10.5 mg, 0.036 mmol), molybdenum rbonyl (192 mg, 0.727 mmol, 1,8-diazabicycloundecene (473 uL, 2.18 mmol) and DMF (5 mL) were placed in a microwave vial and irradiated at 160 °C for 40 minutes. The on mixture was then cooled to room temperature and filtered through a pad of Celite®.

The filtrate was diluted with a saturated solution of NaHCO3 and extracted with dichloromethane. The organic layer was dried (MgSO4), filtered, concnentrated, and the residue was purified by column chromatography (silica gel eluted with 0-10% acetone in chloroform). Trituration of the resulting solid with ethyl ether provided the title nd, a compound of this invention, as a white solid (45 mg). 1H NMR (CDCl3) 8: 9.26 (d, J=2.2 Hz, 1H), 9.09 (d, J=0.9 Hz, 1H), 8.67 (dd, J=4.7, 1.4 Hz, 1H), 8.29 (ddd, J=8.3, 2.6, 1.4 Hz, 1H), 7.92 (dt, J=8.5, 0.9 Hz, 1H), 7.48 (m, 1H), 7.31-7.41 (m, 2H), 6.15 (s, 1H), 4.31-4.41 (m, 1H), 1.33 (d, J=6.6 Hz, 6H).

SYNTHESIS E 4 Preparation of 2-(3-pyridinyl)-N-[1-(2,2,2-trifluoroethy1)]imidazo[1,2-a]pyridine amide und 457) Step A: Preparation of 2-(3 -pyridinyl)imidazo[1 ,2-a]pyridine—6—carboxylic acid methyl ester ing the procedure described in US Patent Application Publication No. 20110189794, to a mixture of methyl 6-aminonicotinate (5.0 g, 33 mmol) in ethanol (140 mL) at 60 °C was added solid sodium bicarbonate (5.52 g, 65.7 mmol), followed by 3- acetyl)pyridine hydrogen bromide salt (10.16 g, 36.2 mmol). The resulting mixture was heated to reflux for 9 hours. The on mixture was then cooled, concentrated, and saturated aqueous sodium bicarbonate solution (50 mL) and dichloromethane (50 mL) were added to the resulting residue. The aqueous phase was ted with dichloromethane (5 X mL). The combined organic phases were concentrated and purified by column chromatography a gel eluted with ethyl acetate) to give the title compound.

Step B: Preparation of 2-(3 -pyridiny1)-N—[1-(2,2,2-trifluoroethyl)]imidazo[l ,2—a] pyridinecarboxamide A mixture of the ester prepared in Step A (0.4 g, 2.4 mmol) and aqueous NaOH (1 N, 7.1 mL, 7.1 mmol) was stirred in methanol (10 mL) for 2 hours. The reaction mixture was then concentrated under reduced pressure to remove methanol, and the resulting aqueous solution was neutralized with 1N HCl to pH 5 to precipitate the carboxylic acid. The solid carboxylic acid was isolated by ion, dried, and used directly in the next step without fiirther purification.

A mixture of the carboxylic acid prepared above (0.31 g, 1.30 mmol), EDC-HCl (0.27 g, 1.43 mmol), HOBt-HZO (0.22 g, 1.43 mmol), and triethylamine (0.72 mL, 5.2 mmol) in DMF (10 mL) was stirred at 40 CC for 30 minutes. A quarter of the reaction mixture volume was then removed, treated with CF3CH2NH2 (0.13 g, 1.3 mmol), and stirred at 40 OC overnight. The reaction mixture was then concentrated under vacuum to remove DMF, and the residue was purified by column chromatography (silica gel eluted with ethyl e:methanol:triethylamine, 8:1:1) to obtain 43.8 mg of the title compound, a compound of this invention.

SYNTHESIS EXAMPLE 5 Preparation of methyl 2-[[2-(3-pyridinyl)-2H-indazolyl]carbonyl]hydrazinecarboxylate (compound 42) Step A: Preparation of 4-nitro-[(3 -pyridinylimino)methyl]benzoic acid methyl ester A solution of methyl 3-formylnitrobenzoate (5 g, 25 mmol) and 3—aminopyridine (2.7 g, 30 mmol) in ethanol (4 mL) was heated to reflux overnight. The reaction mixture was then cooled, concentrated under reduced pressure, and the ing crude solid was purified by silica gel chromatography (eluting with 0-40% ethyl acetate/hexanes) to afford 4.5 g of the title product as an orange solid.

Step B: Preparation of 2-(3 -pyridinyl)—2H—indazolecarboxylic acid methyl ester A solution of the product of Step A (4.5 g, 16 mmol) and sodium azide (1.2 g, 19 mmol) in DMF (20 mL) was heated to 90 CC for 16 hours. The reaction mixture was then cooled to room temperature and diluted with water. The resulting two layers were separated, and the aqueous layer was extracted three times with dichloromethane. The ed organic layers were dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting crude solid was purified by silica gel chromatography (0-30% ethyl e/hexantes ) to afford 4.0 g of the title product as a yellow solid.

Step C: Preparation of 2-(3 -pyridinyl)—2H—indazolecarbonyl chloride The methyl ester prepared in Step B (4.1 g, 16 mmol) was dissolved in ol (150 mL), 50% sodium hydroxide in water (7.1 mL) was added, and the reaction mixture was heated to reflux for 4 hours. The reaction mixture was then cooled to room temperature, and the t was removed under reduced pressure. The crude t was acidified with aqueous 1N HCl, and the resulting precipitate was isolated by filtration, washed with diethyl ether, and dried under reduced pressure at 60 oC overnight. The crude carboxylic acid was then olved in thionyl chloride (60 mL), and the reaction mixture was heated to 75 °C.

The reaction mixture was then cooled to room ature and the solvent was removed under reduced pressure. The crude carbonyl chloride was used in the next step t further purification.

Step D: Preparation of methyl 2-[[2-(3-pyridinyl)-2H-indazol bonyl]hydrazinecarboxylate The acyl chloride prepared in Step C (200 mg, 0.836 mmol) was combined with hydrazinocarboxylate (82 mg, 0.91 mmol) in dichloromethane (5 mL). The reaction mixture was cooled to 0 °C, and triethylamine (360 ul, 2.51 mmol) was added dropwise. The W0 2015f038503 reaction was warmed to room temperature and allowed stirred overnight. The reaction mixture was then cooled and quenched with saturated aqueous sodium bicarbonate solution.

The two layers were ted, and the aqueous layer was extracted three times with dichloromethane. The combined organic layers were dried over magnesium sulfate, d, and concentrated under reduced pressure. The resulting crude solid was purified by silica gel chromatography (20-80% ethyl acetate/hexanes) to yield the title compound, a compound of this invention, as a white solid.

SYNTHESIS EXAMPLE 6 Preparation of 2-(3 -pyridinyl)-N—[(tetrahydrofi1ranyl)methyl]pyrazolo[l ,5-a]pyridine carboxamide (compound 467) Step A: Preparation of 3-(dimethoxymethyl)—5-(3-pyridinyl)-lH—pyrazole Lithium hexamethyldisilane (55 mL of a 1.0M solution in tetrahydrofiiran, 55 mmoles) was added to a solution of 3-acetylpyridine (5.5 mL, 50 mmoles), methyl dimethoxy acetate (6.7 mL, 55 mmoles) and anhydrous tetrahydrofuran (100 mL) with g at -45 0C. The resulting reaction mixture was allowed to warm to 25 0C over 1 hour, and stirred at this temperature for 3 hours. The reaction mixture was then trated under reduced pressure, and the residue was suspended in methanol (50 mL) and concentrated under reduced pressure. The resulting residue was ded in methanol (150 mL) and treated with hydrazine drate (2.62 mL, 55 mmoles) and glacial acetic acid (6.29 mL, 110 mmoles), and the reaction mixture was heated at reflux for 14 hours. The resulting reaction mixture was cooled to 25 oC and concentrated under reduced pressure.

The residue was partitioned between ethyl e (200 mL) and 1N aqueous sodium ide solution (100 mL). The layers were separated, and the organic layer was washed successively with lN aqueous sodium hydroxide solution (50 mL) and brine (50 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to yield 8.83 g of the title compound as a beige solid. 1H NMR ): 8 10.5 (br s, 1H) 9.03 (d, 1H), 8.57 (dd, 1H), 8.09 (dt, 1H), 7.34 (dd, 1H), 6.65 (s, 1H), 5.63 (s, 1H), 3.39 (s, 6H).

Step B: Preparation of 5-(3-pyridinyl)—lH—pyrazolecarboxaldehyde To a solution of the product from Step A (715 mg, 3.3 mmoles) and form (5 mL) was added a solution of trifluoroacetic acid (2.5 mL) and water (2.5 mL); the reaction mixture temperature was maintained below 5 °C with an ice—water bath. The reaction mixture was then stirred at 0-5 °C for 2 hours, treated with triethylamine (5 mL) at 0 °C, stirred for 15 minutes, d with water (10 mL), and filtered to isolate a brown solid. This solid was washed with chloroform (20 mL) and water (20 mL), and air dried to yield 605 mg of the title compound as a light beige solid that was used in the next step without further purification.

Step C: Preparation of 2-(3-pyridinyl)pyrazolo[1,5-a]pyridine—5—carboxylic acid ethyl ester A mixture of the t from Step B (596 mg, 3.4 mmoles), ethyl—4—bromocrotonate (75%, 0.95 mL, 5.2 ), anhydrous potassium carbonate (1.42 g, 10.3 mmoles) and anhydrous N,N—dimethylformamide (17 mL) was stirred at 25 CC for 14 hours. The reaction e was then partitioned between ethyl acetate and saturated aqueous ammonium chloride solution, and the organic layer was separated, washed with water (3X), brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a crude t. This resulting t was d by MPLC on a 24 g silica column eluting with 0 to 100% ethyl acetate in hexanes to give the title nd as a light beige solid (105 mg). 1H NMR ): 8 9.20 (d, 1H), 8.63 (dd, 1H), 8.50 (d, 1H), 8.33 (d, 1H), 8.27 (dt, 1H), 7.43-7.35 (m, 2H), 7.05 (s, 1H), 4.43 (q, 2H), 1.44 (t, 3H).

Step D: Preparation of 2-(3-pyridinyl)-N—[(tetrahydrofuranyl)methyl]pyrazolo[1 ,5- a]pyridinecarboxamide To a solution of the t from Step C (31 mg, 0.11 mmoles), tetrahydrofurfurylamine (0.12 mL, 1.2 mmoles), and anhydrous toluene (2.3 mL) was added trimethylaluminum (0.6 mL of a 2.0M solution in toluene, 1.2 ). The resulting solution was stirred for 2 hours at 25 0C, for 2 hours at 80 oC, and then cooled to 0 °C and treated carefully with water (3 mL). The resulting reaction mixture was stirred at 25 °C for 15 minutes, treated with a saturated aqueous solution of sodium-potassium tartrate (2 mL), stirred for 30 minutes, and then partitioned between dichloromethane and water. The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to isolate a brown residue that was triturated with diethyl ether to yield the title compound, a compound of this invention, as a beige solid (15 mg). 1H NMR(CDC13): 8 9.19 (d, 1H), 8.63 (dd, 1H), 8.51 (d, 1H), 8.26 (dt, 1H), 8.03 (s, 1H), 7.39 (dd, 1H), 7.16 (dd, 1H), 7.00 (s, 1H), 6.60 (br s, 1H), 4.10 (qd, 1H), 3.93 (dt, 1H), 3.89-3.76 (m, 2H), 3.38—3.29 (m, 1H), 2.11-2.02 (m, 1H), 2.00-1.83 (m, 3H).

By the procedures described herein er with methods known in the art, the following nds of Tables 1 to 24d can be prepared. The following abbreviations are used in the Tables which follow: tmeans tertiary, s means secondary, i means iso, 0 means cyclo, Me means methyl, Et means ethyl, Pr means propyl, Bu means butyl, Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, SEt means W0 38503 ethylthio, —CN means cyano, Ph means phenyl, Py means pyridinyl, —N02 means nitro, S(O)Me means methylsulfinyl, and S(O)2Me means methylsulfonyl.

A "-" at the beginning of a fragment definition denotes the attachment point of said fragment to the remainder of the le; for example, "-CH2CH20Me" denotes the fragment 2—methoxyethyl. Cyclic fragments are represented by the use of two H_ H within parentheses; for example, the fragment l-pyrrolidinyl is represented by "N(- CHZCHZCHZCHZO", wherein a nitrogen atom is bonded to both terminal carbon atoms of the arbon chain, as illustrated below. -_N/ €le molecule \ CH C/ 2 H2 ———_ W0 2015I038503 2014/054671 -CH2<4-methoxypyndmy1> W0 38503 PCT/U82014/054671 W0 2015I038503 PCT/U82014/054671 methoxy—2—pyndmy1> -NH<4-methoxy—2—pynmidmy1> -CH2(4-methoxypyfidmyl) -CH2<s-methoxy-2pyridmyn W0 2015I038503 PCT/U82014/054671 -CH2(4—pyrimidiny1) pyridazinyl 6—CF3—3—pyraziny1 AisN § E H T. -CH2(c-Pr) —CH(Me)(c-Pr) US S”g: i-Bu t—Bu -CH2Ph -CH2CH=CH2 -CH2CECH 2CECH -CH2CH2F F2 -CH2CF3 -CH(Me)CF3 -CH2CH2CF3 -CH2CF2CF3 -CH2CF2CH3 -CH2CH2CF2CF3 -CH(i-Pr)CF3 —CH2CH20Me -CH20Et -CH2CHZO(i-Pr) -CH2CH20Et -CH2CH2CH20Me -CH2CH(Me)OMe -CH(Et)CH20Me W0 38503 PCT/U82014/054671 -NH<5-methy1—2—pyridmy1> -NH<4—methoxy—2-pyridmy1> -NH(3 -methoxypyridinyl) -NH(5—methoxypyridinyl) W0 2015I038503 2014/054671 TABLElb W0 2015I038503 PCT/U82014/054671 -CH2(4-methy1—2—pyrimidinyl) -meth0xy—2-pyridiny1) -CH2(3-Ineth0xypyridinyl) -CH2(5-Ineth0xypyridinyl) Ais CF W0 38503 PCT/U82014/054671 W0 2015I038503 PCT/U82014/054671 -NH<4-methoxy—2-pyridmy1> -NH<5methoxy-z-pyndmyn -methy1—2—pyridmy1> -CH2(4-methoxy.2-pyfidmyl) ———_ W0 38503 PCT/U82014/054671 W0 2015f038503 2014/054671 TABLE lc R O /\N/N4<\:N/> A is CH N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2—) N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-) N(-CH2CH2CH2CH2-) N(-CH2CHZSCH2CH2-) N(-CH2CH2CH2CH2CH2-) N(-CH2CH20CH2CH2-) N(-CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-) N(-CH2C(Me)2N=CH-) CH2CH2CH(CF3)CH2-) N<CH2CECH>2 N<Pr>CH2<c-Pr> N<-CHC<0>SCH2CH2-> — N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2-) N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-) W0 2015I038503 PCT/U82014/054671 N(—CH2CH2CH2CH2-) N(-CH2CH23CH2CH2-) N(-CH2CH2CH2CH2CH2-) N(-CH2CH20CH2CH2-) CH2N(C(O)(c-Pr))CHZCH2-) CH2N(MC)CH2CH2-) N(—CH2C(Me)2N=CH-) N(-CH2CH2CH2CH(CF3)CH2—) N(CH2CECH)2 N<Et>2 N(Pr)CH2(c-Pr) N(Et)(c-hexy1) N(—CHC(O)SCH2CH2-) AisN CH2CH2-) N(-CH2CH(OMe)CH2-) N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-) N(-CH2CH2CH2CH2-) N(-CH2CHZSCH2CH2-) N(-CH2CH2CH2CH2CH2-) N(-CH2CH20CH2CH2-) N(-CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-) N(-CH2C(Me)2N=CH-) N(-CH2CH2CH2CH(CF3)CH2-) N(CH2CECH)2 N(Et)2 N(Pr)CH2(c-Pr) N(Et)(c-hexy1) N(—CHC(O)SCH2CH2-) TABLE 1d R O A is CH N(—CH2CH2CH2-) N(-CH2CH(OM6)CH2—) N(—CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2—) N(-CH2CH2CH2CH2-) N(-CH2CH2$CH2CH2-) N(-CH2CH2CH2CH2CH2-) N(-CH2CH20CH2CH2-) N(—CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-) N(—CH2C(Me)2N=CH-) CH2CH2CH(CF3)CH2—) N(CH2CECH)2 N(Et)2 N(Pr)CH2(c-Pr) N(Et)(c-hexy1) W0 2015I038503 N(-CHC(O)SCH2CH2-) A is CF CH2CH2-) N(-CH2CH(OMe)CH2—) N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-) N(-CH2CH2CH2CH2-) N(-CH2CHZSCH2CH2—) N(—CH2CH2CH2CH2CH2-) CH20CH2CH2-) N(-CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2—) N(-CH2C(Me)2N=CH-) N(-CH2CH2CH2CH(CF3)CH2-) N(CH2CECH)2 N(Et)2 N(Pr)CH2(c-Pr) N(Et)(c-hexy1) N(-CHC(O)SCH2CH2-) AisN N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2-) N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-) N(—CH2CH2CH2CH2-) N(-CH2CHZSCH2CH2-) CH2CH2CH2CH2-) N(-CH2CH20CH2CH2-) N(—CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-) N(—CH2C(Me)2N=CH-) N(-CH2CH2CH2CH(CF3)CH2-) N(CH2CECH)2 N(Et)2 N(Pr)CH2(c-Pr) N(Et)(c-hexy1) N(-CHC(O)SCH2CH2-) TABLE 16 G<HN\/N {i} Ais CH 3 1—2-pyridiny1 3 -meth0xy—2—pyridinyl 3—(triflu0r0methy1)pyridiny1 3-(CH(=NOMe))-2—pyridinyl W0 2015I038503 PCT/U82014/054671 y1—2—pyridiny1 fluoromethy1)pyridiny1 4-(CH(=NOMe))pyridinyl -methy1pyridiny1 5-methoxypyridinyl -(triflu0r0methy1)pyridiny1 5-(CH(=I\OMe))pyridiny1 6-methy1—2—pyridmy1 6—(triflu0r0methy1)pyridiny1 2-methy1—3-pyndmy1 flu0r0methy1)-3 -pyridiny1 2-(CH(=\OMe))-3 iny1 4-methy1—3-pyridiny1 4-meth0xy-3 -pyridiny1 4-(triflu0r0methyl)-3 -pyridiny1 4-(CH(=\O\/[e))-3 -pyridiny1 -methy1—3-pyridinyl 5-meth0xy-3 -pyridiny1 -(triflu0r0methyl)-3 -pyridiny1 5-(CH(=\OVIe))-3 -pyridiny1 6-methy1—3-pyridmy1 6—(triflu0r0methy1)pyridiny1 2-methylpyridinyl 2-meth0xypyridinyl 2-(trifluoromethy1)pyridiny1 2-(CH(=\'O\/Ie))—4—pyridinyl 3 1pyridiny1 3 -methoxypyridinyl 3 uoromethy1)pyridiny1 3 -(CH(=NOMe))pyridinyl 3-methy1—2-pyrazmy1 3-(triflu0r0methy1)pyraziny1 3 -(CH(=I\OMe))pyrazinyl -methy1pyrazmy1 —(triflu0r0methy1)pyraziny1 5 -(CH(=‘.\OMe))pyraziny1 6-methy1—2—pyrazinyl 6-meth0xypyraziny1 6—(triflu0r0methyl)pyraziny1 6-(CH(=\OVIe))pyraziny1 4-methy1pyrimidiny1 fluor0methyl)pyrimidinyl 4-(CH(=\OVIe))pyrimidinyl -methy1pyrimidiny1 -(triflu0r0methyl)pyrimidiny1 5-(CH(=\OVIe))pyrimidinyl 2—methy1pyrimidiny1 2-meth0xypyrimidinyl 2-(trifluoromethyl)pyrimidiny1 2-(CH(=\'O\/Ie))pyrimidiny1 —methy1—4-pyrimidinyl 5-methoxypyrimidinyl -(trifluoromethyl)pyrimidiny1 5-(CH(=I\'OMe))pyrimidiny1 6-methy1pyrimidiny1 6-methoxypyrimidinyl 6-(trifluoromethyl)pyrimidiny1 6-(CH(=\'’ OMe))pyrimidinyl 3 -methylpyraz01y1 3 -methoxypyraz01y1 3—(triflu0r0methy1)pyrazoly1 3-(CH(=zOze, — —pyraz01y1 4—methy1— 1 01y1 4-meth0xypyraz01yl W0 2015I038503 PCT/U82014/054671 4-(trifluor0methy1)pyraz01y1 y1pyrazoly1 -(trifluoromethy1)pyrazoly1 4—(triflu0r0methyl)-1,2,3-triaziny1 6—(2—pyrimidiny1)pyridiny1 2—(2—thiaz01y1)thiazoly1 1,3,4-oxadiazoly1 tetrahydm-z-fmanyl 3-isoxazoly1 2-(triflu0r0methyl)pheny1 4-(triflu0r0methy1)phenyl A is CF 3 —_ 3-methy1—2—pyridiny1 3 -(trifluoromethy1)pyridinyl 3 -(CH(=NOMe))pyridinyl 4-methy1pyridiny1 4-methoxypyridinyl 4-(trifluoromethyl)pyridinyl 4-(CH(=I\'OMe))pyridinyl -methy1pyridmy1 —(trifluoromethy1)pyridinyl 6-methy1—2—pyndmy1 6—(triflu0r0methy1)pyridiny1 6-(CH(=\OMe))pyridinyl 2-methylpyridinyl 2-meth0xy-3 -pyridiny1 2-(triflu0r0methyl)-3 -pyridiny1 2-(CH(=\O\/[e))-3 iny1 y1—3-pyridiny1 4-meth0xy-3 -pyridiny1 4-(triflu0r0methyl)-3 -pyridiny1 4-(CH(=\O\/[e))-3 -pyridiny1 y1pyridmy1 flu0r0methyl)-3 -pyridiny1 5-(CH(=\'OV[e))-3—pyridiny1 6-methylpyridinyl 6-meth0xy-3 -pyridinyl 6—(triflu0r0methyl)-3 -pyridiny1 6-(CH(=\'O\/Ie))—3—pyridinyl 2-methy1—4-pyridiny1 2-methoxypyridinyl 2-(triflu0romethy1)pyridiny1 2-(CH(=NOMe))pyridinyl 3-methy1—4—pyridmy1 3 -(triflu0r0methy1)pyridiny1 3—methy1—2-pyraziny1 3-meth0xy—2-pyrazinyl 3—(triflu0r0methyl)pyraziny1 3 -(CH(=‘.\OMe))pyraziny1 W0 2015I038503 PCT/U82014/054671 s-methyI-z-pyrazinyl -(trifluor0methy1)pyraziny1 5-(CH(=NOMe))pyrazinyl 6-methy1pyrazinyl 6-methoxypyrazinyl 6-(triflu0r0methy1)pyraziny1 6-(CH(=NOMe))pyrazmyl 4—methy1pyrimidiny1 4—(trifluoromethyl)pyrimidinyl —methy1pyrimidiny1 —(triflu0r0methyl)pyrimidiny1 5-(CH(=\OVIe))pyrimidiny1 2-methy1pyrimidiny1 2-meth0xypyrimidinyl 2-(triflu0r0methyl)pyrimidiny1 2-(CH(=\OVIe))pyrimidinyl -methy1pyrimidiny1 5-meth0xypyrimidiny1 -(triflu0r0methyl)pyrimidiny1 6-methy1pyrimidiny1 6-(trifluoromethyl)pyrimidiny1 3-methy1—1-pyrazoly1 3-(triflu0romethy1)-1 -pyrazoly1 3-(CH(=\IOMe))- 1 —pyrazolyl 4-methy1—1-pyrazoly1 4-(trifluoromethy1)pyraz01y1 4-(CH(=-Ag(DV\T’ ,_. I’6"<3N.o_.‘5. -methy1- 1 oly1 oxypyrazoly1 flu0r0methy1)pyraz01y1 5-(CH(=-Ag(DVY ’T‘"O'~<BN2.‘5. 4—methy1-1,2, 3 -triazin-2—y1 4-meth0xy-1,2,3 —triazin—2—yl 4—(triflu0r0methy1)- 1 ,2,3 -triaziny1 4-(CH(=NOMe))-1,2,3—triazin—2—y1 6—(2—pyrimidinyl)pyridiny1 2-(2-pyridiny1)thiazoly1 hiaz01y1)thiazoly1 2-(2-pyrimidiny1)ethynyl 1,3,4-oxadiazoly1 tetrahydr0furanyl tetrahydro—Z-furanyl 4,5-dihydr0isoxazolyl 3 -is0xazoly1 phenyl 2-(triflu0r0methyl)pheny1 3 uoromethyl)phenyl 4-(triflu0r0methy1)phenyl fluor0methy1)pyraziny1 AisN 3-methy1pyridiny1 3-methoxypyridinyl 3-(triflu0r0methy1)pyridiny1 3-(CH(=NOMe))pyridinyl 4-methy1—2-pyridiny1 4-methoxypyridinyl 4—(trifluoromethyl)pyridiny1 4-(CH(=NOMe))—2—pyridinyl —methylpyridinyl 5-meth0xypyridinyl W0 2015I038503 PCT/U82014/054671 -(triflu0romethy1)pyridiny1 5 -(CH(=\'O\/Ie))—2—pyridinyl 6-methy1pyridiny1 6-methoxypyridinyl 6-(triflu0romethy1)pyridiny1 6-(CH(=NOMe))pyridinyl 2-methy1pyridiny1 2-methoxypyridinyl 2—(triflu0r0methy1)pyridiny1 4-methy1—3-pyridmy1 4—(triflu0r0methy1)pyridiny1 -methy1—3-pyridiny1 5-meth0xy-3 -pyridiny1 —(triflu0r0methy1)-3 -pyridiny1 5-(CH(=\O\/[e))-3 iny1 6-methy1—3-pyridiny1 6-meth0xy-3 -pyridiny1 6-(triflu0r0methy1)-3 -pyridiny1 6-(CH(=\O\/[e))-3 -pyridiny1 2-methy1—4—pyridmy1 2—(trifluor0methy1)pyridiny1 2-(CH(=\OVIe))-4—pyridiny1 3-methy1—4—pyridmy1 3 uoromethyl)pyridiny1 3 -(CH(=\'OVIe))pyridinyl 3 —methy1—2-pyraziny1 3 -methoxypyrazinyl 3-(trifluor0methy1)pyraziny1 3 NOMe))pyrazmyl -methy1pyraziny1 5-methoxypyrazinyl fluoromethy1)pyraziny1 5-(CH(=I\'OMe))pyrazmyl 6-methy1—2—pyrazmy1 6—(triflu0r0methy1)pyraziny1 4—methy1pyrimidiny1 4—(triflu0r0methy1)pyrimidiny1 4-(CH(=\OMe))pyrimidiny1 -methy1-2—pyrimidiny1 5-meth0xypyrimidinyl -(triflu0r0methy1)pyrimidiny1 5-(CH(=\OVIe))pyrimidinyl 2-methy1pyrimidiny1 2—(triflu0r0methyl)pyrimidiny1 2-(CH(=\OVIe))pyrimidinyl -methy1pyrimidiny1 -(trifluoromethyl)pyrimidiny1 5 -(CH(=\'O\/Ie))pyrimidinyl 6—methy1pyrimidiny1 0xypyrimidinyl 6—(triflu0r0methyl)pyrimidiny1 6-(CH(=\'O\/Ie))-4—pyrimidiny1 3-methy1—1-pyrazoly1 3-(trifluoromethy1)pyrazoly1 3-(CH(=NOMe))- 1-pyrazoly1 4-methy1— 1 -pyrazoly1 4-methoxy- 1 oly1 flu0r0methy1)pyrazoly1 4-(CH(=-A2(DVY 'T‘’U'~<BN2.‘5. —methy1— 1 -pyraz01y1 5-meth0xypyraz01yl —(triflu0r0methy1)pyrazoly1 5-(CH(=NOMe))pyraz01y1 W0 2015I038503 PCT/U82014/054671 O\ OO y1—1,2,3-triaziny1 4-methoxy-1,2,3 -triazin—2—yl 4-(triflu0r0methy1)-1,2,3 -triaziny1 4-(CH(=NOMe))-1,2,3-triaziny1 6-(2-pyrimidinyl)pyridinyl 2-(2-pyridiny1)thiazolyl 2-(2-thiazolyl)thiazoly1 2-(2—pyrimidinyl)ethynyl oxadiaz01y1 tetrahydr0—3—furanyl tetrahydro-Z-furanyl 4,5-dihydr0isoxaz01yl 3 -isoxazoly1 phenyl 2—(triflu0r0methyl)pheny1 3 -(trifluoromethyl)phenyl 4—(triflu0r0methy1)phenyl 6-(triflu0r0methy1)pyraziny1 TABLE 1 f A is CH 3-methy1—2—pyridmy1 3 -(triflu0r0methy1)pyridiny1 4—methy1—2-pyridiny1 4-meth0xy-2—pyridinyl 4—(triflu0r0methyl)pyridiny1 4-(CH(=‘.\OMe))-2—pyridinyl -methylpyridinyl 5-meth0xypyridinyl —(triflu0r0methy1)pyridiny1 5-(CH(=\OVIe))pyridinyl 6-methy1—2—pyndmy1 6-(triflu0r0methy1)pyridiny1 y1—3-pyndmy1 2—(triflu0r0methyl)-3 -pyridiny1 2-(CH(=\OVIe))-3 -pyridiny1 4-methy1—3-pyridiny1 4-meth0xy-3 -pyridinyl 4-(triflu0r0methyl)-3 -pyridiny1 4-(CH(=\'OV[e))-3—pyridinyl -methy1—3-pyridinyl 5-methoxy-3 -pyridinyl -(triflu0romethy1)-3 -pyridiny1 6-methy1pyridiny1 6-(triflu0romethy1)-3 iny1 6-(CH(=NOMe))pyridiny1 2-methy1pyridiny1 oxypyridinyl 2—(trifluoromethy1)pyridinyl 2-(CH(=:\OMe))—4—pyridinyl 3-methy1—4—pyridmy1 W0 2015I038503 PCT/U82014/054671 3-(triflu0romethy1)pyridiny1 3-methy1pyraziny1 3-methoxypyrazinyl 3-(trifluor0methy1)pyraziny1 3-(CH(=NOMe))pyrazmyl y1pyraziny1 5-methoxypyrazinyl —(triflu0r0methy1)pyraziny1 5-(CH(=NOM€))—2—pyrazmyl 6-methy1—2—pyrazmy1 6—(triflu0r0methy1)pyraziny1 4—methy1pyrimidiny1 4-(triflu0r0methy1)pyrimidiny1 4-(CH(=\OVIe))pyrirnidiny1 -methy1pyrimidiny1 0xypyrimidiny1 -(triflu0r0methy1)pyrimidiny1 5-(CH(=\OVIe))pyrimidiny1 2-methy1pyrimidiny1 2-(triflu0r0methy1)pyrimidiny1 —methy1pyrimidiny1 -(trifluoromethyl)pyrimidiny1 5 -(CH(=\'O\/Ie))pyrimidiny1 6—methy1—4-pyrimidiny1 (PB(DHhoxypyrimidiny1 6-(trifluoromethyl)pyrimidiny1 6-(CH(=I\'O_\/Ie))pyrimidiny1 3 -methyl- 1 oly1 3 xypyrazoly1 3-(trifluoromethy1)pyrazoly1 3-(CH(=NOMe))pyrazoly1 4-methy1— 1 -pyrazoly1 4-meth0xypyrazoly1 flu0r0methy1)pyraz01y1 4-(CH(=NOMe))— 1 —pyraz01y1 —methy1— 1 -pyraz01y1 5-meth0xypyraz01yl —(triflu0r0methy1)- 1 oly1 5-(CH(=NOMe))pyrazoly1 4—methy1-1,2, 3 -triaziny1 4-meth0xy-1,2,3 -triazin-2—y1 4-(triflu0r0methy1)-1,2,3 -triaziny1 4-(CH(=NOMe))-1,2,3-triazin—2-y1 6-(2-pyrimidiny1)pyridiny1 2-(2-pyridiny1)thiazolyl 2-(2-thiazoly1)thiazoly1 2-(2-pyrimidiny1)ethynyl 1,3,4-0xadiazoly1 tetrahydro—3-furanyl tetrahydro-Z-furanyl 4,5-dihydr0isoxazolyl 3 -is0xazoly1 phenyl 2-(triflu0romethy1)phenyl 3 -(trifluoromethy1)phenyl 4-(triflu0romethy1)pheny1 6-(trifluoromethy1)pyraziny1 Ais CF 3—methy1—2-pyridiny1 3-meth0xy 2 pyridinyl 3—(triflu0r0methy1) 2 yl 3-(CH(=NOMe))pyr1dmy1 W0 2015I038503 PCT/U82014/054671 4-methy1—2—pyridiny1 4-(trifluoromethy1)pyridiny1 =NOMe))pyridinyl -methy1pyridiny1 oxypyridinyl -(triflu0r0methy1)pyridiny1 5-(CH(=I\OMe))pyridiny1 6-methy1—2—pyridmy1 6—(triflu0r0methy1)pyridiny1 2-methy1—3-pyndmy1 2—(triflu0r0methy1)-3 iny1 2-(CH(=\OMe))-3 -pyridiny1 4-methy1—3-pyridiny1 4-meth0xy-3 -pyridiny1 4-(triflu0r0methyl)-3 -pyridiny1 4-(CH(=\O\/[e))-3 -pyridiny1 -methy1—3-pyridinyl 5-meth0xy-3 -pyridiny1 -(triflu0r0methyl)-3 -pyridiny1 5-(CH(=\OVIe))-3 -pyridiny1 6-methy1—3-pyridmy1 flu0r0methy1)pyridiny1 2-methylpyridinyl 2-meth0xypyridinyl 2-(trifluoromethy1)pyridiny1 2-(CH(=\'O\/Ie))—4—pyridinyl 3 -methy1pyridiny1 3 -methoxypyridinyl 3 -(trifluoromethy1)pyridiny1 3 -(CH(=NOMe))pyridinyl 3-methy1—2-pyrazmy1 3-(triflu0r0methy1)pyraziny1 3 -(CH(=I\OMe))pyrazinyl -methy1pyrazmy1 —(triflu0r0methy1)pyraziny1 5 -(CH(=‘.\OMe))pyraziny1 y1—2—pyrazinyl 6-meth0xypyraziny1 6—(triflu0r0methyl)pyraziny1 6-(CH(=\OVIe))pyraziny1 4-methy1pyrimidiny1 4-(trifluor0methyl)pyrimidinyl 4-(CH(=\OVIe))pyrimidinyl -methy1pyrimidiny1 -(triflu0r0methyl)pyrimidiny1 5-(CH(=\OVIe))pyrimidinyl 2—methy1pyrimidiny1 2-meth0xypyrimidinyl 2-(trifluoromethyl)pyrimidiny1 2-(CH(=\'O\/Ie))pyrimidiny1 —methy1—4-pyrimidinyl 5-methoxypyrimidinyl -(trifluoromethyl)pyrimidiny1 5-(CH(=I\'OMe))pyrimidiny1 6-methy1pyrimidiny1 6-methoxypyrimidinyl 6-(trifluoromethyl)pyrimidiny1 =\'’ OMe))pyrimidinyl 3 -methylpyraz01y1 3 -methoxypyraz01y1 3—(triflu0r0methy1)pyrazoly1 =zOze, — —pyraz01y1 4—methy1— 1 -pyraz01y1 4-meth0xypyraz01yl W0 2015I038503 PCT/U82014/054671 4-(trifluor0methy1)pyraz01y1 -methy1pyrazoly1 -(trifluoromethy1)pyrazoly1 4—(triflu0r0methyl)-1,2,3-triaziny1 6—(2—pyrimidiny1)pyridiny1 2—(2—thiaz01y1)thiazoly1 1,3,4-oxadiazoly1 tetrahydm-z-fmanyl 3-isoxazoly1 2-(triflu0r0methyl)pheny1 4-(triflu0r0methy1)phenyl A is N 3 —_ 3-methy1—2—pyridiny1 3 -(trifluoromethy1)pyridinyl 3 -(CH(=NOMe))pyridinyl 4-methy1pyridiny1 4-methoxypyridinyl 4-(trifluoromethyl)pyridinyl 4-(CH(=I\'OMe))pyridinyl -methy1pyridmy1 —(trifluoromethy1)pyridinyl 6-methy1—2—pyndmy1 6—(triflu0r0methy1)pyridiny1 =\OMe))pyridinyl ylpyridinyl 2-meth0xy-3 iny1 2-(triflu0r0methyl)-3 -pyridiny1 2-(CH(=\O\/[e))-3 -pyridiny1 4-methy1—3-pyridiny1 0xy-3 -pyridiny1 4-(triflu0r0methyl)-3 -pyridiny1 4-(CH(=\O\/[e))-3 -pyridiny1 -methy1pyridmy1 —(triflu0r0methyl)-3 -pyridiny1 5-(CH(=\'OV[e))-3—pyridiny1 6-methylpyridinyl 6-meth0xy-3 -pyridinyl 6—(triflu0r0methyl)-3 iny1 6-(CH(=\'O\/Ie))—3—pyridinyl 2-methy1—4-pyridiny1 2-methoxypyridinyl 2-(triflu0romethy1)pyridiny1 2-(CH(=NOMe))pyridinyl 3-methy1—4—pyridmy1 3 -(triflu0r0methy1)pyridiny1 3—methy1—2-pyraziny1 3-meth0xy—2-pyrazinyl 3—(triflu0r0methyl)pyraziny1 3 -(CH(=‘.\OMe))pyraziny1 W0 2015I038503 PCT/U82014/054671 s-methyI-z-pyrazinyl -(trifluor0methy1)pyraziny1 5-(CH(=NOMe))pyrazinyl 6-methy1pyrazinyl 6-methoxypyrazinyl 6-(triflu0r0methy1)pyraziny1 6-(CH(=NOMe))pyrazmyl 4—methy1pyrimidiny1 4—(trifluoromethyl)pyrimidinyl —methy1pyrimidiny1 —(triflu0r0methyl)pyrimidiny1 5-(CH(=\OVIe))pyrimidiny1 2-methy1pyrimidiny1 2-meth0xypyrimidinyl 2-(triflu0r0methyl)pyrimidiny1 2-(CH(=\OVIe))pyrimidiny1 y1pyrimidiny1 5-meth0xypyrimidiny1 -(triflu0r0methyl)pyrimidiny1 y1pyrimidiny1 6-(trifluoromethyl)pyrimidiny1 3-methy1—1-pyrazoly1 3-(triflu0romethy1)-1 -pyraz01y1 3-(CH(=\IOMe))-1—pyrazolyl 4-methy1—1-pyrazoly1 4-(trifluoromethyl)pyrazoly1 4-(CH(=NOMe))- 1-pyrazolyl -methy1pyrazoly1 -(triflu0r0methy1)-1 -pyraz01y1 5-(CH(=NOMe))pyraz01yl 4—methy1-1,2,3-triazin-2—yl 4—(triflu0r0methyl)-1,2,3-triaziny1 6—(2—pyrimidinyl)pyridiny1 2—(2-thiaz01y1)thiazoly1 0xadiaz01y1 tetrahydro—Z-furanyl 4,5-dihydr0isoxazolyl 3 zoly1 phenyl 2-(triflu0r0methyl)pheny1 3 -(trifluoromethyl)phenyl 4-(triflu0r0methy1)phenyl 6-(trifluoromethy1)-3—pyraziny1 R\N _A A \N/N{N/> WO 38503 PCT/U82014/054671 W0 2015I038503 2014/054671 -NH<5-methy1—2—pyridmy1> -NH(4-methoxypyfidmyl) -NH<5methoxy-z-pyridmyn W0 2015I038503 2014/054671 -NH<s-CF3pyridmy1> -NH<4-methoxy—2-pyridmy1> W0 2015I038503 2014/054671 -CH2<s-methoxypyridmy1> W0 2015I038503 2014/054671 -NH<5-methy1—2—pyridmy1> -NH(4-methoxypyfidmyl) -NH<5methoxy-z-pyridmyn WO 38503 PCT/U82014/054671 —-pyfidmyl -CH2<3-pyridmy1> 2--pyridiny1 2--pyraziny1 -CH2CH2(2-pyridinyl) 4-pyridiny1 4-CF3pyridiny1 -CH2CH2CH2(2-pyridinyl) TABLE 2b R\N —A }II N \N/ \ N/> AisCH W0 38503 PCT/U82014/054671 -NH<5-methy1—2—pyndmy1> -NH<4-methoxy—2-pyridmy1> -NH<5methoxy-z-pyridmyn W0 38503 PCT/U82014/054671 W0 2015I038503 PCT/U82014/054671 -NH<5-methy1—2—pyridmy1> methoxy—2-pyridmy1> -CH2<c-Pr> -<:H(MexcPr) W0 38503 PCT/U82014/054671 W0 2015I038503 PCT/U82014/054671 -CH2<4-methoxy-2pyridmyn -CH2<5-methoxy—2—pyndmy1> -CH2<4-methoxy—2—pyrimidmyn TABLE 20 \N/N4<\:N/>—A R / A is CH N<-CH2CH2CH2-> N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-) N(-CH2CH2CH2CH2-) N(-CH2CH28CH2CH2-) N(-CH2CH2CH2CH2CH2-) N(-CH2CH20CH2CH2-) N(-CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-) C(Me)2N=CH-) N(-CH2CH2CH2CH(CF3)CH2-) N<CH2CECH>2 W0 2015I038503 N(Pr)CH2(c-Pr) N(Et)(c-hexy1) N<-CHC<0>SCH2CH2-> — AjsCF N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2-) N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-) CH2CH2CH2-) CHZSCH2CH2—) N(—CH2CH2CH2CH2CH2-) N(-CH2CHZOCH2CH2—) N(-CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-) N(-CH2C(Me)2N=CH-) N(-CH2CH2CH2CH(CF3)CH2-) N(CH2CECH)2 N(Et)2 N(Pr)CH2(c-Pr) N(Et)(c-hexy1) N(—CHC(O)SCH2CH2-) CH2CH2-) N(-CH2CH(OMe)CH2-) N(—CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-) N(—CH2CH2CH2CH2-) N(-CH2CHZSCH2CH2-) N(—CH2CH2CH2CH2CH2-) N(-CH2CH20CH2CH2-) N(—CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-) C(Me)2N=CH-) N(-CH2CH2CH2CH(CF3)CH2-) N(CH2CECH)2 N(Et)2 N(Pr)CH2(c-Pr) N(Et)(c-hexy1) N(-CHC(O)SCH2CH2-) TABLEZd A$CH N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2-) N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-) W0 2015I038503 2014/054671 N(—CH2CH2CH2CH2-) N(-CH2CH28CH2CH2-) N(-CH2CH2CH2CH2CH2-) N(-CH2CH20CH2CH2-) N(-CH2CH2N(C(O)(c-Pr))CHZCH2-) N(-CH2CH2N(Me)CH2CH2-) N(—CH2C(Me)2N=CH-) CH2CH2CH(CF3)CH2—) N(CH2CECH)2 N(Et)2 N(Pr)CH2(c-Pr) N(Et)(c-hexyl) N(—CHC(O)SCH2CH2-) A is CF N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2-) N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-) N(-CH2CH2CH2CH2-) N(-CH2CHZSCH2CH2-) N(-CH2CH2CH2CH2CH2-) N(-CH2CH20CH2CH2-) N(-CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-) N(-CH2C(Me)2N=CH-) N(-CH2CH2CH2CH(CF3)CH2-) N(CH2CECH)2 N(Et)2 N(Pr)CH2(c-Pr) c-hexy1) N(—CHC(O)SCH2CH2-) AisN N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2-) N(—CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2—) N(-CH2CH2CH2CH2-) CHZSCH2CH2-) N(-CH2CH2CH2CH2CH2-) N(-CH2CHZOCH2CH2-) N(—CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-) N(-CH2C(Me)2N=CH-) N(-CH2CH2CH2CH(CF3)CH2-) N(CH2CECH)2 N(Et)2 N(Pr)CH2(c-Pr) N(Et)(c-hexyl) N(-CHC(O)SCH2CH2-) W0 2015I038503 PCT/U82014/054671 TABLE 26 \N/N \ N/> A is CH 3-methylpyridinyl 0xypyridinyl 3 —(triflu0r0methyl)pyridiny1 3 -(CH(=\OVIe))pyridinyl 4-methy1—2-pyridiny1 4-meth0xypyridinyl 4-(triflu0r0methyl)pyridiny1 4-(CH(=\OVIe))pyridinyl -methy1—2-pyridinyl 5-meth0xypyridinyl —(triflu0r0methy1)pyridiny1 5-(CH(=\OVIe))-2—pyridiny1 6-methy1—2—pyridmy1 6—(trifluoromethy1)pyridinyl 6-(CH(=\'OVIe))-2—pyridinyl 2—methy1—3-pyridiny1 2-methoxypyridinyl flu0romethy1)-3 -pyridiny1 2-(CH(=I\'OMe))pyridiny1 y1pyridiny1 4-methoxypyridinyl 4-(triflu0r0methy1)pyridiny1 -methy1pyridmy1 —(triflu0r0methy1)pyridiny1 6-methylpyridinyl 6-meth0xy-3 -pyridinyl 6—(triflu0r0methyl)-3 -pyridiny1 6-(CH(=\OMe))-3 iny1 2-methylpyridinyl 2-meth0xypyridinyl 2-(triflu0r0methy1)pyridiny1 2-(CH(=\OVIe))pyridinyl 3-methy1—4—pyndmy1 3-(triflu0r0methy1)pyridiny1 3-methy1—2—pyrazmy1 3-(triflu0r0methyl)pyraziny1 3 -(CH(=\'OV[e))-2—pyrazinyl —methy1—2-pyrazinyl 5-meth0xypyrazinyl -(triflu0r0methyl)pyraziny1 5 -(CH(=\'O\/Ie))-2—pyrazinyl 6—methy1—2—pyrazinyl 6-methoxypyrazinyl fluoromethy1)pyraziny1 6-(CH(=NOMe))pyrazinyl 4-methy1—2-pyrimidmy1 4-(trifluoromethyl)pyrimidiny1 —methy1pyrimidiny1 —(trifluoromethyl)pyrimidiny1 5-(CH(=I\OMe))pyrimidiny1 W0 2015I038503 2014/054671 2—methy1—4—pyrimidinyl 2-(trifluoromethyl)pyrimidiny1 -methy1pyrimidiny1 -(triflu0r0methy1)pyrimidiny1 6—methy1pyrimidiny1 6—(trifluoromethyl)pyrimidiny1 3-methy1—1-pyrazoly1 3—(triflu0r0methyl)pyrazoly1 4-methy1—1-pyrazoly1 4-(triflu0r0methyl)pyrazoly1 s-methyl-l-pyrazolyl -(triflu0r0methyl)pyrazoly1 4-methy1-1,2,3-triazinyl 4—(triflu0r0methyl)-1,2,3-triaziny1 6-(2-pyrimidinyl)pyridiny1 2-(2-thiazoly1)thiaz01y1 L3A-oxadiazol—2—y1 tetrahydro-z-furanyl 3-isoxazoly1 A is CF 3 —_ 3-methy1—2—pyridmy1 3 —(triflu0r0methyl)pyridiny1 3 -(CH(=\OVIe))pyridinyl y1—2-pyridiny1 4-meth0xypyridinyl 4-(triflu0r0methyl)pyridiny1 4-(CH(=\OVIe))pyridinyl -methy1pyridmy1 flu0r0methy1)pyridiny1 5-(CH(=\OVIe))-2—pyridinyl 6-methy1—2—pyridmy1 6—(trifluoromethy1)pyridinyl 6-(CH(=\'OV[e))-2—pyridinyl 2—methy1—3-pyridinyl 2-methoxypyridinyl 2-(trifluoromethy1)-3 -pyridiny1 2-(CH(=I\'O.\/Ie))-3 iny1 4-methy1pyridiny1 4-(triflu0romethy1)pyridiny1 -methy1pyridmy1 —(triflu0r0methy1)pyridiny1 6-methy1—3-pyridmy1 W0 2015I038503 PCT/U82014/054671 6—(triflu0romethy1)-3 -pyridiny1 =\'O\/Ie))—3—pyridinyl 2-methy1pyridiny1 2-methoxypyridinyl 2-(triflu0romethy1)pyridiny1 =NOMe))pyridinyl 3 1pyridiny1 3 -methoxypyridinyl 3 —(trifluoromethyl)pyridiny1 3 -(CH(=I\OMe))—4—pyridinyl 3—methy1—2-pyraziny1 3-meth0xy—2-pyrazinyl 3—(triflu0r0methyl)pyraziny1 3 -(CH(=‘.\OMe))pyraziny1 -methy1—2—pyrazinyl 5-meth0xypyrazinyl —(triflu0r0methyl)pyraziny1 5-(CH(=\OVIe))pyraziny1 6-methy1—2-pyrazinyl 6-meth0xypyraziny1 6-(triflu0r0methyl)pyraziny1 6-(CH(=\OVIe))pyraziny1 4-methy1pyrimidiny1 4—(triflu0r0methyl)pyrimidinyl =\OVIe))pyrimidinyl —methy1pyrimidiny1 5-meth0xypyrimidiny1 fluoromethyl)pyrimidiny1 5 -(CH(=\'O\/Ie))pyrimidiny1 y1—4-pyrimidiny1 2-methoxypyrimidinyl 2-(trifluoromethyl)pyrimidiny1 2-(CH(=I\'OMe))pyrimidinyl -methy1pyrimidiny1 5-methoxypyrimidinyl -(triflu0romethy1)pyrimidiny1 5-(CH(=I\'OMe))pyrimidinyl y1pyrimidiny1 6-meth0xypyrimidinyl 6—(trifluoromethyl)pyrimidiny1 6-(CH(=‘.\OMe))-4—pyrimidiny1 3 —methylpyraz01y1 3 -meth0xypyraz01yl 3—(triflu0r0methyl)pyrazoly1 3-(CH(=NOMe))- 1-pyrazoly1 4-methy1— 1 -pyrazoly1 4-meth0xypyrazoly1 4-(triflu0r0methyl)pyrazoly1 4-(CH(=NOMe))- 1-pyrazoly1 -methy1— 1 -pyrazoly1 5-meth0xypyrazoly1 -(triflu0r0methyl)pyrazoly1 5-(CH(=NOMe))- 1-pyrazoly1 4-methy1-1,2, 3 -triaziny1 4-meth0xy-1,2,3 -triazin-2—y1 4-(triflu0r0methyl)-1,2,3 iny1 4-(CH(=NOMe))-1,2,3—triazin—2—y1 6-(2-pyrimidinyl)pyridiny1 2-(2-pyridiny1)-4—thiazolyl 2-(2-thiazolyl)thiazoly1 2-(2-pyrimidiny1)ethynyl 1,3 ,4-0xadiazol-Z-yl tetrahydIo-3 - furanyl tetrahydro-Z-furanyl 4, 5 -dihyd.ro-3 - isoxazolyl 3-is0xazoly1 6-(trifluoromethy1)pyrazinyl AisN W0 2015I038503 PCT/U82014/054671 3-methy1—2—pyridmy1 3 -(trifluoromethy1)pyridinyl 3 -(CH(=NOMe))pyridinyl 4-methy1pyridiny1 4-methoxypyridinyl 4-(trifluoromethyl)pyridinyl 4-(CH(=I\OMe))pyridinyl -methy1pyridiny1 —(triflu0r0methy1)pyridiny1 6-methy1—2—pyridmy1 6—(triflu0r0methy1)pyridiny1 6-(CH(=\OMe))pyridinyl 2-methylpyridinyl 2-meth0xy-3 -pyridiny1 2-(triflu0r0methyl)-3 -pyridiny1 2-(CH(=\O\/[e))-3 -pyridiny1 4-methy1—3-pyridiny1 4-meth0xy-3 -pyridiny1 4-(triflu0r0methyl)-3 -pyridiny1 =\OVIe))-3 -pyridiny1 -methy1pyridmy1 flu0r0methy1)pyridiny1 6-methylpyridinyl 6-meth0xy-3 -pyridinyl 6—(triflu0romethy1)-3 -pyridiny1 6-(CH(=\'O\/Ie))—3—pyridinyl 2-methy1pyridiny1 2-methoxypyridinyl 2-(triflu0romethyl)pyridiny1 2-(CH(=NOMe))pyridinyl 3-methy1—4-pyridmy1 3 -(triflu0r0methy1)pyridiny1 3-methy1—2—pyrazmy1 3—(triflu0r0methyl)pyraziny1 3 ‘.\OMe))pyraziny1 -methy1—2—pyrazinyl 5-meth0xypyrazinyl —(triflu0r0methyl)pyraziny1 5-(CH(=\OVIe))pyraziny1 6-methy1—2-pyrazinyl 6-meth0xypyrazinyl 6-(triflu0r0methyl)pyraziny1 6-(CH(=\OVIe))pyraziny1 4-methy1pyrimidiny1 4—(triflu0r0methyl)pyrimidinyl 4-(CH(=\OVIe))pyrimidinyl —methy1pyrimidiny1 5-meth0xypyrimidiny1 -(trifluoromethyl)pyrimidiny1 5 -(CH(=\'O\/Ie))pyrimidiny1 2—methy1—4-pyrimidinyl oxypyrimidinyl 2-(trifluoromethyl)pyrimidiny1 =I\'OMe))pyrimidinyl -methy1pyrimidiny1 5-methoxypyrimidinyl -(trifluoromethyl)pyrimidiny1 5-(CH(=\cOD Me))pyrimidinyl 6-methy1pyrimidiny1 oxypyrimidinyl 6—(trifluoromethyl)pyrimidiny1 6-(CH(=‘.\OM(I?V V A- —pyrimidiny1 3 —methylpyraz01y1 3 -meth0xypyraz01yl W0 2015/‘038503 PCT/U82014/054671 flu0romethy1)-1 -pyrazoly1 3-(CH(=NOMe))-1—pyrazoly1 4-methy1pyrazoly1 4-methoxypyrazoly1 fluoromethy1)pyrazoly1 4-(CH(=NOMe))- 1-pyrazoly1 -methy1- 1 oly1 5-methoxypyrazoly1 —(triflu0r0methy1)pyraz01y1 5-(CH(=NOMe))— 1 —pyraz01yl 4—methy1-1,2, 3 -triaziny1 4-meth0xy-1,2,3 -triazin—2—yl 4—(triflu0r0methy1)-1,2,3 -triaziny1 4-(CH(=NOMe))—1,2,3—triazin—2—y1 6—(2—pyrimidiny1)pyridiny1 2-(2-pyridiny1)thiazoly1 2—(2-thiaz01y1)thiazoly1 2-(2-pyrimidiny1)ethynyl 1, 3 ,4-oxadiaz01y1 tetrahydro—3 -furanyl ydro—Z-furanyl 4, 5 -dihydr0-3 -isoxazoly1 3 -isoxazoly1 flu0r0methy1)pyrazinyl TABLE2f AECH 3 —methy1—2-pyridiny1 3 -meth0xypyridiny1 3 —(triflu0r0methy1)pyridiny1 3 -(CH(=\OMe))pyridinyl 4-methy1—2-pyridiny1 4-meth0xypyridiny1 4—(triflu0r0methy1)pyridiny1 4-(CH(=\OVIe))pyridinyl -methy1—2-pyridiny1 5-meth0xypyridiny1 -(triflu0r0methy1)pyridiny1 5-(CH(=\OVIe))pyridinyl y1—2-pyridiny1 6-meth0xypyridiny1 6-(triflu0r0methy1)pyridiny1 6-(CH(=\OS8YN—pyridiny1 2—methy1—3 -pyridiny1 2-meth0xy-3 -pyridinyl 2—(trifluoromethyl)-3 -pyridiny1 2-(CH(=\'OVIe))-3—pyridinyl 4-methy1—3 -pyridiny1 hoxypyridinyl 4-(trifluoromethyl)-3 -pyridiny1 4-(CH(=NOMe))pyridinyl -methy1-3 -pyridiny1 5-methoxypyridinyl -(triflu0r0methy1)-3 -pyridiny1 5-(CH(=I\OMe))pyridiny1 6—methy1—3 iny1 6-meth0xy—3 —pyridiny1 6—(triflu0r0methy1)-3 -pyridiny1 6-(CH(=‘.\OMe))-3—pyridiny1 W0 2015I038503 PCT/U82014/054671 2-methy1—4—pyridiny1 flu0romethy1)pyridiny1 2-(CH(=NOMe))pyridinyl 3-methy1pyridiny1 3-methoxypyridinyl 3-(triflu0r0methy1)pyridiny1 3-(CH(=I\OMe))pyridiny1 3-methy1—2—pyrazmy1 3—(triflu0r0methy1)pyraziny1 -methy1pyrazmy1 —(triflu0r0methy1)pyraziny1 =\OMe))pyraziny1 y1—2-pyraziny1 6-meth0xypyrazinyl 6-(triflu0r0methy1)pyraziny1 6-(CH(=\OVIe))pyraziny1 4-methy1pyrimidiny1 4—(triflu0r0methy1)pyrimidiny1 4-(CH(=\OVIe))pyrimidinyl -methy1pyrimidiny1 -(trifluoromethyl)pyrimidiny1 2—methy1pyrimidiny1 2-meth0xypyrimidinyl 2-(triflu0r0methy1)pyrimidiny1 2-(CH(=\'O\/Ie))-4—pyrimidiny1 -methy1pyrimidiny1 oxypyrimidinyl -(trifluoromethyl)pyrimidiny1 5-(CH(=I\'O.\/Ie))pyrimidiny1 6-methy1pyrimidiny1 6-methoxypyrimidinyl 6-(trifluoromethyl)pyrimidiny1 6-(CH(=\OMe))pyrimidiny1 3 —methylpyraz01y1 3 -meth0xy- 1 01yl 3—(triflu0r0methy1)pyrazoly1 3-(CH(=NOMe))pyraz01y1 4-methy1— 1 -pyrazoly1 4-meth0xypyraz01yl 4—(triflu0romethy1)- 1 oly1 4-(CH(=NOMe))pyrazoly1 -methy1— 1 -pyrazoly1 0xypyrazoly1 -(triflu0r0methy1)pyrazoly1 5-(CH(=NOMe))pyraz01y1 4-methy1-1,2, 3 -triaziny1 4-meth0xy-1,2,3 -triazin—2-yl 4-(triflu0r0methy1)-1,2,3 -triaziny1 4-(CH(=NOMe))-1,2,3—triazin—2-y1 6-(2-pyrimidiny1)pyridiny1 2-(2-pyridiny1)-4—thiazolyl 2-(2—thiaz01y1)thiazoly1 2-(2-pyrimidiny1)ethynyl 1,3 ,4—0xadiaz01—2-y1 ydro-3 - furanyl tetrahydro-Z-furanyl 4,5 -dihyd;ro-3 -isoxazoly1 3-isoxazoly1 6-(triflu0romethy1)pyraziny1 Ais CF 3 —methy1—2-pyridiny1 3 -meth0xypyridiny1 W0 2015I038503 PCT/U82014/054671 3 -(triflu0romethy1)pyridiny1 3 -(CH(=\'O\/Ie))—2—pyridinyl 4-methy1pyridiny1 4-methoxypyridinyl fluoromethy1)pyridiny1 4-(CH(=NOMe))pyridinyl -methy1pyridiny1 5-methoxypyridinyl —(trifluoromethy1)pyridinyl 6-methy1—2—pyridmy1 flu0r0methy1)pyridiny1 ylpyridinyl 2-meth0xy-3 inyl 2—(triflu0r0methyl)-3 -pyridiny1 2-(CH(=\O\/[e))-3 -pyridiny1 4-methy1—3-pyridiny1 4-meth0xy-3 -pyridiny1 4-(triflu0r0methyl)-3 -pyridiny1 4-(CH(=\O\/[e))-3 -pyridiny1 -methy1pyndmy1 —(triflu0r0methyl)-3 -pyridiny1 5-(CH(=\OVIe))-3 —pyridiny1 6-methy1—3-pyridmy1 6—(triflu0r0methyl)-3 -pyridiny1 6-(CH(=\'O\/Ie))-3—pyridinyl 2—methy1—4-pyridiny1 2-methoxypyridinyl flu0romethy1)pyridiny1 2-(CH(=NOMe))pyridinyl 3 -methy1pyridiny1 3 -methoxypyridinyl 3 -(triflu0romethy1)pyridiny1 3-methy1—2—pyrazmy1 3—(triflu0r0methyl)pyraziny1 —methy1—2-pyraziny1 5-meth0xy—2-pyrazinyl —(triflu0r0methyl)pyraziny1 =\OMe))pyraziny1 6-methy1—2-pyrazinyl 6-meth0xypyrazinyl 6-(triflu0r0methyl)pyraziny1 6-(CH(=\OVIe))pyraziny1 y1pyrimidiny1 4—(triflu0r0methyl)pyrimidinyl 4-(CH(=\OVIe))pyrimidinyl -methy1pyrimidiny1 -(trifluoromethyl)pyrimidiny1 5 -(CH(=\'O\/Ie))pyrimidinyl 2—methy1pyrimidiny1 2-meth0xypyrimidinyl 2-(triflu0r0methyl)pyrimidiny1 2-(CH(=\'O\/Ie))-4—pyrimidinyl -methy1pyrimidinyl 5-methoxypyrimidinyl -(trifluoromethyl)pyrimidiny1 5-(CH(=NOMe))pyrimidinyl 6-methy1pyrimidiny1 6-methoxypyrimidinyl 6-(t.rifluoromethyl)pyrimidiny1 6-(CH(=\OMe))pyrimidinyl 3 —methylpyraz01y1 3 -meth0xypyraz01yl 3—(triflu0r0methyl)pyrazoly1 3-(CH(=NOMe))pyraz01y1 W0 2015I038503 PCT/U82014/054671 \0 DJ 4-methy1— 1 -pyrazoly1 4-methoxypyrazoly1 4-(triflu0romethy1)-1 -pyraz01y1 =NOMe))- zolyl -methy1pyrazoly1 5-methoxypyrazoly1 -(trifluor0methy1)-1 -pyrazoly1 5-(CH(=NOMe))pyrazolyl 4—methy1-1,2, 3 -triaziny1 4-meth0xy-1,2,3 —triazin—2—y1 4—(triflu0r0methy1)- 1 ,2,3 -triaziny1 4-(CH(=NOMe))-1,2,3—triazin—2—y1 6—(2—pyrimidiny1)pyridiny1 2-(2-pyridiny1)thiaz01yl 2—(2-thiaz01y1)thiazoly1 2-(2-pyrimidiny1)ethynyl 1, 3 ,4-0xadiaz01—2-y1 ydro-3 -furanyl ydro—Z-furanyl 4, 5 -dihydr0-3 -isoxazoly1 3 -is0xazoly1 6-(triflu0r0methy1)pyraziny1 AisN 3 -methy1—2-pyridinyl 3 -meth0xypyridinyl 3 -(triflu0r0methy1)pyridiny1 3-(CH(=\'O\/Ie))—2—pyridinyl 4-methy1pyridiny1 4-methoxypyridinyl 4-(trifluoromethyl)pyridiny1 4-(CH(=NOMe))pyridinyl y1pyridiny1 5-methoxypyridinyl flu0r0methy1)pyridiny1 5-(CH(=\OMe))pyridinyl 6—methylpyridinyl 6-meth0xypyridinyl 6—(triflu0r0methyl)pyridiny1 6-(CH(=\ -pyridiny1 2-methy1—3 -pyridiny1 2-meth0xy-3 -pyridinyl 2—(triflu0romethy1)-3 -pyridiny1 2-(CH(=\OVIe))pyridinyl 4-methy1—3 -pyridiny1 4-meth0xy-3 -pyridiny1 4-(triflu0r0methy1)-3 -pyridiny1 4-(CH(=\OS8V U.) -pyridiny1 -methy1—3 -pyridiny1 5-meth0xy-3 -pyridinyl —(triflu0r0methy1)-3 -pyridiny1 =\OS8V U.) —pyridiny1 6-methy1—3 iny1 6-meth0xy-3 -pyridinyl 6—(trifluoromethyl)-3 -pyridiny1 6-(CH(=\'OS8V- U.) —pyridinyl 2-methy1—4-pyridinyl 2-methoxypyridinyl 2-(trifluoromethyl)pyridiny1 2-(CH(=NOMe))pyridinyl 3 -methy1pyridiny1 3-methoxypyridinyl 3 -(triflu0r0methy1)pyridiny1 3-(CH(=\'OMe))pyridinylD 3 -methy1pyrazinyl 3 -methoxypyrazinyl 3—(triflu0r0methy1)pyraziny1 3 -(CH(=\OM> (I?VY [\J—pyraziny1 —methy1—2-pyraziny1 5-meth0xy—2-pyrazinyl W0 2015I038503 PCT/U82014/054671 -(trifluoromethyl)pyraziny1 6-methylpyrazinyl 6-methoxypyrazinyl 6-(trifluoromethyl)pyrazinyl 4-methy1—2-pyrimidmy1 fluorornethyl)pyrirnidinyl —methylpyrirnidinyl —(trifluorornethyl)pyrirnidinyl 2—mcthylpyrirnidinyl 2-(trifluorornethyl)pyrirnidinyl 2-(CH(=\OVIe))pyrirnidinyl -mcthylpyrirnidinyl 5 -rnethoxypyrirnidinyl -(trifluorornethyl)pyrimidinyl 5-(CH(=\OVIe))pyrirnidinyl 6-methylpyrirnidinyl 6-(trifluoromethyl)pyrimidinyl 3-methy1—1-pyrazoly1 3-(trifluorornethyl)-l-pyrazolyl 4-methy1—1-pyrazoly1 4-(trifluoromethy1)pyrazolyl -methy1pyrazoly1 -(trifluoromethyl)-l-pyrazolyl 4-methyl- l ,2, 3 -triazinyl 4—(trifluorornethyl)-l,2,3-triazinyl 6—(2—pyrirnidinyl)pyridinyl 2-(2-pyridinyl)thiazolyl 2—(2-thiazolyl)thiazolyl 2-(2-pyrimidinyl)ethynyl 1,3,4-oxadiazolyl tetrahydro-S-furanyl ydro-z-furanyl 3-isoxazolyl fluorornethyl)pyrazinyl TABLE 3a H \ R/N \N/«\ N/> Table 3a is identical to Table 1a, except that the ure shown under the heading "Table la" is replaced by the structure shown above.

PCT/USZOl4/054671 TABLE 3c Table 3c is identical to Table lc, except that the structure shown under the heading "Table 1c" is replaced by the structure shown above.

TABLE 3e Table 3c is identical to Table le, except that the structure shown under the heading "Table 1c" is replaced by the structure shown above.

TABLE 4a / {3 \N/ \ N/ N O A Table 4a is identical to Table la, except that the structure shown under the heading "Table la" is replaced by the ure shown above.

TABLE 4c Table 40 is identical to Table lc, except that the ure shown under the heading "Table 10" is replaced by the structure shown above.

PCT/USZOl4/054671 TABLE 46 \N/ \ N/> Table 4e is identical to Table le, except that the structure shown under the heading "Table 1e" is ed by the structure shown above.

TABLE 5a N O / {3 \N/ \ N/ Table 5a is identical to Table 1a, except that the ure shown under the heading "Table 1a" is replaced by the structure shown above.

TABLE 5b H3CYO N o Table 5b is identical to Table la, except that the structure shown under the heading "Table la" is replaced by the structure shown above.

TABLE 5c 0 O N O R/ Eff Table Sc is identical to Table la, except that the structure shown under the heading "Table la" is replaced by the structure shown above.

WO 38503 PCT/USZOl4/054671 TABLE 5d \CH2 N O K/tEF:I:JE _A Table 5d is identical to Table la, except that the structure shown under the heading "Table la" is replaced by the structure shown above.

TABLE 5e 143(:\/oW N O /—C3N\3( \ I( Table Se is identical to Table la, except that the structure shown under the g "Table la" is replaced by the structure shown above.

TABLE 5f NC/jl O Table 5f is identical to Table la, except that the structure shown under the heading "Table la" is replaced by the structure shown above.

TABLE 6a N O F _A /mr<2 Table 6a is identical to Table la, except that the structure shown under the heading "Table 1a" is replaced by the structure shown above.

TABLE 6c R O Table 60 is identical to Table 1c, except that the structure shown under the heading "Table 1c" is ed by the structure shown above.

TABLE 6e Table 6e is cal to Table le, except that the structure shown under the heading "Table 1e" is replaced by the structure shown above.

TABLE 7a N O \N/ 4<\:N/> Table 7a is identical to Table la, except that the structure shown under the heading "Table la" is replaced by the structure shown above.

TABLE 7c Table 7c is identical to Table lc, except that the structure shown under the heading "Table 1c" is replaced by the structure shown above.

TABLE 7e @{:> Table 7c is identical to Table 1e, except that the structure shown under the heading "Table 1e" is replaced by the structure shown above.

TABLE 8a 0 F H \N/1%\ N/> Table 8a is identical to Table 1a, except that the structure shown under the g "Table 1a" is replaced by the structure shown above.

TABLE 8c 0 F ”C?HN\N/ {3\ N/ Table 8c is identical to Table 1c, except that the structure shown under the heading "Table 1c" is replaced by the structure shown above.

TABLE 8e Table 8e is identical to Table 1e, except that the structure shown under the heading "Table 1e" is replaced by the structure shown above.

PCT/USZOl4/054671 TABLE 9a R\ _A N / ' N{ Table 9a is identical to Table la, except that the structure shown under the heading "Table la" is replaced by the structure shown above.

TABLE 90 R / {3 \N/ \ N/ Table 9c is identical to Table 1c, except that the structure shown under the heading "Table 10" is replaced by the structure shown above.

TABLE 9e Table 9e is identical to Table le, except that the structure shown under the heading "Table 1e" is ed by the structure shown above.

TABLE lOa A o R N/ H F \ N/> Table 10a is identical to Table 1a, except that the structure shown under the heading "Table 1a" is replaced by the structure shown above.

PCT/USZOl4/054671 TABLE 10b N O R [I/ H CF3 \N {—A\N Table 10b is identical to Table 1a, except that the structure shown under the heading "Table 1a" is ed by the structure shown above.

TABLE 10c N O R E I H CH3 \N/ fiA\ Table 10c is identical to Table 1a, except that the structure shown under the heading "Table 1a" is replaced by the structure shown above.

TABLE 10d N o R/ I I H OCH3 2NfiA\ /> \N N Table 10d is identical to Table 1a, except that the structure shown under the heading "Table 1a" is replaced by the structure shown above.

TABLE 1 1a H F *@t‘| N H \N/ \ N/> Table 11a is identical to Table 1a, except that the structure shown under the g "Table la" is replaced by the structure shown above.

PCT/USZOl4/054671 TABLE 11b H CF3 < ‘tA H / /> \N \ Table 11b is identical to Table la, except that the structure shown under the heading "Table la" is replaced by the structure shown above.

TABLE 1 lc H CH3 R\N _A | N H /> \N/ \ Table 11c is identical to Table la, except that the structure shown under the heading "Table 1a" is replaced by the structure shown above.

TABLE 1 1d H OCH3 H /> \ \N/ N Table 11d is identical to Table la, except that the structure shown under the heading "Table la" is replaced by the structure shown above.

TABLE 12a R/l 0 / / —A \ N\N/ \ N/> Table 12a is identical to Table la, except that the structure shown under the heading "Table 1a" is replaced by the structure shown above.

PCT/USZOl4/054671 TABLE 120 R O / / _A \ N\N/ \ N/> Table 120 is identical to Table lc, except that the structure shown under the heading "Table 1c" is replaced by the structure shown above.

TABLE 12e Table 12c is cal to Table le, except that the structure shown under the heading "Table 1c" is replaced by the structure shown above.

TABLE 13a \T / / _A> Table 13a is cal to Table la, except that the structure shown under the heading "Table la" is replaced by the structure shown above.

TABLE 13c R / / \ M/ \—A>N/ Table 13c is identical to Table lc, except that the structure shown under the heading "Table 1c" is replaced by the structure shown above.

TABLE 136 RWG\ M/ \ N/ Table 13c is identical to Table le, except that the structure shown under the heading "Table 1e" is replaced by the structure shown above. 2014/054671 TABLE 14a R} 0 %/ WC“\N/> Table 14a is cal to Table la, except that the structure shown under the heading "Table la" is replaced by the structure shown above.

TABLE l4c Table 140 is identical to Table 1c, except that the structure shown under the heading "Table 1c" is replaced by the structure shown above.

TABLE l4e / NWA> \ \N \ N/ Table Me is identical to Table le, except that the structure shown under the heading "Table le" is replaced by the structure shown above.

TABLE 15a \NHm/ N I S—C_A\ \ /> Table 15a is identical to Table 1a, except that the structure shown under the heading "Table 1a" is replaced by the structure shown above.

PCT/USZOl4/054671 TABLE 15c Table 150 is identical to Table lc, except that the structure shown under the g "Table lc" is replaced by the structure shown above.

TABLE 156 / N \ \ —A> \N \ N/ Table 15e is identical to Table le, except that the structure shown under the heading "Table 1e" is replaced by the structure shown above.

TABLE 16a RA 0 S _A Table 16a is identical to Table la, except that the ure shown under the heading "Table la" is replaced by the structure shown above.

TABLE 16c (EEK? Table 16c is identical to Table lc, except that the structure shown under the heading "Table 1c" is replaced by the structure shown above.

TABLE 166 61.2%} Table 16e is identical to Table le, except that the structure shown under the heading "Table 1e" is replaced by the structure shown above.

TABLE 17a Table 17a is identical to Table la, except that the structure shown under the heading "Table 1a" is replaced by the structure shown above.

TABLE 170 Table 17c is identical to Table lc, except that the ure shown under the heading "Table lc" is replaced by the structure shown above.

TABLE 17e 73CM4\ /> N N Table 17e is identical to Table 1e, except that the ure shown under the heading "Table 1e" is replaced by the structure shown above.

TABLE 18a (EQQ Table 18a is identical to Table la, except that the structure shown under the heading "Table 1a" is replaced by the structure shown above.

PCT/USZOl4/054671 TABLE 18c éflixc? Table 180 is identical to Table lc, except that the structure shown under the heading "Table 1c" is replaced by the structure shown above.

TABLE 18e 51.2%} Table 18c is identical to Table le, except that the ure shown under the heading "Table 1c" is replaced by the structure shown above.

Table 19a is identical to Table la, except that the structure shown under the heading "Table la" is replaced by the structure shown above.

TABLE 19c Table 19c is cal to Table lc, except that the structure shown under the heading "Table 1c" is replaced by the structure shown above.

TABLE 196 RUEH—A\ /> N N Table 1% is identical to Table le, except that the structure shown under the heading "Table 1e" is replaced by the structure shown above.

RAN/H Table 20a is identical to Table 1a, except that the structure shown under the heading "Table 1a" is replaced by the structure shown above.

TABLE 20b RJI\N/H \N/ \ N/> Table 20b is identical to Table 1e, except that the structure shown under the heading "Table 1e" is replaced by the structure shown above.

TABLE 21a T@{>_A Table 21a is identical to Table 1a, except that the structure shown under the heading "Table 1a" is replaced by the structure shown above.

TABLE 21b rCC@ Table 21b is cal to Table 1e, except that the ure shown under the heading "Table 1e" is replaced by the structure shown above.

PCT/USZOl4/054671 TABLE 22a R NOMe (E{3N\N/ \ N/ Table 22a is identical to Table la, except that the structure shown under the heading "Table la" is replaced by the structure shown above.

TABLE 22b R NOMe (E{3N\N/ \ N/ Table 22b is identical to Table le, except that the structure shown under the heading "Table le" is ed by the structure shown above.

TABLE 23a NOMe / /> \ \N N Table 23a is identical to Table la, except that the ure shown under the heading "Table la" is replaced by the structure shown above.

TABLE 23b NOMe / /> \N \ Table 23b is identical to Table le, except that the structure shown under the heading "Table le" is replaced by the structure shown above.

Table 24a is identical to Table la, except that the ure shown under the heading "Table la" is replaced by the ure shown above.

TABLE 24b Table 24b is identical to Table 1c, except that the structure shown under the heading "Table 1c" is replaced by the structure shown above.

TABLE 25a R\N)‘\©f<HN{—AIH \N/ \ N/> Table 25a is identical to Table la, except that the structure shown under the heading "Table la" is replaced by the structure shown above.

TABLE 25b Table 25b is identical to Table 1c, except that the structure shown under the heading "Table lc" is replaced by the structure shown above.

A compound of this invention will generally be used as an invertebrate pest control active ingredient in a composition, i.e. formulation, with at least one onal component W0 2015f038503 selected from the group consisting of surfactants, solid diluents and liquid diluents, which serves as a carrier. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ient, mode of application and environmental factors such as soil type, moisture and temperature.

Useful formulations include both liquid and solid compositions. Liquid compositions include ons (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil in water emulsions, e concentrates and/or suspoemulsions) and the like, which optionally can be thickened into gels. The general types of aqueous liquid compositions are soluble concentrate, sion concentrate, e suspension, concentrated emulsion, microemulsion, oil in water emulsion, flowable concentrate and suspoemulsion. The general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsiflable concentrate, dispersible concentrate and oil dispersion.

The general types of solid compositions are dusts, powders, granules, pellets, prills, pastilles, s, 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 ularly useful for seed ent. Active ingredient can be (micro)encapsu1ated and r formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or “overcoated”). Encapsulation can control or delay release of the active ingredient. An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.

Sprayable formulations are lly extended in a suitable medium before spraying.

Such liquid and solid formulations are formulated to be readily diluted in the spray medium, y water, but occasionally another le 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. ble 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 ations can be applied onto seeds of crops and other desirable vegetation as seed treatments before planting to protect developing roots and other subterranean plant parts and/or foliage h ic uptake.

The ations will lly contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.

W0 2015f038503 2014/054671 Weight Percent Active Ingredient Diluent Surfactant Water-Dispersible and Water— 0.001—90 0—99.999 0—1 5 soluble Granules, Tablets and Powders Oil Dispersions, Suspensions, 1—50 40—99 0—50 ons, Solutions ding Emulsifiable Concentrates) Dusts 1—25 70—99 0—5 Granules and Pellets 0.001—99 5—99.999 0—1 5 High Strength Compositions 90—99 0—10 0—2 Solid diluents include, for example, clays such as bentonite, rillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed, Dorland Books, Caldwell, New .

Liquid diluents include, for example, water, N,N—dimethylalkanamides (e.g., N,N—dimethylformamide), limonene, dimethyl sulfoxide, N—alkylpyrrolidones (e.g., N—methylpyrrolidinone), alkyl phosphates (e.g., triethylphosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene ate, butylene carbonate, paraffins (e.g., white l oils, normal paraffins, isoparaffms), alkylbenzenes, alkylnaphthalenes, ine, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and oxymethylpentanone, acetates such as isoamyl e, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobomyl e, other esters such as alkylated lactate esters, dibasic esters alkyl and aryl benzoates, y-butyrolactone, and alcohols, which can be linear, branched, saturated or unsaturated, such as methanol, ethanol, n-propanol, isopropyl alcohol, nol, yl alcohol, n-hexanol, 2-ethy1hexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl l, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol and benzyl alcohol. Liquid ts 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), , sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish W0 2015f038503 oil), and mixtures thereof. Liquid diluents also include ted fatty acids (e.g., methylated, ted, 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 present invention often include one or more surfactants. When added to a liquid, surfactants (also known as “surface—active agents”) generally modify, most often , the surface n of the liquid. Depending on the nature of the hydrophilic and ilic groups in a surfactant molecule, surfactants can be useful as g agents, dispersants, emulsifiers or defoaming agents.

Surfactants can be classified as nonionic, anionic or cationic. ic surfactants useful for the present compositions include, but are not limited to: alcohol lates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, ene oxide, butylene oxide or mixtures thereof; amine lates, lamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; henol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide; lated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated rylphenol (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, grafi or comb polymers and star rs; polyethylene glycols (pegs); hylene glycol fatty acid esters; silicone-based surfactants; and sugar-derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.

Usefiil anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; yl sulfonate derivatives; lignin and lignin derivatives such as ulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of lated ls; sulfonates of amines and W0 2015f038503 amides such as N,N-alky1taurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkyl naphthalene; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their derivatives such as dialkyl uccinate salts.

Useful cationic tants include, but are not limited to: amides and ethoxylated amides; amines such as N—alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and lated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and e salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquatemary salts; and amine oxides such as alkyldimethylamine oxides and -hydroxyethyl)-alkylamine oxides.

Also useful for the present compositions are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, c and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon’s fiers and Detergents, annual American and International Editions published by McCutcheon’s Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic ents, Seventh n, John Wiley and Sons, New York, 1987.

Compositions of this invention 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), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), ation (evaporation retardants), and other formulation attributes. Film formers include, for example, polyvinyl acetates, nyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl ls, polyvinyl alcohol copolymers and waxes. Examples of formulation auxiliaries and additives include those listed in McCutcheon’s Volume 2: onal Materials, annual International and North American editions published by McCutcheon’s Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 222.

The compound of Formula 1 and any other active ingredients are lly orated into the present compositions by ving the active ingredient in a solvent or by ng in a liquid or dry diluent. Solutions, ing emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended W0 2015l038503 for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water. Active ingredient es, with particle diameters of up to 2,000 um can be wet milled using media mills to obtain particles with average diameters below 3 um. Aqueous slurries can be made into finished suspension concentrates (see, for example, US. 3,060,084) or further sed by spray drying to form water-dispersible es. Dry formulations usually require dry milling processes, which e average particle diameters in the 2 to 10 um range. Dusts and powders can be ed by blending and usually grinding (such as with a hammer mill or nergy mill). es and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, meration”, Chemical Engineering, December 4, 1967, pp 147—48, Perry ’s Chemical Engineer’s Handbook, 4th Ed., -Hill, New York, 1963, pages 8—57 and following, and WO 91/13546. Pellets can be prepared as described in US. 4,172,714.

Water-dispersible and water-soluble granules can be prepared as taught in US. 4,144,050, US. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in US. 5,180,587, US. ,232,701 and US. 5,208,030. Films can be prepared as taught in GB 558 and US. 3,299,566.

For further information regarding the art of formulation, see T. S. Woods, “The Formulator’s x — Product Forms for Modern Agriculture” in Pesticide Chemistry and Bioscience, The Food—Environment Challenge, T. Brooks and T. R. Roberts, Eds, Proceedings of the 9th International Congress on ide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120—133. See also US. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10—41; US. 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; US. 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 ific Publications, Oxford, 1989; and Developments informulation technology, PJB Publications, Richmond, UK, 2000.

In the following Examples, all formulations are prepared in conventional ways. nd numbers refer to nds in Index Tables A—N. Without fiirther elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following es 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.

W0 2015I038503 2014/054671 1 16 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 16 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 19 25.0% anhydrous sodium e 10.0% crude m ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0% Example E Emulsifiable Concentrate Compound 41 10.0% polyoxyethylene ol hexoleate 20.0% C6—C10 fatty acid methyl ester 70.0% Example F Microemulsion Compound 42 5.0% polyvinylpyrrolidone-Vinyl acetate copolymer 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water 20.0% W0 2015I038503 PCT/U82014/054671 1 17 Example G Seed Treatment Compound 51 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 54 2.5% idone-styrene copolymer 4.8% rylphenyl 16-ethoxy1ate 2.3% talc 0.8% corn starch 5.0% elease fertilizer 36.0% kaolin 38.0% water 1 0.6% Example I Suspension Concentrate compound 55 35% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic olyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% ne based defoamer 0.1% 1 ,2-benzisothiazolin-3 -one 0. 1% water 53.7% Example J Emulsion in Water compound 76 10.0% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0% W0 2015I038503 PCT/U82014/054671 1 18 styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1% 1 zisothiazolin-3 -one 0. 1% ic petroleum based arbon 20.0 water 58.7% Example K Oil Dispersion compound 19 25% polyoxyethylene ol hexaoleate 15% organically modified bentonite clay 2.5% fatty acid methyl ester 57.5% Example L Suspoemulsion compound 42 10.0% imidacloprid 5 .0% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1% 1 ,2-benzisothiazolin-3 -one 0. 1% aromatic petroleum based hydrocarbon 20.0% water 53.7% Compounds of this invention exhibit activity against a wide spectrum of invertebrate pests. These pests include invertebrates inhabiting a variety of nments such as, for example, plant foliage, roots, soil, harvested crops or other foodstuffs, building ures 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 e, growing or stored agronomic crops, forests, greenhouse crops, omamentals, nursery crops, stored foodstuffs or fiber ts, or houses or other structures or their contents, or being harmful to animal health or public health. Those skilled in the art will appreciate that not all compounds are equally ive against all growth stages of all pests.

W0 2015f038503 These present compounds and compositions are thus useful agronomically for protecting field crops from phytophagous invertebrate pests, and also nonagronomically for protecting other horticultural crops and plants from phytophagous invertebrate pests. This utility includes ting crops and other plants (i.e. both agronomic and nonagronomic) that contain genetic material introduced by genetic engineering (i.e. transgenic) or d by mutagenesis to provide advantageous traits. Examples of such traits include nce to herbicides, resistance to phytophagous pests (e. g., insects, mites, , spiders, nematodes, snails, plant—pathogenic fimgi, ia and viruses), improved plant growth, increased tolerance of adverse growing conditions such as high or low temperatures, low or high soil moisture, and high salinity, increased flowering or fruiting, greater t yields, more rapid maturation, higher quality and/or nutritional value of the harvested product, or improved storage or s properties of the harvested products. Transgenic plants can be modified to s multiple traits. Examples of plants ning traits provided by genetic engineering or mutagenesis include varieties of corn, cotton, n and potato sing an insecticidal Bacillus thuringiensis toxin such as YIELD GARD®, KNOCKOUT®, STARLINK®, BOLLGARD®, NuCOTN® and F®, INVICTA RR2 mom, 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 yltransferase (GAT) to provide resistance to glyphosate ide, or crops containing the HRA gene providing resistance to herbicides inhibiting acetolactate synthase (ALS).

The present compounds and compositions may interact synergistically with traits introduced by genetic engineering or modified by mutagenesis, thus enhancing phenotypic expression or effectiveness of the traits or increasing the invertebrate pest control effectiveness of the present compounds and compositions. In particular, the present compounds and itions may interact synergistically with the phenotypic expression of proteins or other natural products toxic to invertebrate pests to provide greater-than-additive control of these pests.

Compositions of this invention can also optionally comprise plant nutrients, e.g., a fertilizer composition comprising at least one plant nt selected from nitrogen, phosphorus, potassium, sulfur, calcium, magnesium, iron, copper, boron, manganese, zinc, and molybdenum. Of note are compositions comprising at least one fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfiir, m and magnesium. Compositions of the present ion which further comprise at least one plant nutrient can be in the form of liquids or . Of note are solid formulations in the form of granules, small sticks or tablets. Solid formulations sing a fertilizer composition can be prepared by mixing the compound or composition of the present invention with the fertilizer composition together with formulating ients and then preparing the formulation by methods such as granulation or extrusion. Alternatively solid W0 2015f038503 formulations can be ed by spraying a solution or suspension of a compound or ition of the present invention in a volatile t onto a previous ed 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 present nds and compositions include control of invertebrate pests in stored grains, beans and other foodstuffs, and in textiles such as clothing and carpets. Nonagronomic uses of the present compounds and itions also include invertebrate pest control in ornamental plants, forests, in yards, along roadsides and railroad rights of way, and on turf such as lawns, golf courses and pastures. Nonagronomic uses of the present compounds and compositions also include ebrate pest control in houses and other buildings which may be occupied by humans and/or companion, farm, ranch, 200 or other animals. Nonagronomic uses of the present compounds and itions also include the control of pests such as es that can damage wood or other structural materials used in ngs.

Nonagronomic uses of the t compounds and compositions also include ting human and animal health by controlling invertebrate pests that are parasitic or transmit infectious diseases. The controlling of animal parasites includes controlling external parasites that are tic to the surface of the body of the host animal (e.g., shoulders, armpits, abdomen, inner part of the thighs) and internal 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). External parasitic or disease transmitting pests include, for example, chiggers, ticks, lice, mosquitoes, flies, mites and fleas. Internal tes include heartworms, hookworms and helminths. Compounds and compositions of the present invention are suitable for systemic and/or non-systemic control of infestation or infection by parasites on animals. Compounds and compositions of the present invention are particularly suitable for combating external parasitic or disease transmitting pests. nds and compositions of the present invention are suitable for combating parasites that infest agricultural working animals, such as cattle, sheep, goats, horses, pigs, donkeys, camels, os, rabbits, hens, turkeys, ducks, geese and bees; pet animals and domestic animals such as dogs, cats, pet birds and um fish; as well as led experimental animals, such as hamsters, guinea pigs, rats and mice. By ing these parasites, fatalities and performance reduction (in terms of meat, milk, wool, skins, eggs, honey, etc.) are reduced, so that applying a composition comprising a compound of the present invention allows more economic and simple husbandry of animals.

Examples of agronomic or nonagronomic invertebrate pests include eggs, larvae and adults of the order Lepidoptera, such as armyworms, cutworms, loopers, and heliothines in the family Noctuidae (e.g., pink stem borer (Sesamz'a inferens Walker), corn stalk borer W0 2015f038503 (Sesamz‘a nonagrz’oides Lefebvre), southern armyworm (Spodoptera erz’dam'a Cramer), fall armyworrn (Spodoptera frugz'perda J. E. , beet armyworm (Spodoptera exigua Hubner), cotton rm ptera littoralz's Boisduval), yellowstriped armyworm (Spodoptera ogalli Guenée), black cutworm (Agrotz's z'psz'lon Hufnagel), velvetbean caterpillar arsia gemmatalz's ), green fruitworm (Lithophane ata Walker), cabbage armyworm (Barathra brassz'cae us), soybean looper (Pseudoplusia ens Walker), cabbage looper oplusz’a m' Hiibner), tobacco budworm thz's virescens Fabricius)); borers, casebearers, webworms, coneworms, cabbageworrns and skeletonizers from the family Pyralidae (e.g., European corn borer m'a nubilalz's Hiibner), navel orangeworm (Amyeloz's transitella Walker), corn root webworrn (Crambus caligz'nosellus Clemens), sod webworms (Pyralidae: Crambz'nae) such as sod worm (Herpetogramma licarsz'salz's Walker), sugarcane stem borer (Chilo atellus Snellen), tomato small borer (Neoleucinodes elegantalz's Guenée), green leafroller alocrocis medinalz‘s), grape leaffolder (Desmz'a funeralz's Hiibner), melon worm (Diapham'a nitz'dalz's Stoll), cabbage center grub (Helluala hydralz's Guenée), yellow stem borer (Scirpophaga incertulas Walker), early shoot borer (Scirpophaga infuscatellus Snellen), white stem borer (Scirpophaga innotata Walker), top shoot borer (Scirpophaga m‘vella Fabricius), dark- headed rice borer (Chilo polychrysus Meyrick), d riceborer (Chilo suppressalz’s Walker), cabbage cluster caterpillar 'dolomz‘a binotalz‘s English)); leafrollers, budworms, seed worms, and fruit worms in the family Tortricidae (e. g., codling moth (Cydz'a pomonella Linnaeus), grape berry moth (Endopz'za viteana Clemens), oriental fruit moth (Grapholita molesta Busck), citrus false codling moth (Cryptophlebz'a [eucotreta Meyrick), citrus borer (Ecdytolopha aurantz’ana Lima), redbanded ller otaenia velutinana Walker), obliquebanded leafroller (Choristoneura rosaceana Harris), light brown apple moth (Epiphyas postvz'ttana Walker), European grape berry moth (Eupoecilz'a ambiguella Hiibner), apple bud moth (Pandemis pyrusana Kearfott), omnivorous leafroller nota stultana Walsingham), barred fruit-tree tortrix (Pandemis cerasana Hubner), apple brown tortriX (Pandemis heparana Denis & Schiffermiiller)); and many other economically important lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypz'ella Saunders), gypsy moth (Lymantrz'a dispar Linnaeus), peach fruit borer (Carposz'na m'ponensz's Walsingham), peach twig borer (Anarsz’a Zineatella ), potato tuberworm (Phthorz'maea operculella Zeller), spotted teniform leafminer (Lithocolletz's blancardella Fabricius), Asiatic apple ner (Lithocolletz’s ringom’ella Matsumura), rice leaffolder (Lerodea eufala Edwards), apple leafminer (Leucoptera la 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 ica Linnaeus), brownbanded cockroach la longz'palpa Fabricius), American cockroach W0 2015f038503 (Periplaneta amerz’cana Linnaeus), brown cockroach (Periplaneta brunnea Burmeister), Madeira cockroach (Leucophaea maderae Fabricius)), smoky brown ach planeta fulz‘gz‘nosa Service), lian Cockroach planeta australasiae Fabr.), r cockroach (Nauphoeta cinerea r) and smooth cockroach (Symploce pallens Stephens)); eggs, foliar g, fruit feeding, root feeding, seed feeding and lar tissue feeding larvae and adults of the order Coleoptera including weevils from the families Anthribidae, Bruchidae, and Curculionidae (e.g., boll weevil (Anthonomus s Boheman), rice water weevil (Lissorhoptrus oryzophilus Kuschel), granary weevil (Sitophz'lus granarius Linnaeus), rice weevil (Sitophilus oryzae Linnaeus)), annual bluegrass weevil (Listronotus maculz'collz's Dietz), bluegrass billbug (Sphenophorus parvulus hal), hunting billbug (Sphenophorus venatus vestitus), Denver billbug ophorus cicatrz'strialus us)); flea beetles, cucumber beetles, rootworms, leaf beetles, potato beetles, and leafminers in the family Chrysomelidae (e.g., Colorado potato beetle (Leptinotarsa decemlz'neata Say), western corn rootworm (Diabrotica virgifera virgz'fera l5 LeConte)); chafers and other beetles from the family Scarabaeidae (e.g., se beetle (Papillz‘a japonica Newman), al beetle (Anomala orientalz‘s Waterhouse, Exomala orientalz's house) Baraud), northern masked chafer (Cyclocephala borealz’s Arrow), southern masked chafer (Cyclocephala immaculata Olivier or C. [under Bland), dung beetle and white grub (Aphodius spp.), black turfgrass ataenius (Ataem'us spretulus Haldeman), green June beetle (Cotim's nitz'da Linnaeus), Asiatic garden beetle (Maladera castanea Arrow), May/June beetles (Phyllophaga spp.) and European chafer (Rhizotrogus majalz's Razoumowsky)); carpet beetles from the family Dermestidae; wireworms from the family Elateridae; bark beetles from the family Scolytidae and flour beetles from the family Tenebrionidae.

In addition, agronomic and nonagronomic pests include: eggs, adults and larvae of the order Derrnaptera including earwigs from the family Forficulidae (e.g., European earwig (Forficula auricularz'a Linnaeus), black earwig (Chelz'soches morio Fabricius»; eggs, immatures, adults and nymphs of the orders Hemiptera and Homoptera such as, plant bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g. Empoasca spp.) from the family Cicadellidae, bed bugs (e.g., Cimex lectularius Linnaeus) from the family Cimicidae, planthoppers from the families Fulgoroidae and Delphacidae, treehoppers from the family Membracidae, psyllids from the family Psyllidae, whiteflies from the family Aleyrodidae, aphids from the family dae, phylloxera from the family Phylloxeridae, mealybugs from the family Pseudococcidae, scales from the es Coccidae, Diaspididae and Margarodidae, lace bugs from the family Tingidae, stink bugs from the family Pentatomidae, chinch bugs (e.g., hairy chinch bug us Zeucopterus hirtus Montandon) and southern chinch bug (Blissus insularz's Barber)) and other seed bugs from the family W0 2015f038503 Lygaeidae, spittlebugs from the family Cercopidae squash bugs from the family Coreidae, and red bugs and cotton stainers from the family Pyrrhocoridae. mic 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 ulmz' Koch), two d spider mite (Tetranychus urticae Koch), McDaniel mite nychus mcdam'elz' McGregor)); flat mites in the family alpidae (e.g., citrus flat mite (Brevz'palpus lewz'sz' McGregor)); rust and bud mites in the family Eriophyidae and other foliar feeding mites and mites important in human and animal health, i.e. dust mites in the family Epidermoptidae, follicle mites in the family Demodicidae, grain mites in the family Glycyphagidae; ticks in the family Ixodidae, commonly known as hard ticks (e.g., deer tick (Ixodes scapularz's Say), Australian paralysis tick (Ixodes clus Neumann), American dog tick (Dermacentor variabilis Say), lone star tick (Amblyomma anum Linnaeus)) and ticks in the family Argasidae, commonly known as soft ticks (e.g., relapsing fever tick (Ornithadaros turz'cata), common fowl tick (Argas radiatus»; scab and itch mites in the es Psoroptidae, idae, and Sarcoptidae; eggs, adults and immatures of the order Orthoptera including grasshoppers, locusts and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguim’pes Fabricius, M. dz'fi’eremz’alz’s Thomas), American grasshoppers (e.g., Schistocerca amerz’cana Drury), desert locust tocerca gregaria Forskal), migratory locust (Locusta migratorz’a Linnaeus), bush locust (Zonocerus spp.), house cricket (Acheta domesticus Linnaeus), mole crickets (e.g., tawny mole cricket (Scapterz'scus vicinus Scudder) and southern mole cricket eriscus l'l' GigliO-TOS)); eggs, adults and immatures of the order Diptera including leafminers (e. g., Lirz'omyza spp. such as serpentine vegetable leafminer (Lirz'omyza e Blanchard)), , fruit flies (Tephritidae), frit flies (e.g., Oscinellafrit Linnaeus), soil maggots, house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g., Fannia canicularz's Linnaeus, F. femoralz's Stein), stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g., Chrysomya spp., Phormz'a spp.), and other muscoid fly pests, horse flies (e.g., Tabanus spp.), bot flies (e.g., Gastrophilus spp., Oestrus spp.), cattle grubs (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.), keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g., Prosz'mulz'um spp., Simulz'um spp.), biting midges, sand flies, sciarids, and other Nematocera; eggs, adults and immatures of the order Thysanoptera including onion thrips (Thrips tabacz' Lindeman), flower thrips (Franklim‘ella 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 lvanicus De Geer), white—footed ant (Technomyrmex albz’pes fr. Smith), big headed ants (Pheidole sp.), ghost ant (Tapinoma cephalum Fabricius); Pharaoh ant (Monomorium pharaonis W0 2015f038503 Linnaeus), little fire ant nm’a auropunctata Roger), fire ant (Solenopsz’s gemz’nata ius), red imported fire ant (Solenopsz's invicta Buren), Argentine ant myrmex humilis Mayr), crazy ant (Paratrechz’na longicorm‘s Latreille), pavement ant (Tetramorz'um caespz'tum Linnaeus), cornfield ant (Lasz'us alienus Forster) and odorous house ant (Tapinoma sessile Say). Other Hymenoptera including bees (including ter bees), hornets, yellow jackets, wasps, and sawflies (Neodz'prz'on spp.; Cephus spp.); insect pests of the order Isoptera ing termites in the Termitidae (e. g., ermes sp., Odontotermes obesus Rambur), Kalotermitidae (e.g., Cryptotermes sp.), and Rhinotermitidae (e.g., Reticulz'termes sp., Coptotermes sp., Heterotermes tenuis Hagen) es, the eastern subterranean termite (Reticulz'termes fiavz’pes Kollar), western subterranean e ulz'termes hesperus , Formosan subterranean termite (Coptotermes formosanus Shiraki), West Indian drywood termite (Incisitermes immigrans Snyder), powder post termite (Cryptotermes brevis Walker), drywood termite itermes snyderz' Light), southeastern subterranean termite (Reticulz'termes virginicus Banks), western drywood termite itermes minor Hagen), arboreal termites such as Nasutz'termes sp. and other termites of economic importance; insect pests of the order Thysanura such as fish (Lepz‘sma saccharine: Linnaeus) and firebrat obia domestica Packard); insect pests of the order Mallophaga and including the head louse (Pediculus hummus capitz's De Geer), body louse (Pediculus humanus Linnaeus), chicken body louse anthus stramz’neus Nitszch), dog biting louse odectes canis De Geer), fluff louse (Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank), short-nosed cattle louse (Haematopinus eurjystemus Nitzsch), long-nosed cattle louse (Linognathus vitulz' Linnaeus) and other sucking and chewing parasitic lice that attack man and animals; insect pests of the order Siphonoptera including the oriental rat flea (Xenopsylla cheapis Rothschild), cat flea (Ctenocephalides felis Bouche), dog flea (Ctenocephalz’des cams Curtis), hen flea (Ceratophyllus gallinae Schrank), sticktight flea (Echidnophaga gallinacea Westwood), human flea (Pulex irritans Linnaeus) and other fleas afflicting mammals and birds.

Additional arthropod pests covered include: spiders in the order Araneae such as the brown recluse spider (Loxosceles reclusa h & Mulaik) and the black widow spider (Latrodectus mactans Fabricius), and edes in the order Scutigeromorpha such as the house centipede (Scutigera coleoptrata Linnaeus).

Examples of invertebrate pests of stored grain include larger grain borer (Prostephanus truncatus), lesser grain borer (Rhyzopertha dominica), rice weevil (Stiophz'lus orjyzae), maize weevil (Stiophz’lus zeamaz’s), cowpea weevil (Callosobruchus maculatus), red flour beetle (Tribolz'um castaneum), granary weevil (Stiophz'lus granarz‘us), Indian meal moth (Plodz'a interpunctella), Mediterranean flour beetle (Ephestz'a kuhm'ella) and flat or rusty grain beetle (Cryptolestisfermgineus).

W0 38503 Compounds of the present invention may have activity on members of the Classes Nematoda, Cestoda, Trematoda, and Acanthocephala including economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida such as but not limited to economically important agricultural pests (i.e. root knot nematodes in the genus Meloidogyne, lesion nematodes in the genus Pratylenchus, stubby root nematodes in the genus Trichodoras, etc.) and animal and human health pests (i.e. all economically important flukes, tapeworms, and roundworms, such as Strongylas valgarz's in , Toxocara canis in dogs, Haemonchas contortas in sheep, Dirofilaria immitz's Leidy in dogs, Anoplocephala z'ata in horses, ola hepatica Linnaeus in ruminants, etc.).

Compounds of the invention may have activity against pests in the order Lepidoptera (e.g., Alabama argz'llacea Hiibner (cotton leaf worm), Archips argyrospz'la Walker (fruit tree leaf roller), A. rosana Linnaeus (European leaf roller) and other Archips species, Chilo ssalis Walker (rice stem borer), Cnaphalocrosz’s medinalz's Guenee (rice leaf roller), Crambas caliginosellas Clemens (corn root webworm), s teterrellas Zincken (bluegrass webworm), Cydz'a pomonella Linnaeus (codling moth), Earias insalana val (spiny bollworm), Earz’as vittella Fabricius (spotted bollworm), Helicoverpa armigera Hubner (American bollworm), Helicoverpa zea Boddie (corn earworm), Heliothz's virescens Fabricius (tobacco budworm), Herpetogramma licarsisalz’s Walker (sod webworm), Lobesz’a botrana Denis & Schiffermiiller (grape berry moth), ophora gossypz'ella Saunders (pink rm), Phyllocm'stz's citrella Stainton (citrus leafminer), Pierz's brassicae Linnaeus (large white butterfly), Pierz's rapae us (small white butterfly), la xylostella Linnaeus (diamondback moth), Spoa’optera exigua Hiibner (beet armyworm), Spodoptera litara ius (tobacco cutworm, cluster caterpillar), Spoa’optera fragiperda J. E. Smith (fall armyworm), Trichoplasia ni Hubner ge ) and Tata absolata Meyrick o leafminer)).

Compounds of the ion have significant activity on members from the order Homoptera including: Acyrthosz'phon pisam Harris (pea , Aphis craccz'vora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomz' De Geer (apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacortham solam' Kaltenbach (foxglove aphid), Chaetosiphon fragaefolz'z' Cockerell (strawberry aphid), Diaraphz's noxia mov/Mordvilko (Russian wheat aphid), Dysaphz’s plantagz'nea Paaserini (rosy apple aphid), Eriosoma lam’geram Hausmann (woolly apple aphid), Hyalopteras pram’ Geoffroy (mealy plum aphid), Lipaphz’s erysz'mz' Kaltenbach (turnip aphid), Metopolophz'am dirrhoa’am Walker (cereal aphid), Macrosz'pham eaphorbz’ae Thomas (potato aphid), Myzus ae Sulzer (peach—potato aphid, green peach aphid), via ribisnigrz' Mosley (lettuce aphid), 'gas spp. (root aphids and gall aphids), Rhopalosiphum maidz's Fitch (corn leaf aphid), Rhopalosz'pham padi Linnaeus (bird cherry-oat aphid), Schizaphz's gramz'nam Rondani bug), Sitobion avenae Fabricius W0 2015f038503 (English grain aphid), Therioaphz's maculata Buckton (spotted alfalfa aphid), era aurantz‘z‘ Boyer de Fonscolombe (black citrus aphid), and Toxoptem citricz’da dy (brown citrus aphid); Adelges spp. (adelgids); Phylloxera devastam’x Pergande (pecan phylloxera); Bemz’sz’a tabacz' Gennadius (tobacco whitefly, sweetpotato whitefly), 'a argentz'folii Bellows & Perring (silverleaf y), Dialeurodes citri d (citrus whitefly) and Trialeurodes vaporarz'orum Westwood (greenhouse whitefly); Empoasca fabae Harris (potato leafhopper), Laodelphax striatellus Fallen (smaller brown planthopper), Macrolestes quadrilz'neatus Forbes (aster leafhopper), Nephotettz'x cinticeps Uhler (green leafhopper), Nephotettz'x nigropz'ctus Sté’tl (rice leafhopper), Nilaparvata lugens Stéil (brown planthopper), Peregrinus maidz's Ashmead (corn planthopper), Sogatella furcz'fera Horvath (white-backed planthopper), Sogatodes orizz'cola Muir (rice delphacid), Typhlocyba pomarz’a McAtee white apple leafhopper, Erythroneoura spp. (grape leafhoppers); Magicidada septendecz'm Linnaeus (periodical cicada); Icerya purchasz' Maskell (cottony cushion scale), Quadraspz'diotus perniciosus Comstock (San Jose ; Planococcus citrz' Risso (citrus mealybug); Pseudococcus spp. (other mealybug complex); Cacopsylla pyricola Foerster (pear psylla), Trioza diospyrz' Ashmead (persimmon psylla).

Compounds of this invention also have activity on members from the order Hemiptera including: Acrostemum hilare Say (green stink bug), Anasa 's De Geer h bug), Blissus leucopterus leucopterus Say (chinch bug), Cz'mex lectularz'us Linnaeus (bed bug) Corythuca gossypii Fabricius (cotton lace bug), Cyrtopeltz's modesta Distant (tomato bug), Dysdercus suturellus Herrich-Schaffer (cotton r), Euchistus servus Say (brown stink bug), Euckistus variolarius Palisot de Beauvois (one-spotted stink bug), Graptosthetus spp. (complex of seed bugs), Halymorpha halys Sté’tl (brown marmorated stink bug), Leptoglossus corculus Say (leaf-footed pine seed bug), Lygus arz's Palisot de Beauvois (tarnished plant bug), Nezara viridula Linnaeus (southern green stink bug), Oebalus pugnax ius (rice stink bug), Oncopeltus fasciatus Dallas (large ed bug), Pseudatomoscelz’s seriatus Reuter (cotton fleahopper). Other insect orders controlled by compounds of the invention include Thysanoptera (e.g., im'ella occidentalz's Pergande (western flower thrips), Scirthothrips citrz' n (citrus thrips), Sericothrz'ps variabilis Beach (soybean thrips), and Thrips tabacz' Lindeman (onion thrips); and the order Coleoptera (e.g., Leptinotarsa ineata Say (Colorado potato beetle), Epilachmz stis t an bean beetle) and wireworms of the genera Agriotes, Athous or Limom’us).

Note that some contemporary fication systems place Homoptera as a suborder within the order Hemiptera.

Of note is use of nds of this invention for controlling western flower thrips (Franklz'niella occidentalis). Of note is use of compounds of this invention for lling potato leafhopper (Empoasca fabae). Of note is use of compounds of this invention for lling cotton melon aphid (Aphis gossypz'z'). Of note is use of compounds of this W0 2015f038503 invention for controlling green peach aphid (Myzus persicae). Of note is use of compounds of this invention for controlling otato y (Bemz'sz'a tabacz').

Compounds of the present invention may also be useful for increasing vigor of a crop plant. This method ses 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 e the desired plant vigor effect (i.e. biologically effective amount).

Typically the compound of Formula 1 is applied in a formulated composition. Although the compound of Formula 1 is often applied directly to the crop plant or its seed, it can also be applied to the locus of the crop plant, i.e. the environment of the crop plant, particularly the portion of the environment in close enough proximity to allow the compound of Formula 1 to migrate to the crop plant. The locus relevant to this method most commonly comprises the growth medium (i.e. medium providing nutrients to the plant), typically soil in which the plant is grown. Treatment of a crop plant to increase vigor of the crop plant thus comprises contacting the crop plant, the seed from which the crop plant is grown or the locus of the crop plant with a biologically effective amount of a compound of Formula 1.

Increased crop vigor can result in one or more of the following ed s: (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 , number of tillers (e.g., for rice), root mass and overall dry weight of vegetative mass of the crop; (0) improved crop yields, as demonstrated by time to flowering, duration of flowering, number of flowers, total biomass lation (i.e. yield ty) and/or fruit or grain grade marketability of produce (i.e. yield quality); ((1) 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 re to thermal extremes, suboptimal moisture or phytotoxic chemicals.

The compounds of the present invention may increase the vigor of treated plants compared to untreated plants by killing or ise preventing g of phytophagous invertebrate pests in the environment of the plants. In the e of such control of phytophagous invertebrate pests, the pests reduce plant vigor by consuming plant s or sap, or transmiting plant pathogens such as viruses. Even in the absence of phytophagous invertebrate pests, the nds of the ion 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 nd of the invention if the plant is grown in a nonideal environment, i.e. an environment comprising one or more aspects adverse to the plant achieving the full genetic potential it would exhibit in an ideal environment.

Of note is 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 W0 2015f038503 method for increasing vigor of a crop plant wherein the crop plant is grown in an nment 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 ideal for supporting growth of the crop plant.

Of note is a method for increasing vigor of a crop plant wherein the crop is rice. Also of note is a method for sing 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 invention can also be mixed with one or more other biologically active compounds or agents including insecticides, fungicides, nematocides, bactericides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other ically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agronomic and nonagronomic y. Thus the present invention also ns 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 present ion, the other biologically active compounds or agents can be formulated together with the present compounds, including the nds of Formula 1, to form a premix, or the other biologically active compounds or agents can be ated separately from the present nds, including the compounds of Formula 1, and the two formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession. es of such biologically active compounds or agents with which nds of this invention can be formulated are insecticides such as abamectin, te, nocyl, acetamiprid, acrinathrin, afidopyropen ([(3S,4R,4aR,6S,6aS,l2R,12aS,12bS)-3 - [(cyclopropylcarbonyl)oxy]- l ,3 ,4,4a,5 ,6,6a, 12,12a,le-decahydro-6,lZ-dihydroxy-4,6a, 12b- trimethyl-l l-oxo(3 -pyridinyl)—2H,l 1H-naphtho [2, l -b]pyrano [3 ,4-e]pyranyl]methyl cyclopropanecarboxylate), amidoflumet, amitraz, avermectin, achtin, azinphos-methyl, acarb, bensultap, bifenthrin, bifenazate, bistrifluron, borate, , buprofezin, cadusafos, carbaryl, carbofiiran, cartap, carzol, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin, cyantraniliprole (3-bromo- l -(3 -chloropyridinyl)-N-[4-cyanomethy1 [(methylamino)carbonyl]pheny1]-lH-pyrazole-S-carboxamide), cyclaniliprole (Ci-bromofifl {2—bromo—4~chioro~6—lR l -cchopropyiethylfimino}carbonyl]phenyl] ~ 1 —{3—chioro—2— pyridinyl}iH—pyrazoiewfi—carboxamide), cycloprothrin, cycloxaprid ({53,8R}«1—{{6~chloro~3w pyridinyifinethy@231 , S ,6,7’_,8—l'iexahydro~9Ani tro~5 , 8~ Epoxy— l {LimidazoE E ,2vajazepine) cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda- cyhalothrin, ethrin, alpha-cypermethrin, ypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimehypo, oate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, prox, ole, fenbutatin oxide, othion, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flometoquin (2-ethyl-3,7-dimethyl[4- (trifluoromethoxy)phenoxy]quinolinyl methyl carbonate), flonicamid, flubendiamide, flucythrinate, flufenerim, flufenoxuron, flufenoxystrobin (methyl (αE)[[2-chloro (trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)benzeneacetate), fluensulfone (5- chloro[(3,4,4-trifluorobutenyl)sulfonyl]thiazole), fluhexafon, fluopyram, flupiprole (1-[2,6-dichloro(trifluoromethyl)phenyl][(2-methylpropenyl)amino] [(trifluoromethyl)sulfinyl]-1H-pyrazolecarbonitrile), flupyradifurone (4-[[(6-chloro pyridinyl)methyl](2,2-difluoroethyl)amino]-2(5H)-furanone), fluvalinate, tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide, heptafluthrin ([2,3,5,6-tetrafluoro (methoxymethyl)phenyl]methyl 2,2-dimethyl[(1Z)-3,3,3-trifluoropropen yl]cyclopropanecarboxylate), hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, carb, icidal soaps, isofenphos, ron, malathion, meperfluthrin ([2,3,5,6- tetrafluoro(methoxymethyl)phenyl]methyl (1R,3S)(2,2-dichloroethenyl)-2,2- dimethylcyclopropanecarboxylate), metaflumizone, metaldehyde, methamidophos, methidathion, methiodicarb, methomyl, methoprene, methoxychlor, metofluthrin, methoxyfenozide, metofluthrin, otophos, monofluorothrin ([2,3,5,6-tetrafluoro (methoxymethyl)phenyl]methyl 3-(2-cyanopropenyl)-2,2- dimethylcyclopropanecarboxylate), nicotine, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, propargite, protrifenbute, pyflubumide (1,3,5-trimethyl-N-(2-methyloxopropyl)-N-[3-(2-methylpropyl)[2,2,2- trifluoromethoxy(trifluoromethyl)ethyl]phenyl]-1H-pyrazolecarboxamide), pymetrozine, pyrafluprole, rin, pyridaben, lyl, pyrifluquinazon, pyriminostrobin (methyl (αE)[[[2-[(2,4-dichlorophenyl)amino](trifluoromethyl) pyrimidinyl]oxy]methyl]-α-(methoxymethylene)benzeneacetate), ole, oxyfen, rotenone, ryanodine, uofen, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulprofos, sulfoxaflor (N-[methyloxido[1-[6-(trifluoromethyl) pyridinyl]ethyl]-λ4-sulfanylidene]cyanamide), tebufenozide, npyrad, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethylfluthrin ([2,3,5,6-tetrafluoro- 4-(methoxymethyl)phenyl]methyl 2,2,3,3-tetramethylcyclopropanecarboxylate), tetraniliprole, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tioxazafen (3- phenyl(2-thienyl)-1,2,4-oxadiazole), tolfenpyrad, tralomethrin, triazamate, trichlorfon, triflumezopyrim (2,4-dioxo(5-pyrimidinylmethyl)[3-(trifluoromethyl)phenyl]-2H- pyrido[1,2-a]pyrimidinium inner salt), triflumuron, Bacillus thuringiensis delta-endotoxins, pathogenic bacteria, entomopathogenic viruses and entomopathogenic fungi.

Of note are insecticides such as abamectin, acetamiprid, thrin, yropen, amitraz, avermectin, azadirachtin, benfuracarb, bensultap, bifenthrin, buprofezin, cadusafos, carbaryl, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zetacypermethrin , cyromazine, deltamethrin, in, furan, 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, methiodicarb, methomyl, methoprene, methoxyfenozide, metofluthrin, uorothrin, 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, mezopyrim, triflumuron, Bacillus thuringiensis delta-endotoxins, all strains of Bacillus giensis and all strains of nucleo polyhedrosis viruses.

One embodiment of ical agents for mixing with compounds of this invention include entomopathogenic ia 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, apolis, Indiana, USA); pathogenic fungi such as green muscardine fungus; and entomopathogenic (both naturally occurring and cally modified) viruses including baculovirus, nucleopolyhedro virus (NPV) such as Helicoverpa zea nucleopolyhedrovirus (HzNPV), Anagrapha falcifera nucleopolyhedrovirus (AfNPV); and granulosis virus (GV) such as Cydia pomonella granulosis virus (CpGV).

Of particular note is such a combination where the other invertebrate pest control active ingredient belongs to a different chemical class or has a different site of action than the nd of Formula 1. In certain instances, a combination with at least one other invertebrate pest control active ingredient having a similar spectrum of control but a different site of action will be particularly ageous for resistance management. Thus, a composition of the present invention can further se a biologically effective amount of at least one additional invertebrate pest control active ingredient having a similar spectrum of control but belonging to a different chemical class or having a different site of action.

These additional biologically active nds 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 nists such as the cyclodienes dieldrin and endosulfan, and the phenylpyrazoles ethiprole and fipronil; sodium channel modulators such as the pyrethroids bifenthrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda—cyhalothrin, cypermethrin, deltamethrin, dimefluthrin, esfenvalerate, metofluthrin and profluthrin; nicotinic acetylcholinereceptor (nAChR) agonists such as the neonicotinoids acetamiprid, clothianidin, dinotefuran, loprid, yram, nithiazine, thiacloprid, and thiamethoxam, and sulfoxaflor; nicotinic choline receptor (nAChR) allosteric tors such as the spinosyns spinetoram and spinosad; chloride channel activators such as the avermectins abamectin and emamectin; juvenile hormone mimics such as diofenolan, methoprene, carb and pyriproxyfen; ive homopteran feeding blockers such as pymetrozine and flonicamid; mite growth inhibitors such as etoxazole; inhibitors of mitochondrial ATP synthase such as propargite; ucouplers of oxidative phosphorylation via disruption of the proton gradient such as chlorfenapyr; nicotinic acetylcholine receptor (nAChR) channel blockers such as the nereistoxin analogs cartap; tors of chitin biosynthesis such as the benzoylureas flufenoxuron, hexaflumuron, lufenuron, ron, noviflumuron and triflumuron, and buprofezin; dipteran moulting disrupters such as cyromazine; ecdysone receptor agonists such as the hydrazines methoxyfenozide and tebufenozide; octopamine receptor agonists such as amitraz; mitochondrial complex 111 electron transport inhibitors such as hydramethylnon; mitochondrial complex I electron 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 x I] electron transport inhibitors such as the nitriles cyenopyrafen and cyflumetofen; ryanidine receptor modulators such as the nilic diamides ntraniliprole, cyantraniliprole and cyantraniliprole, diamides such as flubendiamide, and ryanodine receptor ligands such as ine; compounds wherein the target site responsible for biological activity is unknown or uncharacterized such as azadirachtin, bifenazate, pyridalyl, pyrifluquinazon and triflumezopyrim; ial disrupters of insect midgut membranes such as Bacillus thuringensis and the delta-endotoxins they produce and Bacillus icus; and biological agents including nucleo polyhedro viruses (NPV) and other naturally occurring or cally modified insecticidal s.

Further examples of biologically active compounds or agents with which compounds of this invention can be formulated are: fungicides such as acibenzolar—S—methyl, aldimorph, ametoctradin, amisulbrom, anilazine, azaconazole, azoxystrobin, benalaxyl (including benalaxyl—M), benodanil, benomyl, benthiavalicarb (including benthiavalicarb-isopropyl), indiflupyr, bethoxazin, cryl, biphenyl, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, carboxin, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, chlozolinate, copper hydroxide, copper oride, copper sulfate, coumoxystrobin, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole (including diniconazole-M), dinocap, dithianon, dithiolanes, dodemorph, , econazole, etaconazole, edifenphos, enoxastrobin (also known as enestroburin), epoxiconazole, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, fenaminstrobin, fenarimol, fenbuconazole, fenfuram, fenhexamide, fenoxanil, fenpiclonil, fenpropidin, pimorph, fenpyrazamine, fentin e, fentin hydroxide, ferbam, ferimzone, flometoquin, fluazinam, fludioxonil, flufenoxystrobin, flumorph, fluopicolide, fluopyram, fluoxastrobin, fluquinconazole, flusilazole, amide, flutianil, flutolanil, flutriafol, roxad, folpet, fthalide (also known as phthalide), dazole, fiJralaxyl, fiirametpyr, hexaconazole, hymexazole, ine, imazalil, imibenconazole, iminoctadine albesilate, iminoctadine triacetate, rb, ipconazole, isofetamid, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam, nil, kasugamycin, kresoxim-methyl, eb, mandipropamid, mandestrobin, maneb, mapanipyrin, mepronil, meptyldinocap, metalaxyl (including metalaxyl-M/mefenoxam), metconazole, ulfocarb, m, metominostrobin, metrafenone, myclobutanil, naftitine, neo-asozin (ferric earsonate), nuarimol, octhilinone, ofurace, orysastrobin, oxadixyl, oxathiapiprolin, oxolinic acid, oxpoconazole, oxycarboxin, oxytetracycline, penconazole, uron, penflufen, penthiopyrad, perfurazoate, phosphorous acid (including salts thereof, e.g., fosetylaluminm ), picoxystrobin, lin, polyoxin, probenazole, prochloraz, procymidone, ocarb, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, ostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributacarb, pyrifenox, pyriofenone, perisoxazole, pyrimethanil, pyrifenox, pyrrolnitrin, pyroquilon, quinconazole, quinmethionate, yfen, quintozene, silthiofam, sedaxane, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, tebufloquin, teclofihalam, tecloftalam, tecnazene, terbinafine, tetraconazole, thiabendazole, thifluzamide, thiophanate, thiophanate- methyl, thiram, tiadinil, fos-methyl, tolprocarb, tolyfluanid, triadimefon, triadimenol, triarimol, triazoxide, tribasic copper sulfate, triclopyricarb, tridemorph, trifloxystrobin, triflumizole, trimoprhamide tricyclazole, trifloxystrobin, triforine, triticonazole, azole, validamycin, valifenalate (also known as valifenal), Vinclozolin, zineb, ziram, zoxamide and 1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydroisoxazolyl]thiazolyl]piperidinyl][5- methyl—3-(trifluoromethyl)-lH-pyrazol-l-yl]ethanone; nematocides such as am, spirotetramat, thiodicarb, fosthiazate, abamectin, iprodione, fluensulfone, dimethyl disulfide, tioxazafen, 1,3—dichloropropene (1,3-D), metam (sodium and potassium), dazomet, chloropicrin, fenamiphos, ethoprophos, cadusaphos, terbufos, imicyafos, oxamyl, W0 2015l038503 carbofuran, tioxazafen, Bacillus firmus and Pasteurz'a nz'shz‘zawae; bactericides such as streptomycin; ides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, hlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and npyrad.

In certain instances, combinations of a compound of this invention with other biologically active (particularly invertebrate pest control) compounds or agents (i.e. active ingredients) can result in a r-than-additive (i.e. synergistic) effect. Reducing the quantity of active ients ed in the environment while ng effective pest control is always ble. When ism of invertebrate pest l active ingredients occurs at ation 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 invention and compositions thereof can be applied to plants genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis delta-endotoxins). Such an application may provide a broader spectrum of plant protection and be advantageous for resistance ment. The effect of the exogenously applied invertebrate pest control compounds of this ion may be synergistic with the expressed toxin proteins.

General references for these agricultural protectants (i.e. insecticides, fungicides, nematocides, acaricides, herbicides and biological agents) include The ide Manual, 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2003 and The BioPestl'cide Manual, 2nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2001.

For ments where one or more of these various mixing rs are used, the weight ratio of these various mixing partners (in total) to the compound of Formula 1 is typically n about 13000 and about 3000:1. Of note are weight ratios between about 1:300 and about 300:1 (for example ratios between about 1:30 and about 30:1). One skilled in the art can easily determine through simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity. It will be evident that including these additional components can expand the spectrum of invertebrate pests controlled beyond the spectrum controlled by the compound of Formula 1 alone.

Table A lists specific combinations of a compound of Formula 1 with other invertebrate pest control agents illustrative of the mixtures, compositions and methods of the present invention. The first column of Table A lists the specific invertebrate pest l 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 colunm of Table A lists embodiment(s) of ranges of weight ratios for rates at which the invertebrate 2014/054671 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 tin can be applied in a weight ratio between 50:1 to 1:50. The remaining lines of Table A are to be construed rly. Of further note Table A lists specific combinations of a compound of Formula 1 with other ebrate pest control agents illustrative of the es, itions and methods of the present invention and includes additional embodiments of weight ratio ranges for application rates.

Table A Invertebrate Pest Mode ofAction or Chemical Class Typical Control Aent Weiht Ratio chloride channel tor 50:1 to 1:50 Acetamiprid nicotinic acetylcholinereceptor (nAChR) 150:1 to 1:200 agonist Cartap nicotinic acetylcholine receptor (nAChR) 100:1 to 1:200 channel r 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 acetylcholine receptor (nAChR) 100:1 to 1:400 agonist Dinotefuran nicotinic acetylcholine receptor (nAChR) 150:1 to 1:200 agonist 150:1 to 1:200 chloride channel activator 50:1 to 1:10 1 3 5 Invertebrate Pest Mode ofAction or Chemical Class l Control A_ent Wei _ht Ratio Endosulfan GABA-gated chloride channel antagonist 200:1 to 1:100 sodium channel modulator 100:1 to 1:400 Ethiprole GABA-regulated de channel 200:1 to 1:100 antagonist ——150:1 to 1:200 500:1t01:100 sodium channel modulator 1501 to 1:200 Fipronil egulated chloride channel 150:1 to 1:100 antagonist transport inhibitors blocker Lambda—cyhalothrin sodium channel modulator 50:1 to 1:250 chitin biosynthesis inhibitor 5001 to 1:250 Metaflumizone voltage-dependent sodium channel 200:1 to 1:200 blocker Methomyl acetylcholinesterase inhibitor 500:1 to 1:100 500:1to 1:100 Methoxyfenozide ecdysone receptor agonist 50:1 to 1:50 agonist agonist Control A_ent Wei _ht Ratio allosteric activator allosteric activators Spirodiclofen acetyl CoA ylase inhibitor 200:1 to 1:200 acetyl CoA carboxylase inhibitor 200:1 to 1:200 Tebufenozide ecdysone receptor t 500:1 to 1:250 agonist agonist Thiodicarb acetylcholinesterase inhibitors 500:1 to l :400 Thiosultap-sodium Nicotinic acetylcholine receptor (nAChR) 150:1 to 1:100 channel blocker us thuringiensis biological agents 50:1 to 1:10 delta-endotoxin NPV (e.g., Gemstar) biological agents 50:1 to 1:10 Ofnote is the composition of the present invention wherein the at least one additional ically active compound or agent is selected from the Invertebrate Pest Control Agents listed in Table A above.

The weight ratios of a compound, including a compound of Formula 1, an N—oxide or a salt thereof, to the additional invertebrate pest control agent typically are between 1000:1 and 121000, with one embodiment being between 500:1 and 1:500, another embodiment being n 250:1 and 1:200 and another embodiment being between 100:1 and 1:50.

W0 038503 2014/054671 Listed below in Tables B1 to B10 are embodiments of specific compositions comprising a compound of Formula 1 (compound numbers refer to compounds in Index Tables A-N) and an additional invertebrate pest control agent.

Table B 1 e Cmpd. and Invertebrate Pest Control Mixture Cmpd and Invertebrate Pest No. No. Aent No. No. Control Aent 8 Abamectin B l -3 8 8 and Indoxacarb 8 ACetamiprid B l -3 9 8 and Lambda—cyhalothrin 8 Amitraz B l -40 8 and Lufenuron 8 Avermectin B l -4 l 8 and Metaflumizone 8 Azadirachtin B l -42 8 and Methomyl 8 Bensultap B l -43 8 and Methoprene 8 Beta—cyfluthrin B l -44 8 and Methoxyfenozide 8 Bifenthrin B l -45 8 and Nitenpyram 8 Buprofezin B1-46 8 and Nithiazine 8 Cartap B 1 —47 8 and ron 8 Chlorantraniliprole B 1 -4 8 8 and Oxamyl 8 enapyr B 1 —49 8 and Phosmet 8 Chlorpyrifos B l -5 0 8 and Pymetrozine 8 Clothianidin B 1 -5 1 8 and Pyrethrin 8 Cyantraniliprole B 1 —52 8 and Pyridaben 8 Cyfluthrin B l -53 8 and Pyridalyl 8 thrin B l -54 8 and Pyriproxyfen 8 Cypermethrin B l -55 8 and ine 8 Cyromazine B l -56 8 and Spinetoram 8 Deltamethrin B 1 —5 7 8 and Spinosad 8 Dieldrin B l -5 8 8 and Spirodiclofen 8 Dinotefuran B 1 —59 8 and Spiromesifen 8 Diofenolan B l -60 8 and Spirotetramat 8 Emamectin B l -6 l 8 and Sulfoxaflor 8 Endosulfan B l -62 8 and ozide 8 Esfenvalerate B 1 -63 8 and Tefluthrin 8 Ethiprole B l -64 8 and Thiacloprid 8 Fenothiocarb B1-65 8 and Thiamethoxam 8 Fenoxycarb B1-66 8 and Thiodicarb 8 Fenvalerate B 1 -67 8 and Thiosultap-sodiurn 8 FipTOI'lil B l -68 8 and Tolfenpyrad 8 Flonicamid B 1 —69 8 and Tralornethrin W0 2015f038503 Cmpd. and Invertebrate Pest Control Invertebrate Pest No. No. A_ent Flubendiarnide Triazamate Flufenoxuron Triflumezopyrim Hexaflurnuron Triflumuron Hydramethylnon Baciiius lhuringiensis Bacillus thuringiensis Imidacloprld. . delta-endotoxm.

NPV (e.g., Gemstar) Table B2 Table B2 is cal to Table B l that each reference to compound 8 in the column , except headed “Cmpd. No.” is replaced by a reference to compound 14. For example, the first mixture in Table B2 is designated B2-l and is a mixture of compound 14 and the additional ebrate pest control agent abamectin.

Table B3 Table B3 is identical to Table B 1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 16. For example, the first mixture in Table B3 is designated B3-1 and is a mixture of compound 16 and the onal ebrate pest control agent abamectin.

Table B4 Table B4 is identical to Table B l that each reference to compound 8 in the column , except headed “Cmpd. No.” is replaced by a nce to compound 19. For example, the first mixture in Table B4 is designated B4-l and is a mixture of compound 19 and the additional invertebrate pest control agent abamectin.

Table B5 Table B5 is identical to Table B l that each reference to compound 8 in the column , except headed “Cmpd. No.” is replaced by a reference to compound 41. For example, the first mixture in Table B5 is ated B5-l and is a e of compound 41 and the additional invertebrate pest l agent abamectin.

Table B6 Table B6 is identical to Table B 1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a nce to compound 42. For example, the first mixture in Table B6 is designated B6-l and is a mixture of compound 42 and the additional invertebrate pest control agent abamectin.

W0 2015/‘038503 Table B7 Table B7 is identical to Table B 1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 51. For example, the first mixture in Table B7 is ated B7-l and is a mixture of compound 51 and the additional invertebrate pest control agent abamectin.

Table B8 Table B8 is cal to Table Bl, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 54. For e, the first mixture in Table B8 is designated B8-l and is a mixture of compound 54 and the additional invertebrate pest control agent abamectin.

Table B9 Table B9 is identical to Table B l that each nce to compound 8 in the column , except headed “Cmpd. No.” is replaced by a reference to nd 55. For example, the first mixture in Table B9 is designated B9-l and is a mixture of compound 55 and the onal ebrate pest control agent abamectin.

Table B 10 Table B10 is identical to Table B1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 76. For example, the first mixture in Table B10 is designated BlO-l and is a mixture of compound 76 and the additional invertebrate pest control agent abamectin.

The specific mixtures listed in Tables B1 to BlO typically combine a compound of Formula 1 with the other invertebrate pest agent in the ratios specified in Table A.

Listed below in Tables C1 to C10 are specific mixtures comprising a compound of Formula 1 und numbers (Cmpd. No.) refer to compounds in Index Tables A-N) and an additional invertebrate pest control agent. Tables C1 to C10 flirther list specific weight ratios typical of the mixtures of Tables C1 to C10. For example, the first weight ratio entry of the first line of Table Cl specifically discloses the mixture of Compound 8 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound I to 1 part abamectin.

Table Cl Mixture Cmpd. Invertebrate Pest and Typical Mixture Ratios (by weight). . . .

No. Control Aent 8 and Abamectm 100=11=100 8 and Acetamiprid won we won we won me W0 2015I038503 :10 1:100 8 and Bensultap 100:1 10:1 :10 1:100 8 and Beta-cyfluthrin 100:1 10:1 :10 1:100 8 and hrin 100:1 10:1 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 yrifos 100: 1 10: 1 :10 1:100 Clothianidin 100: 1 10:1 :10 1:100 Cyantraniliprole 100:1 10.1 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 and Deltamethrin 100:1 10:1 :10 1:100 8 and Dieldrin 100:1 10:1 :10 1:100 8 and Dinotefuran 100:1 10:1 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 Ethiprole 100: 1 10:1 :10 1:100 Fenothiocarb 100: 1 10: 1 :10 1:100 Fenoxycarb 100: 1 10: 1 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 Flufenoxuron 100: 1 10: 1 :10 1:100 and Hexaflumuron 100:1 10:1 :10 1:100 8 and Hydramethylnon 100:1 10:1 :10 1:100 :10 1:100 :10 1:100 Lambda- C1—39 : 5:1 2:1 1: 2 :10 1:100 cyhalothrin C1-40 Lufenuron 100: 1 10: 1 1: 10 1:100 W0 2015/‘038503 PCT/U82014/054671 :10 1:100 8 and yl 100:1 10:1 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 :10 1:100 8 Triflumuron 100:1 101I :10 1:100 Bacillus C1-73 1: l\.) :10 1:100 thuringiensis I Bacillus C1-74 thuringiensis :10 1:100 delta-endotoxin I W0 2015f038503 NPV(e.g., C1-75 8 and 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 Gemstar) Table C2 Table C2 is identical to Table C1, 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 ses the mixture of nd 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 nd 16. For example, the first weight ratio entry of the first line of Table C3 specifically discloses the mixture of nd 16 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C4 Table C4 is cal to Table C1, 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 C4 specifically discloses the mixture of nd 19 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 nd 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 41. For example, the first weight ratio entry of the first line of Table C5 specifically discloses the mixture of Compound 41 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 42. For example, the first weight ratio entry of the first line of Table C6 specifically discloses the mixture of Compound 42 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C7 Table C7 is identical to Table Cl, except that each nce to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 51. For example, the W0 2015f038503 first weight ratio entry of the first line of Table C7 specifically ses the mixture of Compound 51 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C8 Table C8 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 54. For example, the first weight ratio entry of the first line of Table C8 specifically discloses the mixture of Compound 54 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C9 Table C9 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 55. For example, the first weight ratio entry of the first line of Table C9 specifically discloses the mixture of Compound 55 with abamectin d in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C10 Table C10 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 76. For example, the first weight ratio entry of the first line of Table C10 specifically discloses the mixture of Compound 76 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Listed below in Tables D1 to D10 are ments of specific compositions comprising a compound of Formula 1 (compound numbers (Cmpd. No.) refer to compounds in Index Tables A-N) and an additional fungicide.

T—ableDl Cmpd Cmpd ide Fungicide 8 azole Difcnoconazole 8 il Cyproconazole 8 Isotianil Propiconazole 8 Pyroquilon Fenoxanil 8 Metominostrobin Ferimzone 8 Flutolanil Fthalide 8 Validamycin Kasugamycin 8 Furametpyr Picoxystrobin 8 uron OOOOOOOOOOOO Penthiopyrad W0 2015f038503 Cmpd Cmpd Fungicide Fungicide Simeconazole - Famoxadone Orysastrobin - Cymoxanil Trifloxystrobin - Proquinazid Isoprothiolane - Flusilazole Azoxystrobin - Mancozeb Tricyclazole - Copper hydroxide Hexaconazole - (a) (a) l-[4-[4-[5-(2,6—difluorophenyl)-4,5-dihydroisoxazolyl] thiazolyl]— l -piperidiny1][5—methyl oromethy1)-lH-pyrazol- l -yl] ne Table D2 Table D2 is identical to Table D1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 14. For e, the first mixture in Table D2 is designated D2-l and is a mixture of compound 14 and the additional ide probenazole.

Table D3 Table D3 is identical to Table D1, except that each reference to compound 8 in the column headed “Cmpd. No.” is ed by a reference to compound 16. For example, the first mixture in Table D3 is designated D3-l and is a mixture of compound 16 and the additional fungicide probenazole.

Table D4 Table D4 is identical to Table D1, 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 D4 is designated D4-l and is a e of compound 19 and the additional fiangicide probenazole.

Table D5 Table D5 is identical to Table D1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 41. For example, the first mixture in Table D5 is ated D5-l and is a mixture of compound 41 and the additional fungicide probenazole.

Table D6 Table D6 is cal to Table D1, except that each reference to compound 8 in the column headed “Cmpd. N0.” is replaced by a reference to compound 42. For example, the first mixture in Table D6 is designated D6-l and is a mixture of compound 42 and the additional fungicide probenazole.

W0 2015f038503 Table D7 Table D7 is identical to Table D1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 51. For example, the first mixture in Table D7 is designated D7-1 and is a e of compound 51 and the additional ide azole.

Table D8 Table D8 is identical to Table D1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 54. For example, the first mixture in Table D8 is designated D8-1 and is a mixture of compound 54 and the additional fiJngicide probenazole.

Table D9 Table D9 is identical to Table D1, except that each reference to compound 8 in the column headed “Cmpd. No.” is ed by a reference to compound 55. For example, the first mixture in Table D9 is designated D9-1 and is a mixture of compound 55 and the additional fiJngicide probenazole.

Table D10 Table D10 is identical to Table D1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 76. For example, the first mixture in Table D10 is designated D10-l and is a mixture of compound 76 and the additional fungicide probenazole.

Invertebrate pests are controlled in agronomic and nonagronomic applications by ng one or more compounds of this invention, typically in the form of a composition, in a biologically effective amount, to the environment of the pests, including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or ly on the pests to be lled.

Thus the present invention comprises a method for controlling an invertebrate pest in agronomic and/or nonagronomic applications, sing contacting the invertebrate pest or its environment with a biologically effective amount of one or more of the compounds of the ion, or with a composition comprising at least one such compound or a composition comprising at least one such compound and a ically effective amount of at least one additional biologically active compound or agent. Examples of le compositions comprising a compound of the invention and a biologically effective amount of at least one additional biologically active compound or agent include granular compositions wherein the additional active compound is present on the same granule as the compound of the invention or on granules separate from those of the nd of the invention.

W0 2015f038503 To achieve contact with a compound or composition of the invention to protect a field crop from ebrate pests, the compound or composition is typically applied to the seed of the crop before planting, to the foliage (e.g., leaves, stems, flowers, fiuits) of crop plants, or to the soil or other growth medium before or after the crop is planted.

One ment of a method of contact is by spraying. atively, a granular composition comprising a compound of the invention can be applied to the plant foliage or the soil. Compounds of this invention can also be ively delivered through plant uptake by contacting the plant with a composition comprising a compound of this invention applied as a soil drench of a liquid formulation, a granular ation to the soil, a nursery box treatment or a dip of transplants. Of note is a composition of the present invention in the form of a soil drench liquid ation. Also of note is a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of the present invention or with a ition comprising a biologically effective amount of a compound of the present invention. Of fiirther 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 ion are also effective by localized application to the locus of infestation. Other methods of t include application of a compound or a composition of the invention by direct and residual sprays, aerial sprays, gels, seed coatings, microencapsulations, systemic uptake, baits, ear tags, boluses, s, fumigants, aerosols, dusts and many others. One embodiment of a method of contact is a dimensionally stable fertilizer granule, stick or tablet comprising a compound or composition of the invention. The compounds of this invention can also be impregnated into materials for fabricating invertebrate control devices (e.g., insect netting).

Compounds of the invention are useful in treating all plants, plant parts and seeds.

Plant and seed varieties and cultivars can be ed by conventional propagation and breeding methods or by c engineering s. Genetically modified plants or seeds (transgenic plants or seeds) are those in which a heterologous gene gene) has been stably integrated into the plant's or seed's genome. A transgene that is defined 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 invention e those that are resistant against one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, cold temperature, soil salinity, etc.), or that contain other desirable characteristics. Plants and seeds can be genetically modified to exhibit traits of, for e, herbicide tolerance, -resistance, modified oil profiles or drought tolerance. Useful genetically modified plants and seeds containing single gene transformation events or ations 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: W0 2015/‘038503 PCT/USZOl4/054671 http://www2.oecd.org/biotech/byidentifier.aspx http://www.aphis.usda.go /gmoinfo.jrc.ec.europa.eu The following abbreviations are used in Table Z which follows: tol. is tolerance, res. is resistance, 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 MON8 Glyphosate tol. cp4 epsps (aroA:CP4) Alfalfa J163 MON-001634 Glyphosate tol. cp4 epsps (aroA:CP4) * 2317 (Event 465-2 High lauric acid oil te Canola* ;§?198 (Event 23) CGN2 High lauric acid oil te Canola* 61061 DP7 Glyphosate tol. gat4621 Canola* 73496 DP-Q73496-4 sate tol. gat4621 Canola* GT200 (RT200) MON2 Glyphosate tol. cp4 epsps (aroAzCP4); goxv247 Canola* GT73 (RT73) MON-000734 Glyphosate tol. cp4 epsps CP4); goxv247 Canola* HCN10 (Topas NA inate tol. bar Canola* 111963228 (T45) ACS-BN008-2 Glufosinate tol. pat (syn) Canola* HCN92 (Topas ACS-BN007-1 Glufosinate tol. bar Canola* 1126212188302 MON-883029 Glyphosate tol. cp4 epsps (aroAzCP4) Canola* MPS961 NA e breakdown phyA Canola* MPS962 NA Phytate breakdown phyA Canola* MPS963 NA Phytate breakdown phyA Canola* MPS964 NA Phytate breakdown phyA Canola* MPS965 NA e breakdown phyA * MSl (B91-4) ACS-BN004-7 Glufosinate tol. bar Canola* M88 ACS-BN005-8 Glufosinate tol. bar Canola* 5 ACS-BNQl 1-5 Oxynil tol. bxn Canola* PHY14 NA Glufosinate tol. bar Canola* PHY23 NA Glufosinate tol. bar Canola* PHY35 NA inate tol. bar Canola* PHY36 NA Glufosinate tol. bar Canola* RFl (B93-101) ACS-BN®®1-4 Glufosinate tol. bar Canola* RF2 (B94-2) ACS-BNQQZ-S Glufosinate tol. bar Canola* RF3 ACS-BN003-6 Glufosinate tol. bar Bean EMBRAPA 5.1 EMB—PVOSl-l Disease res. acl (sense and antisense) Brinj a1 EE—l Insect res. crylAc (Eggplant) W0 38503 Carnation 11(7442) FLO4 SL tol..; modified flower surB; dfr; hfl (f3'5'h) color Carnation 11363(1363A) FLO1 SL' tol.; modified flower surB; dfr; bp40 (B'S'h) color Carnation 1226A(11226) FLO8 SU tol.; modified flower surB; dfr; bp40 (13'5'h) color Carnation 123.2.2 (40619) FLO-406194 SL tol.; modified flower surB; dfr; hfl (B'S'h) color Carnation 123.2.38 (40644) FLO—406444 SL tol.; modified flower surB; dfr; hfl (f3'5'h) color Carnation 123.812 6896 SL tol.; modified flower surB; dfr; bp40 (B'S'h) color Carnation 123.8.8 ) FLO-406854 SL tol.; modified flower surB; dfr; bp40 (B'S'h) color Carnation 1351A (11351) FLO7 SL tol.; modified flower surB; dfr; bp40 (13'5'h) color Carnation 1400;1(11400) FLO-1 1400-2 SL tol.; modified flower surB; dfr; bp40 (B'S'h) color Carnation 15 FLO-000152 SL tol.; d flower surB; dfr; hfl (B'S‘h) color Carnation 16 FLO-000166 SL tol.; modified flower surB; dfr; hfl (B'S'h) color Carnation 4 FLO-$00049 SL tol.; modified flower surB; dfr; hfl (f3'5'h) color ion 66 FLO-000668 SL tol.; delayed senescence surB; acc Carnation 959A (11959) FLO3 SI: tol.; modified flower surB; dfr; bp40 (f3'5'h) color Carnation 988A(11988) FLO7 SU tol.; modified flower surB; dfr; bp40 (13'5'h) color Carnation 26407 IFD2 SI: tol.; modified flower surB; dfr; bp40 (B'S’h) color Carnation 25958 IFD3 SL tol.; modified flower surB; dfr; bp40 (f3'5'h) color Chicory RM3-3 NA Glufosinate tol. bar y RM3-4 NA Glufosinate tol. bar Chicory RM3—6 NA Glufosinate tol. bar Cotton 19-51a DD-01951A-7 ALS herbicide tol. S4-HrA Cotton -23 6 DAS5 Glufosinate tol.; insect res. pat (syn); crylF Cotton 300623 DAS-21023 -5 Glufosinate tol.; insect res. pat (syn); crylAc Cotton 31707 NA Oxynil tol.; insect res. bxn; crylAc Cotton 31803 NA Oxynil tol.; insect res. bxn; crylAc Cotton 31807 NA Oxynil tol.; insect res. bxn; crylAc Cotton 31808 NA Oxynil tol.; insect res. bxn; crylAc Cotton 42317 NA Oxynil tol.; insect res. bxn; crylAc Cotton BNLA—601 NA Insect res. crylAc Cotton BXN1021 1 BXN1021 1-9 Oxynil tol. bxn; crylAc Cotton 15 BXN10215-4 Oxynil tol. bxn; crylAc Cotton 22 BXN10222-2 Oxynil tol. bxn; crylAc Cotton BXN10224 BXN10224-4 Oxynil tol. bxn; crylAc Cotton COT102 SYN-1R1 02-7 Insect res. a) Cotton COT67B SYN-IR67B-1 Insect res. crylAb PCT/U82014/054671 Cotton COT202 Insect res. Vip3A Cotton Event 1 NA Insect res. cry 1Ac Cotton GMF CrylA GTL-GMF31 1- Insect res. cry 1 Ab-Ac Cotton GHBl 19 BCS-GI-IOOS-S Insect res. cry2Ae Cotton GHB614 002-5 Glyphosate tol. 2mepsps Cotton GK12 NA Insect res. crylAb-Ac Cotton LLCotton25 ACS-GH001-3 Glufosinate tol. bar Cotton MLS 9124 \IA Insect res. 01'le Cotton MON1076 MON2 Insect res. crylAc Cotton MON1445 VION—01445-2 Glyphosate tol. cp4 epsps (aroA:CP4) Cotton MON15985 MON-159854 Insect res. crylAc; cry2Ab2 Cotton MON1698 MON-893 83-1 Glyphosate tol. cp4 epsps (aroA:CP4) Cotton MON531 MON-005316 Insect res. crylAc Cotton MON757 MON-007574 Insect res. crylAc Cotton MON88913 MON-8891344 Glyphosate tol. cp4 epsps (aroAzCP4) Cotton que Chi 6 Bt VA Insect res. NA? Cotton SKG321 VA Insect res. crylA; CpTI Cotton T303-3 BCS-GH003-6 Insect res.; inate tol. crylAb; bar Cotton T304-40 BCS-GH004-7 Insect res.; inate tol. crylAb; bar Cotton CE43-67B Insect res. crylAb Cotton CE46-02A Insect res. crylAb Cotton CE44-69D Insect res. crylAb Cotton l l43-l4A Insect res. crylAb Cotton 1 143-5 1B Insect res. crylAb Cotton T342—l42 Insect res. crylAb Cotton PV—GHGT07 Glyphosate tol. cp4 epsps (aroAzCP4) (1445) Cotton EE-GH3 Glyphosate tol. mepsps Cotton EE-GHS Insect res. crylAb Cotton 0 1 MON3 Dicarnba & glufosinate tol. Modified dmo; bar Cotton OsCrl 1 llergy Modified Cry j Creeping ASR368 SMG-36800—2 sate tol. cp4 epsps (aroAzCP4) Bentgrass Eucalyptus 20—C Salt tol. codA Eucalyptus l2-5C Salt tol. codA Eucalyptus l2—5B Salt tol. codA Eucalyptus 107-1 Salt tol. codA Eucalyptus 1/9/2001 Salt tol. codA ptus 2/1/2001 Salt tol. codA Eucalyptus Cold tol. des9 Flax FP967 CDC-FL001-2 ALS herbicide tol. als Lentil RH44 Imidazolinone tol. als W0 20157038503 PCT/U82014/054671 Maize 3272 SYN—£32726 Modified alpha-amylase amy797E Maize 5307 3074 Insect res. ecry3 . 1 Ab Maize 59 122 DASr-SQI 239-7 Insect res.; glufosinate tol. cry34Abl; cry3 5Ab1; Maize 676 I’ll-(Hm676-7 Glufosinate tol.; pollination pat; dam control Maize 678 E’H($96739 Glufosinate tol.; pollination pat; dam Maize 680 I’ll-(kimfjgfi-Q Glufosinate tol.; pollination pat; dam control Maize 98140 DPvUQS 4 (3—6 Glyphosate toll; ALS gat462l; zrn-hra ide tol.

Maize Bt10 NA Insect res.; glufosinate tol. crylAb; pat Maize Bt176 (176) SYN-13371769 Insect res.; glufosinate tol. crylAb; bar Maize BVLA430101 NA Phytate breakdown phyA2 Maize CBH-35 1 751032140043 Insect res.; glufosinate tol. cry9C; bar Maize DAS40278—9 DAS40278—9 2,4-D tol. aad- 1 Maize DBT41 8 DKB-9 Insect res.; glufosinate tol. cry 1 Ac; pinII; bar Maize DLL25 (B16) DEB-SQVQG—‘j Glufosinate tol. bar Maize GA2 1 ivii'iN—ncnz 14: Glyphosate tol. mepsps Maize GG25 sate tol. mepsps Maize GJ l l Glyphosate tol. mepsps Maize Fl 1 l7 Glyphosate tol. mepsps Maize GAT-ZM 1 Glufosinate tol. pat Maize LY03 8 REN—0003 8-3 Increased lysine cordapA Maize MIR 1 62 SYN-IR 1 62-4 Insect res. Vip3Aa20 Maize MIR604 SYN—136046 Insect res. mcry3A Maize MON80 1 1311(er 81') l Insect res.; glyphosate tol. crylAb; cp4 epsps (MON80 100) (aroA:CP4); goxv247 Maize MON802 200—7 Insect res.; glyphosate tol. crylAb; cp4 epsps (aroA:CP4); goxv247 Maize MON809 PHAMON -809—2 Insect res.; glyphosate tol. crylAb; cp4 epsps (aroA:CP4); goxv247 Maize MON810 vlt'iNuooaic—(s Insect res.; glyphosate tol. crylAb; cp4 epsps (aroA:CP4); goxv247 Maize MON832 s Glyphosate tol. cp4 epsps (aroA:CP4); goxv247 Maize MON863 AIR-008635 Insect res. cry3Bb1 Maize MON87427 MON~87427~7 Glyphosate tol. cp4 epsps (aroA:CP4) Maize MON87460 \IlON-S7460~4- Drought tol. cspB Maize MON88017 MON-880 7-13 Insect res.; glyphosate tol. 1; cp4 epsps (aroA:CP4) Maize MON89034 034—3 Insect res. cry2Ab2; 105 Maize MS3 AC8 -ZMQOI --9 Glufosinate tol.; pollination bar; barnase control Maize MS6 ACS -Zlv’{005--4 Glufosinate tol.; pollination bar; barnase control Maize NK603 MON-(mom-é Glyphosate tol. cp4 epsps (aroA:CP4) Maize T14 ACS~ZMUGZJ Glufosinate tol. pat (Syn) W0 2015I038503 PCT/U82014/054671 T25 ACSZMOOffi-Z inate tol. pat (syn) TC 1 507 OAS—0 507v} Insect res.; glufosinate tol. cry 1 Fa2; pat TC6275 DASr-06275u8 Insect res.; glufosinate tol. mocry 1 F; bar VIP1034 Insect res.; glufosinate tol. vip3A; pat 43A47 131104391473 Insect res.; glufosinate tol. crylF; cry34Abl; cry35Abl; pat 40416 131104104168 Insect res.; glufosinate tol. crylF; cry34Abl; cry35Abl; pat Maize 32316 DP-032316~8 Insect res.; glufosinate tol. crylF; cry34Abl; cry35Abl; pat VIaize 4114 DPIHMI l4~3 Insect res.; inate tol. crylF; cry34Abl; cry35Abl; pat Vlelon Melon A NA Delayed ripening/senescence sam-k Vlelon Melon B NA d ripening/senescence sarn—k Papaya 55-1 551-8 Disease res. prsv cp Papaya 63-1 CUH-CP63 1-7 Disease res. prsv cp Papaya Huanong No. l \A Disease res. prsv rep Papaya X17-2 L'FL-Xl 7CP-6 Disease res. prsv cp Petunia a-CH8 \'A Modified product quality CHS suppression Plum C-5 ARS-PLMC5-6 Disease res. ppV Cp ** ZSRSOO \IA Glyphosate tol. cp4 epsps (aroA:CP4); goxv247 Canola** ZSR502 NA Glyphosate tol. cp4 epsps (aroA:CP4); goxv247 Canola** ZSR503 Glyphosate tol. cp4 epsps (aroA:CP4); goxv247 Poplar Bt poplar Insect res. crylAc; API Poplar Hybrid poplar Insect res. crylAc; API clone 741 Poplar trg3 00— 1 High ose AaXEG2 Poplar trg300—2 High cellulose AaXEG2 Potato 1210 amk cry3A Insect res.

Potato 2904/1 kgs /// >>> Insect res. cry3A Canola* * ZSR500 Glyphosate tol. cp4 epsps (aroA:CP4); goxv247 Canola* * ZSR502 /> Glyphosate tol. cp4 epsps CP4); goxv247 Potato ATBT04-27 /./././VIK8 Insect res. cry3A Potato ATBT04-3 0 VIK-896l3-2 Insect res. cry3A Potato ATBT04—3 l VIK-89l70-9 Insect res. cry3A Potato ATBT04—3 6 VIK1 Insect res. cry3A Potato ATBT04-6 NMK6 Insect res. cry3A Potato BT06 NMK3 Insect res. cry3A Potato ET 1 0 NMK5 Insect res. cry3A Potato ET 1 2 RMK8 Insect res. cry3A Potato ET 1 6 RMK-89l67-6 Insect res. cry3A Potato BTl 7 RMK9 Insect res. cry3A W0 38503 PCT/U82014/054671 1 52 Potato BT18 VMK7 Insect res. cry3A Potato BT23 NMK1 Insect res. cry3A Potato EH921 BPS9 Modified starch/carbohydrate gbss (antisense) Potato HLMT15-15 NA Insect & disease res. cry3A; pvy cp Potato HLMT15-3 I\A Insect & disease res. cry3A; pvy cp Potato HLMT15-46 I\A Insect & disease res. cry3A; pvy cp Potato RBMT15—101 9653-6 Insect & disease res. cry3A; pvy cp Potato RBMT21—129 684-1 Insect & disease res. cry3A; per orfl; per orf2 Potato RBMT21-152 \A Insect & e res. cry3A; per orfl; per orf2 Potato RBMT21-350 \MK6 Insect & e res. cry3A; per orfl; pIrV orf2 Potato RBMT22-082 \MK6 Insect & disease res.; cry3A; per orf1; per Glyphosate tol. orf2; cp4 epsps CP4) Potato RBMT22-186 \A Insect & disease res.; cry3A; pIrV orf1; pIrV Glyphosate tol. orf2; cp4 epsps (aroA:CP4) Potato RBMT22-238 \IA Insect & disease res.; cry3A; plrv orf1; pIrV Glyphosate tol. orf2; cp4 epsps (aroA:CP4) Potato RBMT22—262 VA Insect & disease res.; cry3A; plrv orfl; per Glyphosate tol. orf2; cp4 epsps (aroA:CP4) Potato SEMT15-02 NMK9 Insect & disease res. cry3A; pvy cp Potato SEMT15-07 NA Insect & disease res. cry3A; pvy cp Potato SEMTlS-IS I\MK4 Insect & disease res. cry3A; pvy cp Potato SPBT02—5 :\MK1 Insect res. cry3A Potato SPBT02—7 :\MK5 Insect res. cry3A Rice 7Crp#2427 Anti-allergy 7crp Rice 7Crp#10 \A Anti-allergy 7crp Rice GM u 63 \A Insect res. crylAb; crylAc Rice -l/TTSI-I \A Insect res. crylAb; crylAc Rice LLRICE06 ACS-OSOO I -4 Glufosinate tol. bar Rice LLRICE601 BCS-OSOO3 -7 Glufosinate tol. bar Rice LLRICE62 ACS-OSOO2-5 Glufosinate tol. bar Rice Tarom molaii + NA Insect res. crylAb (truncated) cry 1 Ab Rice GAT—OS2 Glufosinate tol. bar Rice GAT—OS3 Glufosinate tol. bar Rice PE-7 Insect res. CrylAc Rice 7Crp#10 NA Anti-allergy 7crp Rice KPD627-8 High tryptophan OASAlD Rice KPD722-4 High tryptophan OASAlD Rice KA317 High tryptophan OASAlD Rice HW5 High tryptophan OASA 1D W0 2015I038503 PCT/USZOl4/054671 Rice HWl High tryptophan OASA 1D Rice B1-18 Erect leaves semidwarf A OsBRIl Rice 22 Semidwarf OSGAZox 1 Rice AD77 Disease res. DEF Rice AD51 Disease res. DEF Rice AD48 Disease res. DEF Rice AD41 Disease res. DEF Rice 13pNasNaatAprtl Low iron tol. HVNASl; HVNAAT-A; APRT Rice l 3pAp111 Low iron tol. APRT Rice gHVNAS l - Low iron tol. HvNASl; HVNAAT-A; TB Rice gHVIDS3 - 1 Low iron tol. HvIDS3 Rice gHVNAAT 1 Low iron tol. HvNAAT-A; HvNAAT-B Rice gHvNASl-l Low iron tol. HvNASl Rice NIA-OSOO6-4 Disease res. WRKY45 Rice NIA—OSOOS-3 Disease res. WRKY45 Rice NIA-OSOO4-2 Disease res. WRKY45 Rice NIA-OSOO3-1 Disease res. WRKY45 Rice NIA-OSOOZ-9 e res. WRKY45 Rice NIA-OSOOl-8 Disease res. WRKY45 Rice OsCrll Anti-allergy Modified Cry j Rice 17053 Glyphosate tol. cp4 epsps (aroA:CP4) Rice 17314 Glyphosate tol. cp4 epsps (aroAzCP4) Rose WKSSZ / 1301 IFD4 d flower color SAT; bp40 (B'S'h) Rose WKS