AU2007240952A1 - Five-membered heterocyclic invertebrate pest control agents - Google Patents

Five-membered heterocyclic invertebrate pest control agents Download PDF

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Publication number
AU2007240952A1
AU2007240952A1 AU2007240952A AU2007240952A AU2007240952A1 AU 2007240952 A1 AU2007240952 A1 AU 2007240952A1 AU 2007240952 A AU2007240952 A AU 2007240952A AU 2007240952 A AU2007240952 A AU 2007240952A AU 2007240952 A1 AU2007240952 A1 AU 2007240952A1
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Australia
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compound
alkyl
nhch
halogen
composition
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AU2007240952A
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Dominic Ming-Tak Chan
Jeffrey Keith Long
Thomas Martin Stevenson
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/30—Oxygen or sulfur atoms
    • C07D233/32—One oxygen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/18—Oxygen atoms
    • C07D263/20—Oxygen atoms attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D291/00—Heterocyclic compounds containing rings having nitrogen, oxygen and sulfur atoms as the only ring hetero atoms
    • C07D291/02—Heterocyclic compounds containing rings having nitrogen, oxygen and sulfur atoms as the only ring hetero atoms not condensed with other rings
    • C07D291/04—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D419/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms
    • C07D419/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D419/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings

Description

WO 2007/123853 PCT/US2007/009181 1 TITLE FIVE-MEMBERED HETEROCYCLIC INVERTEBRATE PEST CONTROL AGENTS FIELD OF THE INVENTION This invention relates to certain five-membered heterocyclic derivatives, their 5 N-oxides, salts and compositions suitable for agronomic and nonagronomic uses, including those uses listed below, 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 10 efficiency. Damage by invertebrate pests to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, turf, wood products, and public and animal health is also important. Many products are commercially available for these 15 purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different modes of action. PCT Patent Publication WO 93/22298 discloses oxazolindine derivatives and pharmaceutically acceptable salts thereof as antihyperlipidemics. Japanese Patent Publication 03176476 discloses imidazolidinones as useful chiral 20 auxiliaries for producing penem or carbapenem antibiotics. U.S. Patent 4186129 discloses oxazolidinones useful as neuroleptics and phosphodiesterase inhibitors. SUMMARY OF THE INVENTION This invention is directed to compounds of Formula 1 including all geometric and 25 stereoisomers, N-oxides, and salts thereof, and compositions containing them and their use for controlling invertebrate pests:
R
1 G_~U Z N" 3,A 4 Ll At IkI nr "'A
(R
2 1 Q 30 wherein G is O or NR 3 ; U is C(=O), S(--O), C(=S), or S(0)2 Z is N or CR 2
;
WO 2007/123853 PCT/US2007/009181 2
A
1 is CR 4 or N;
A
2 is CR 5 or N;
A
3 is CR 6 or N;
A
4 is CR 7 or N; 5 Q is a 5- or 6-membered saturated or unsaturated heterocycle optionally substituted with one or more substituents independently selected from halogen, C 1
-C
6 alkyl,
CI-C
6 haloalkyl, C 3
-C
6 cycloalkyl, C 3
-C
6 halocycloalkyl, CI-C 6 alkoxy, Ci-C 6 haloalkoxy, C 1
-C
6 alkylthio, CI-C 6 haloalkylthio, C 1
-C
6 alkylsulfinyl, CI-C 6 haloalkylsulfinyl, CI-C 6 alkylsulfonyl, CI-C 6 haloalkylsulfonyl, CI-C 6 10 alkylamino, C 2
-C
8 dialkylamino, cyano, nitro, C(O)NR 8
R
9 , C(O)ORo 10 , phenyl and pyridinyl, each phenyl or pyridinyl optionally substituted with one or more substituents independently selected from R 11; or Q is C(O)NR 12
RI
3 , C(S)NR 1 2
R
13 , S(O) 2
NR
14
R
15 or R 1 6 ;
R
1 is cyano; or C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 2
-C
6 alkynyl, C 3
-C
6 cycloalkyl, C 4
-C
7 15 alkylcycloalkyl or C 4
-C
7 cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from R1 7 ; each R 2 is independently H, halogen, CI-C 6 alkyl, CI-C 6 haloalkyl, CI-C 6 alkoxy, C 1
-C
6 haloalkoxy, CI-C 6 alkylthio, CI-C 6 haloalkylthio, C 1
-C
6 alkylsulfinyl, C 1
-C
6 haloalkylsulfinyl, Cl-C 6 alkylsulfonyl, CI-C 6 haloalkylsulfonyl, CI-C 6 20 alkylamino, C 2
-C
8 dialkylamino, C 2
-C
4 alkoxycarbonyl, C 2
-C
4 alkylaminocarbonyl, C 3
-C
9 dialkylaminocarbonyl, cyano or nitro;
R
3 is H, cyano or -CHO; or CI-C 6 alkyl, C 2
-C
6 alkenyl, C 2
-C
6 alkynyl, C 3
-C
6 cycloalkyl, C 4
-C
7 alkylcycloalkyl, C 4
-C
7 cycloalkylalkyl, phenyl, Cl-C 6 alkylcarbonyl, C 1
-C
6 alkoxycarbonyl, C 2
-C
6 alkylaminocarbonyl or C3-C 9 25 dialkylaminocarbonyl, each optionally substituted with one or more substituents independently selected from RI8;
R
4 , R 5 , R 6 and R 7 are independently selected from H, halogen, C 1
-C
6 alkyl, CI-C 6 haloalkyl, C 3
-C
6 cycloalkyl, C 3
-C
6 halocycloalkyl, CI-C 6 alkoxy, CI-C 6 haloalkoxy, CI-C 6 alkylthio, CI-C 6 haloalkylthio, CI-C 6 alkylsulfinyl, CI-C 6 30 haloalkylsulfinyl, CI-C 6 alkylsulfonyl, C 1
-C
6 haloalkylsulfonyl, CI-C 6 alkylamino, C 2
-C
8 dialkylamino, cyano and nitro; or
R
6 and R 7 are taken together to form a fused aromatic ring, the fused aromatic ring containing as ring members in addition to the A 3 and A 4 bridgehead atoms, 3 atoms selected from 1 to 2 carbon atoms, 0 to 2 nitrogen atoms, 0 to 1 oxygen 35 atom and 0 to I sulfur atom, or 4 atoms selected from 2 to 4 carbon atoms and 0 to 2 nitrogen atoms; WO 2007/123853 PCT/US2007/009181 3 each R 8 , R 12 and R 14 is independently H, CI-C 6 alkyl, CI-C 6 haloalkyl, C 2
-C
6 alkenyl,
C
2
-C
6 alkynyl, C 3
-C
6 cycloalkyl, C 4
-C
7 alkylcycloalkyl, C 4
-C
7 cycloalkylalkyl,
C
2
-C
7 alkylcarbonyl, C 2
-C
6 alkoxyalkyl or C 2
-C
7 alkoxycarbonyl; each R 9 , R 10 , R 13 and R 15 is independently H; or C 1
-C
6 alkyl, C 2
-C
6 alkenyl, C 2
-C
6 5 alkynyl, C 3
-C
6 cycloalkyl, C 4
-C
7 alkylcycloalkyl or C 4
-C
7 cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from RI9; each R 11 , R 23 and R 24 is independently halogen, CI-C 6 alkyl, C 1
-C
6 haloalkyl, C 1
-C
6 alkoxy, CI-C 6 haloalkoxy, C 1
-C
6 alkylthio, CI-C 6 haloalkylthio, CI-C 6 10 alkylsulfinyl, C 1
-C
6 haloalkylsulfinyl, CI-C 6 alkylsulfonyl, CI-C 6 haloalkylsulfonyl, CI-C 6 alkylaminosulfonyl, CI-C 8 alkylamino, C 2
-C
8 dialkylamino, C 2
-C
4 alkoxycarbonyl, cyano or nitro;
R
16 is halogen, CI-C 6 alkyl, CI-C 6 haloalkyl, C 3
-C
6 cycloalkyl, C 3
-C
6 halocycloalkyl, CI-C 6 alkoxy, C 1
-C
6 haloalkoxy, Ct-C 6 alkylthio, C 1
-C
6 15 haloalkylthio, C 1
-C
6 alkylsulfinyl, C 1
-C
6 haloalkylsulfinyl, C 1
-C
6 alkylsulfonyl,
CI-C
6 haloalkylsulfonyl, C 1
-C
6 alkylamino, C 2
-C
8 dialkylamino, cyano or nitro; each R 17 and R 18 is independently halogen, CI-C 6 alkyl, CI-C 6 alkoxy, CI-C 6 alkylthio,
CI-C
6 alkylsulfinyl, CI-C 6 alkylsulfonyl, cyano or nitro; each R 19 is independently halogen, Cl-C 6 alkyl, CI-C 6 alkoxy, CI-C 6 alkylthio, CI-C 6 20 alkylsulfinyl, CI-C 6 alkylsulfonyl, C 2
-C
6 alkylcarbonyl, C 2
-C
6 alkoxycarbonyl, trimethylsilyl, cyano, nitro or QI; each QI is independently a phenyl or a 5- or 6-membered saturated or unsaturated heterocycle, each optionally substituted with one or more substituents independently selected from halogen, C 1
-C
6 alkyl, C 1
-C
6 haloalkyl, C 3
-C
6 25 cycloalkyl, C 3
-C
6 halocycloalkyl, CI-C 6 alkoxy, C 1
-C
6 haloalkoxy, CI-C 6 alkylthio, C 1
-C
6 haloalkylthio, CI-C 6 alkylsulfinyl, CI-C 6 haloalkylsulfinyl,
CI-C
6 alkylsulfonyl, CI-C 6 haloalkylsulfonyl, CI-C 6 alkylamino, C 2
-C
8 dialkylamino, cyano, nitro, C(O)NR 20
R
2 1 , C(O)OR 22 , phenyl or pyridinyl, each phenyl or pyridinyl optionally substituted with one or more substituents 30 independently selected from R 23 ; each R 2 0 is independently H, CI-C 6 alkyl, CI-C 6 haloalkyl, C 2
-C
6 alkenyl, C 2
-C
6 alkynyl,
C
3
-C
6 cycloalkyl, C 4
-C
7 alkylcycloalkyl, C 4
-C
7 cycloalkylalkyl, C 2
-C
7 alkylcarbonyl or C 2
-C
7 alkoxycarbonyl; each R 2 1 and R 22 is independently H; or CI-C 6 alkyl, CI-C 6 haloalkyl, C 2
-C
6 alkenyl, 35 C 2
-C
6 alkynyl, C 3
-C
6 cycloalkyl, C 4
-C
7 alkylcycloalkyl, C 4
-C
7 cycloalkylalkyl, phenyl or pyridinyl; each phenyl or pyridinyl optionally substituted with one or more substituents independently selected from R 24 ; and n is 1, 2, 3 or 4; and WO 2007/123853 PCT/US2007/009181 4 provided that R 16 is other than methoxy. This invention also provides a composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula 1, an N-oxide or a salt thereof, and at least one additional component selected from the group consisting of a 5 surfactant, a solid diluent and a liquid diluent, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent. This invention further provides a spray composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula 1, an N-oxide or a salt 10 thereof, or the composition described above, and a propellant. This invention also provides a bait composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula 1, an N-oxide or a salt thereof, or the composition described above, one or more food materials, optionally an attractant, and optionally a humectant. 15 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 20 near a locus of potential or known activity for the invertebrate pest. This invention also provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula 1, an N-oxide or a salt thereof, (e.g., as a composition described herein). This invention also relates to such method wherein the invertebrate pest or its 25 environment is contacted with a composition comprising a biologically effective amount of a compound of Formula 1, an N-oxide or a salt thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent. 30 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 N-oxide or a salt thereof, (e.g., as a composition 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 35 animal a parasiticidally effective amount of a compound of Formula 1, an N-oxide or a salt thereof, (e.g., as a composition described herein).
WO 2007/123853 PCT/US2007/009181 5 DETAILS OF THE INVENTION As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, a mixture, process, method, article, or 5 apparatus 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, method, article, or apparatus. 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 10 is false (or not present) and B is true (or present), and both A and B are true (or present). Also, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore "a" or "an" should be read to include one or at least one, and the singular word form of the element or component also includes 15 the plural unless the number is obviously meant to be singular. As referred to in this disclosure, the term "invertebrate pest" includes arthropods, gastropods and nematodes of economic importance as pests. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans. The term "gastropod" includes snails, slugs and other Stylommatophora. The term "helminths" 20 includes worms in the phylum of Nemathelminth, Platyhelminth and Acanthocephala such as: round worms, heartworms, and phytophagous nematodes (Nematoda), flukes (Trematoda), tape worms (Cestoda) and throny-headed worms. In the context of this disclosure "invertebrate pest control" means inhibition of invertebrate pest development (including mortality, feeding reduction, and/or mating 25 disruption), and related expressions are defined analogously. The term "agronomic" refers to the production of field crops such as for food and fiber and includes the growth of corn, soybeans and other legumes, rice, cereal (e.g., wheat, oats, barley, rye, rice, maize), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers and cucurbits), potatoes, 30 sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruit (berries, cherries) and other specialty crops (e.g., canola, sunflower, olives). The term "nonagronomic" refers to other horticultural crops (e.g., greenhouse, nursery or ornamental plants not grown in a field), residential and commercial structures in urban and industrial settings, turf (e.g., sod farm, pasture, golf course, residential lawn, recreational sports field, 35 etc.), wood products, stored product, agro-forestry and vegetation management, public health (human) and animal health (e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife) applications.
WO 2007/123853 PCT/US2007/009181 6 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 ethenyl, 1-propenyl, 2-propenyl, and the different 5 butenyl, pentenyl and hexenyl isomers. "Alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl" can also include moieties comprising multiple triple bonds such as 2,5-hexadiynyl. 10 "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. "Alkylsulfinyl" includes both enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" include CH 3 S(O)-, CH 3
CH
2 S(O)-, 15 CH 3
CH
2
CH
2 S(O)-, (CH 3
)
2 CHS(O)- and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH 3 S(0) 2 -, CH 3
CH
2
S(O)
2 -,
CH
3
CH
2
CH
2
S(O)
2 -, (CH 3
)
2 CHS(0) 2 -, and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. "Alkylamino", "dialkylamino", and the like, are defined analogously to the above examples. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, 20 cyclopentyl and cyclohexyl. The term "alkylcycloalkyl" denotes alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, i-propylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. The term "cycloalkylalkyl" denotes cycloalkyl substitution on an alkyl moiety. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain 25 or branched alkyl groups. The term "halogen", either alone or in compound words such as "haloalkyl", or when used in descriptions such as "alkyl substituted with halogen" includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", or when used in descriptions such as "alkyl substituted with halogen" said alkyl may be partially or 30 fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" or "alkyl substituted with halogen" include F 3 C-, CICH 2 -, CF 3
CH
2 - and
CF
3
CCI
2 -. The terms "halocycloalkyl", "haloalkoxy", "haloalkylthio", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkoxy" include CF30-,
CCI
3
CH
2 0-, HCF 2
CH
2
CH
2 0- and CF 3
CH
2 0-. Examples of "haloalkylthio" include 35 CCI 3 S-, CF 3 S-, CCI 3
CH
2 S- and CICH 2
CH
2
CH
2 S-. Examples of "haloalkylsulfinyl" include
CF
3 S(O)-, CC1 3 S(O)-, CF 3
CH
2 S(O)- and CF 3
CF
2 S(O)-. Examples of "haloalkylsulfonyl" include CF 3
S(O)
2 -, CCI 3
S(O)
2 -, CF 3
CH
2
S(O)
2 - and CF 3
CF
2
S(O)
2
-.
WO 2007/123853 PCT/US2007/009181 7 "Alkylcarbonyl" denotes a straight-chain or branched alkyl moieties bonded to a C(=O) moiety. Examples of "alkylcarbonyl" include CH 3 C(=O)-, CH 3
CH
2
CH
2 C(--O)- and
(CH
3
)
2 CHC(--O)-. Examples of "alkoxycarbonyl" include CH 3 OC(--O)-, CH 3
CH
2 OC(=O),
CH
3
CH
2
CH
2 OC(-O)-, (CH 3
)
2 CHOC(-O)- and the different butoxy- or pentoxycarbonyl 5 isomers. The total number of carbon atoms in a substituent group is indicated by the "Ci-C " prefix where i and j are integers from 1 to 9. For example, C 1
-C
4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl; C 2 alkoxyalkyl designates CH 3
OCH
2 ; C 3 alkoxyalkyl designates, for example, CH 3
CH(OCH
3 ), CH 3
OCH
2
CH
2 or CH 3
CH
2
OCH
2 ; and C 4 10 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3
CH
2
CH
2
OCH
2 and
CH
3
CH
2
OCH
2
CH
2 . When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are 15 independently selected from the group of defined substituents, e.g., (R 2 )n, n is 1, 2, 3 or 4. When a group contains a substituent which can be hydrogen, for example R 2 , then when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. The term "heterocycle", "heterocyclic ring" or "heterocyclic ring system" denotes 20 rings or ring systems in which at least one ring atom is not carbon, e.g., nitrogen, oxygen or sulfur. Typically a heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. The heterocyclic ring can be attached through any available carbon or nitrogen by replacement of hydrogen on said carbon or nitrogen. The heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a 25 fully unsaturated heterocyclic ring satifies the Hiickel rule, then said ring is also called a "heteroaromatic ring" or "aromatic heterocyclic ring". The term "aromatic ring"' or "aromatic ring system" denotes fully unsaturated carbocycles and heterocycles in which at least one ring of the polycyclic ring system is aromatic (where aromatic indicates that the Hickel rule is satisfied for the ring system). 30 The term "fused bicyclic ring system" denotes a ring system containing two fused rings in which either ring can be saturated, partially unsaturated, or fully unsaturated. The term "fused heterobicyclic ring system" denotes a ring system containing two fused rings in which at least one ring atom is not carbon and which can be aromatic or nonaromatic, as defined above. 35 The term "optionally substituted" in connection with the heterocyclic rings refers to groups which are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the biological activity possessed by the unsubstituted analog. As used herein, the following definitions shall apply unless otherwise indicated. The term "optionally WO 2007/123853 PCT/US2007/009181 8 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. 5 When Q or QI is a 5- or 6-membered nitrogen-containing heterocycle, it may be attached to the remainder of Formula 1 through any available carbon or nitrogen ring atom, unless otherwise indicated. One skilled in the art recognizes that "pyridinyl" and "pyridyl" are equivalent alternative names for an organic radical formed by removing a hydrogen atom from a pyridine ring to form an attachment point; accordingly "pyridinyl" and "pyridyl" are 10 used herein as synonyms. As noted above, Q1 can be (among others) phenyl optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of Invention. An example of phenyl optionally substituted with from one or more substituents is the ring illustrated as U-1 in Exhibit 1, wherein Rv is any substituent as defined in the 15 Summary of the Invention for Q 1 and r is an integer from 0 to 5. As noted above, Q or Q1 can be (among others) 5- or 6-membered saturated or unsaturated heterocycles optionally substituted with one or more substituents selected from the group of substituents as defined in the Summary of Invention. Examples of 5- or 6-membered unsaturated aromatic heterocycles optionally substituted with from one or more 20 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 Q or Q1, and r is an integer from 0 to 4. Note that some U groups can only be substituted with less than 4 Rv groups (e.g., U 2 through U-5, U-7 through U-48, and U-52 through U-61). Although Rv groups are shown in the structures U-1 through U-61, it is noted that they 25 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)r can be attached to any available carbon atom or nitrogen atom of the U group. 30 Exhibit 1 (RV)r 3 (RV)r 4 (R)r 3 (RV)r 4 (RV)r , 4 5 4 2 5 U U5 -5 2 S 0 2 U-1 U-2 U-3 U-4 U-5 WO 2007/123853 PCT/US2007/009181 9 (RV)r (RV)r (RV), N
(R
)r ( R v)r N 4 2 5 5 0 U-6 U-7 U-8 U-9 U-10 4 (RV)r (RV)r (RV)r 4 (RV)r (RV)r U-I U-12 U-13 U-14 U-15 (Rv ) r (R )r (R)r 4 (RV)r 3 (RV)r N 4N-4 NN N- N 5 5 N U-16 U-17 U-18 U-19 U-20 4 (RV)r 4 (R")r 3 (RV)r 4 (RV)r (RV)r O-N N-S S S-N U-21 U-22 U-23 U-24 U-25 4 (RV)r 3 (RV)r 4 (R)r (N N
(S
N N N N5 N N () r
(RN)
r U-26 U-27 U-28 U-29 U-30 (RV)r (R")r N(R )r N
(
R)r N (R )r N-NN N N N5 N-N N-N~ NR~ U-3 1 U-32 U-33 U-34 U-35 (R v)r (Rv)r (Rv)r (Rv)r (RV)r U-36 U-37 U-38 U-39 U-40 N SN (R") (R)r N (i N CN (RY)r (R)r (N R)r NN N U-41 U-42 U-43 U-44 U-45 WO 2007/123853 PCT/US2007/009181 10 S4 (RV) r 5 (Rv)r (Rv)r (RV)r (R )r 34/ N 6 N N NN N-N N-N N=N 2 U-46 U-47 U-48 U-49 U-50 6 (RV)r (RV)r (RV)r (RV)r 6 (RV)r -~N 2 N 2 3 U-51 U-52 U-53 U-54 U-55
S(R
v )r N(R) N (R v )r N (Rv)r (RV)r NN and * N NN 6 N 4 N U-56 U-57 U-58 U-59 U-60 4 (RV)r N N N6 U-61 Note that when Q or Q1 is a 5- or 6-membered saturated or unsaturated non-aromatic heterocycle optionally substituted with one or more substituents selected from the group of substituents as defined in the Summary of Invention for Q or Q1, one or two carbon ring members of the heterocycle can optionally be in the oxidized form of a carbonyl moiety. 5 Examples of 5- or 6-membered saturated or non-aromatic unsaturated heterocycles include the rings Q-1 through Q-35 as illustrated in Exhibit 2, wherein Rv is any substituent as defined in the Summary of the Invention for Q 1 . Note that when the attachment point between (RV)r and the Q or Q 1 group is illustrated as floating, (RV)r can be attached to any available carbon atom or nitrogen atom of the U group. Note that when the attachment point 10 on the Q or QI group is illustrated as floating, the Q or QI group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the Q or QI group by replacement of a hydrogen atom. The optional substituents can be attached to any available carbon or nitrogen by replacing a hydrogen atom. Note that when Q or Q 1 comprises a ring selected from Q-28 through Q-35, Q 2 is 15 selected from O, S or N. Note that when Q 2 is N, the nitrogen atom can complete its valence by substitution with either H or the substituents as defined in the Summary of Invention for Q orQ 1
.
WO 2007/123853 PCT/US2007/009181 11 Exhibit 2 .(R)r (RV)r (Rv) r )r )r Q-1 Q-2 Q-3 Q-4 Q-5 0 R )r N(R)r (R ()r (NRv)r i7 (R')r K 7_ N 0,N O . ... Q-6 Q-7 Q-8 Q-9 Q-1O (Rv)r
(R
v )r 7 R(R) ) S (Rv) oo r ' o , )r , 2R )r , > r%, Q-11 Q-12 Q-13 Q-14 Q-15 (RV)r -7. (Rv)r (R) r(RV) (R)r 0>)2< NI r $7) Q-16 Q-17 Q-18 Q-19 Q-20 (RV)r (RV)r (R v )r (RV)r
N
(R
v )r 2 -' 20 Q-21 Q-22 Q-23 Q-24 Q-25 (Rv), (Rv)r (R )rO (Rv)r 0
O
[ v o2 , , O2. 0 N Dk. ' K-Q Q-26 Q-27 Q-28 Q-29 Q-30 (Rv)r )O 0 e)r 0 (R)r0 O (RV)r _ Q2 Q2 , Q2 and Q2 Q-31 Q-32 Q-33 Q-34 Q-35 Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may WO 2007/123853 PCT/US2007/009181 12 exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, the present invention comprises compounds selected from Formula 1, N-oxides and agriculturally 5 suitable salts thereof. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers or as an optically active form. One skilled in the art will appreciate that not all nitrogen-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 10 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 heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, 15 and dioxiranes such as dimethyldioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and 20 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. 25 The salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. The salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine or triethylamine) or inorganic bases (e.g., 30 hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic moiety such as when QI is phenyl substituted with C(O)OR 22 and R 22 is H. Accordingly, the present invention comprises compounds selected from Formula 1, N-oxides and salts thereof. 35 Embodiments of the present invention as described in the Summary of the Invention include: Embodiment 1. A compound of Formula 1 wherein G is O. Embodiment 2. A compound of Formula 1 wherein G is NR 3
.
WO 2007/123853 PCT/US2007/009181 13 Embodiment 3. A compound of Formula 1 wherein R 3 is H or cyano; or C 1
-C
4 alkyl optionally substituted with one or more substituents selected from halogen. Embodiment 4. A compound of Embodiment 3 wherein R 3 is CH 3 , CH 2
CH
3 or
CH
2
CF
3 . 5 Embodiment 5. A compound of Formula 1 wherein U is C(=O). Embodiment 6. A compound of Formula 1 wherein Z is CR 2 . Embodiment 7. A compound of Formula 1 wherein each R 2 is independently selected from H, halogen or C 1
-C
2 haloalkyl. Embodiment 8. A compound of Embodiment 7 wherein each R 2 is independently H, 10 halogen or CF 3 . Embodiment 9. A compound of Formula 1 wherein A l is CR 4 . Embodiment 10. A compound of Formula 1 wherein A 2 is CR 5 . Embodiment 11. A compound of Formula 1 wherein A 3 is CR 6 . Embodiment 12. A compound of Formula I wherein A 4 is CR 7 . 15 Embodiment 13. A compound of Formula 1 wherein R 4 and R 5 are independently selected from H, halogen, C 1
-C
3 alkyl, Cl-C 3 haloalkyl, cyano and nitro. Embodiment 14. A compound for Formula 1 wherein R 6 and R 7 are independently selected from H, halogen, C 1
-C
3 alkyl, C 1
-C
3 haloalkyl, cyano and nitro; or R 6 and R 7 are taken together to form a fused aromatic ring, the fused aromatic ring 20 containing as ring members in addition to the A 3 and A 4 bridgehead atoms, 4 atoms selected from 3 to 4 carbon atoms and 0 to 1 nitrogen atom. Embodiment 15. A compound of Embodiment 14 wherein R 6 and R 7 are independently selected from H, halogen, C 1
-C
3 alkyl, CI-C 3 haloalkyl, cyano and nitro. 25 Embodiment 16. A compound of Embodiment 14 wherein R 6 and R 7 are taken together to form a fused aromatic ring, the fused aromatic ring containing as ring members in addition to the A 3 and A 4 bridgehead atoms, 4 atoms selected from 3 to 4 carbon atoms and 0 to 1 nitrogen atom. Embodiment 17. A compound of Embodiment 14 or 16 wherein the fused aromatic ring 30 contains 4 carbon atoms as ring members in addition to the A 3 and A 4 bridgehead atoms. Embodiment 18. A compound of Formula 1 wherein Q is a pyridinyl ring, a pyrimidinyl ring, a triazinyl ring, a pyrazolyl ring, a triazolyl ring, an imidazolyl ring, an oxazolyl ring, an isoxazolyl ring, a thiazolyl ring or an isothiazolyl ring, 35 each ring optionally substituted with one or more substituents independently selected from halogen, CI-C 6 alkyl, CI-C 6 haloalkyl, C 3
-C
6 cycloalkyl, C 3
-C
6 halocycloalkyl, C 1
-C
6 alkoxy, C 1
-C
6 haloalkoxy, CI-C 6 alkylthio, Cl-C 6 haloalkylthio, C 1
-C
6 alkylsulfinyl, C 1
-C
6 haloalkylsulfinyl, CI-C 6 alkylsulfonyl, WO 2007/123853 PCT/US2007/009181 14
CI-C
6 haloalkylsulfonyl, Cl-C 6 alkylamino, C 2
-C
8 dialkylamino, cyano, nitro,
C(O)NR
8
R
9 , C(O)ORo 10 , phenyl and pyridinyl, each phenyl and pyridinyl optionally substituted with one or more substituents independently selected from
R
11 ; or Q is C(=O)NRI 2
R
13 , S(0) 2
NRI
4
R
15 or R 16 . 5 Embodiment 19. A compound of Embodiment 18 wherein Q is a pyridinyl ring, a pyrimidinyl ring, a triazinyl ring, a pyrazolyl ring, a triazolyl ring, an imidazolyl ring, an oxazolyl ring, an isoxazolyl ring, a thiazolyl ring or an isothiazolyl ring, each ring optionally substituted with one or more substituents independently selected from halogen, CI-C 6 alkyl, CI-C 6 haloalkyl, C 3
-C
6 cycloalkyl, C 3
-C
6 10 halocycloalkyl, C 1
-C
6 alkoxy, C 1
-C
6 haloalkoxy, CI-C 6 alkylthio, CI-C 6 haloalkylthio, CI-C 6 alkylsulfinyl, CI-C 6 haloalkylsulfinyl, C 1 -C6.alkylsulfonyl, Cl-C 6 haloalkylsulfonyl, CI-C 6 alkylamino, C 2
-C
8 dialkylamino, cyano, nitro,
C(O)NR
8
R
9 , C(O)ORo 0 , phenyl and pyridinyl, each phenyl and pyridinyl optionally substituted with one or more substituents independently selected from 15 R 11 . Embodiment 20. A compound of Embodiment 19 wherein Q is a pyrazolyl ring, a triazolyl ring or an imidazolyl ring, each ring attached through nitrogen and optionally substituted with one or more substituents independently selected from halogen, CI-C 4 alkyl, CI-C 4 haloalkyl, C 3
-C
6 cycloalkyl, C 3
-C
6 halocycloalkyl, 20 C 1
-C
4 alkoxy, C 1
-C
4 haloalkoxy, C 1
-C
4 alkylamino, C 2
-C
4 dialkylamino, cyano, nitro, C(O)NR8R 9 , C(O)OR 1 IO, phenyl and pyridinyl, each phenyl and pyridinyl optionally substituted with one or more substituents independently selected from .Rll. Embodiment 21. A compound of Embodiment 20 wherein Q is a pyrazolyl ring, a 25 triazolyl ring or an imidazolyl ring, each ring attached through nitrogen and optionally substituted with one or more substituents independently selected from halogen, CI-C 4 alkyl, CI-C 4 haloalkyl, CI-C 4 alkoxy, CI-C 4 haloalkoxy, cyano, nitro, C(O)NR 8
R
9 and C(O)ORIO. Embodiment 22. A compound of Embodiment 21 wherein Q is a pyrazolyl ring, a 30 triazolyl ring or an imidazolyl ring, each ring attached through nitrogen and optionally substituted with one or more substituents independently selected from halogen, Cl-C 3 alkyl and C 1
-C
3 haloalkyl. Embodiment 23. A compound of Embodiment 22 wherein Q is a triazolyl ring or an imidazolyl ring, each ring attached through nitrogen and optionally substituted 35 with one or more substituents independently selected from halogen, CI-C 3 alkyl and C 1
-C
3 haloalkyl. Embodiment 24. A compound of Formula 1 wherein each R 8 is independently H, Ct-C 6 alkyl, C 2
-C
7 alkylcarbonyl or C 2
-C
7 alkoxycarbonyl.
WO 2007/123853 PCT/US2007/009181 15 Embodiment 25. A compound of Embodiment 24 wherein each R 8 is H. Embodiment 26. A compound of Formula 1 wherein each R 9 is independently H; or
C
1
-C
4 alkyl, C 2
-C
4 alkenyl, C 2
-C
4 alkynyl, C 3
-C
4 cycloalkyl, C 4
-C
7 alkylcycloalkyl or C 4
-C
7 cycloalkylalkyl, each optionally substituted with one or 5 more substituents selected from R 19 . Embodiment 27. A compound of Embodiment 26 wherein each R 9 is independently
CI-C
4 alkyl optionally substituted with one or more substituents selected from
RI
9 . Embodiment 28. A compound of Embodiment 27 wherein each R 9 is independently 10 C 1
-C
4 alkyl optionally substituted with one QI and optionally substituted with one or more substituents selected from halogen, CI-C 4 alkyl, C 1
-C
4 alkoxy, C 1 C 4 alkylthio, CI-C 4 alkylsulfonyl and cyano. Embodiment 29. A compound of Formula 1 wherein each R 10 is independently H; or
CI-C
4 alkyl, C 2
-C
4 alkenyl, C 2
-C
4 alkynyl, C 3
-C
4 cycloalkyl, C 4
-C
7 15 alkylcycloalkyl or C 4
-C
7 cycloalkylalkyl, each optionally substituted with one or more substituents selected from R 1 9 Embodiment 30. A compound of Embodiment 29 wherein each RI 0 is independently
C
1
-C
4 alkyl optionally substituted with one or more substituents selected from R19. 20 Embodiment 31. A compound of Embodiment 30 wherein each RI 0 is independently
C
1
-C
4 alkyl optionally substituted with one QI and optionally substituted with one or more substituents selected from halogen, CI-C 4 alkyl, CI-C 4 alkoxy,
CI-C
4 alkylthio, CI-C 4 alkylsulfonyl and cyano. Embodiment 32. A compound of Formula 1 wherein each R 1 9 is independently selected 25 - from halogen, CI-C 4 alkyl, CI-C 4 alkoxy, CI-C 4 alkylthio, C 1
-C
4 alkylsulfonyl, cyano, nitro and Q 1l Embodiment 33. A compound of Embodiment 32 wherein each R 19 is independently selected from halogen, CI-C 4 alkyl, C 1
-C
4 alkoxy, C 1
-C
4 alkylthio, C 1
-C
4 alkylsulfonyl and cyano. 30 Embodiment 34. A compound of Embodiment 18 wherein Q is C(=O)NRI 2
RI
3 . Embodiment 35. A compound of Formula 1 wherein R 12 is H, CI-C 6 alkyl, C 2
-C
7 alkylcarbonyl or C 2
-C
7 alkoxycarbonyl. Embodiment 36. A compound of Embodiment 35 wherein Rt 2 is H. Embodiment 37. A compound of Formula 1 wherein R 13 is H; or CI-C 4 alkyl, C 2
-C
4 35 alkenyl, C 2
-C
4 alkynyl, C 3
-C
4 cycloalkyl, C 4
-C
7 alkylcycloalkyl or C4-C 7 cycloalkylalkyl, each optionally substituted with one or more substituents selected from R 1 9
.
WO 2007/123853 PCT/US2007/009181 16 Embodiment 38. A compound of Embodiment 37 wherein R 13 is H; or Cl-C 4 alkyl optionally substituted with one or more substituents selected from R 1 9 . Embodiment 39. A compound of Embodiment 38 wherein R 13 is H; or Cl-C 4 alkyl optionally substituted with one Q 1 and optionally substituted with one or more 5 substituents selected from halogen, C 1
-C
4 alkyl, Cl-C 4 alkoxy, Cl-C 4 alkylthio,
CI-C
4 alkylsulfinyl, Ci-C 4 alkylsulfonyl, C 2
-C
4 alkylcarbonyl, C 2
-C
4 alkoxycarbonyl and cyano. Embodiment 40. A compound of Embodiment 39 wherein R 13 is H; or C 1
-C
4 alkyl optionally substituted with one Q1 and optionally substituted with one or more 10 fluorine. Embodiment 41. A compound of Formula 1 wherein each R 19 is independently selected from halogen, CI-C 4 alkyl, C 1
-C
4 alkoxy, CI-C 4 alkylthio, C 1
-C
4 alkylsulfinyl,
C
1
-C
4 alkylsulfonyl, C 2
-C
4 alkylcarbonyl, C 2
-C
4 alkoxycarbonyl, cyano, nitro and Q1. 15 Embodiment 42. A compound of Embodiment 41 wherein each R 19 is independently selected from halogen and Q1. Embodiment 43. A compound of Formula 1.wherein each QI is independently selected from phenyl, pyridinyl and thiazolyl, each optionally substituted with one or more substituents independently selected from halogen, CI-C 3 alkyl, CI-C 3 20 haloalkyl, cyano, phenyl and pyridinyl. Embodiment 44. A compound of Embodiment 43 wherein Q 1 is phenyl, pyridinyl or thiazolyl. Embodiment 45. A compound of Embodiment 18 wherein Q is R 16 . Embodiment 46. A compound of Embodiment 18 wherein Q is S(O) 2
NR
1 4
R
15 . 25 Embodiment 47. A compound of Formula 1 wherein R 14 is H, CI-C 6 alkyl, C 2
-C
7 alkylcarbonyl or C 2
-C
7 alkoxycarbonyl. Embodiment 48. A compound of Embodiment 47 wherein R 1 4 is H. Embodiment 49. A compound of Formula 1 wherein R 15 is H; or C 1
-C
4 alkyl, C 2
-C
4 alkenyl, C 2
-C
4 alkynyl, C 3
-C
4 cycloalkyl, C 4
-C
7 alkylcycloalkyl or C 4
-C
7 30 cycloalkylalkyl, each optionally substituted with one or more substituents selected from R 19 . Embodiment 50. A compound of Embodiment 49 wherein R 1 5 is H; or CI-C 4 alkyl optionally substituted with one or more substituents selected from R 1 9 . Embodiment 51. A compound of Embodiment 50 wherein R 15 is H; or CI-C 4 alkyl 35 optionally substituted with one or more substituents selected from halogen,
C
1
-C
4 alkyl, C 1
-C
4 alkoxy, C 1
-C
4 alkylthio, CI 1
-C
4 alkylsulfinyl, C 1
-C
4 alkylsulfonyl, C 2
-C
4 alkylcarbonyl, C 2
-C
4 alkoxycarbonyl, cyano and at most one Q 1
.
WO 2007/123853 PCT/US2007/009181 17 Embodiment 52. A compound of Embodiment 51 wherein R 15 is H; or CI-C 4 alkyl optionally substituted with one or more fluorine and at most one QI. Embodiment 53. A compound of Formula 1 wherein Q is other than R 1 6 . Embodiment 54. A compound of Formula 1 wherein R 1 6 is halogen, CI-C 3 haloalkyl, 5 C 2
-C
4 dialkylamino, cyano or nitro. Embodiment 55. A compound of Formula 1 wherein R 1 is CI-C 3 alkyl optionally substituted with one or more substituents independently selected from R 17 . Embodiment 56. A compound of Embodiment 55 wherein R 1 is C 1
-C
3 alkyl substituted with one or more halogen. 10 Embodiment 57. A compound of Embodiment 56 wherein R 1 is CF 3 . Embodiment 58. A compound of Formula 1 wherein n is 1 or 2. Embodiment 59. A compound of Formula 1 wherein at most 3 of A 1 , A 2 , A 3 and A 4 are N. Embodiment 60. A compound of Embodiment 59 wherein at most 2 of A l , A 2 , A 3 and 15 A 4 are N. Embodiment 61. A compound of Embodiment 60 wherein at most 1 of A 1 , A 2 , A 3 and
A
4 is N. Embodiment 62. A compound of Embodiment 61 wherein A 1 , A 2 , A 3 and A 4 are each other than N. 20 Embodiment 63. A compound of Formula 1 wherein when Z is CH, and one R 2 is attached to the phenyl ring at the 4-position, then said R 2 is other than C 1
-C
6 alkoxy. Embodiment 64. A compound of Formula 1 wherein when U is C(--O) and G is NR 3 , then R 3 is other than H. 25 Embodiments of this invention, including Embodiments 1-64 above as well as any other embodiments described herein, can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula 1 but also to the starting compounds and intermediate compounds. In addition, embodiments of this invention, including Embodiments 1-64 above as well as any other embodiments described 30 herein, and any combination thereof, pertain to the compositions and methods of the present invention. Combinations of Embodiments 1-64 are illustrated by: Embodiment A. A compound of Formula 1 wherein Q is a pyridinyl ring, a pyrimidinyl ring, a triazinyl ring, a pyrazolyl ring, a triazolyl 35 ring, an imidazolyl ring, an oxazolyl ring, an isoxazolyl ring, a thiazolyl ring or an isothiazolyl ring, each ring optionally substituted with one or more substituents independently selected from halogen, Cl-C 6 alkyl, Cl-C 6 haloalkyl,
C
3
-C
6 cycloalkyl, C 3
-C
6 halocycloalkyl, C 1
-C
6 alkoxy, C 1
-C
6 haloalkoxy, WO 2007/123853 PCT/US2007/009181 18
C
1
-C
6 alkylthio, C 1
-C
6 haloalkylthio, C 1
-C
6 alkylsulfinyl, C 1
-C
6 haloalkylsulfinyl, Cl-C 6 alkylsulfonyl, CI-C 6 haloalkylsulfonyl, CI-C 6 alkylamino, C 2
-C
8 dialkylamino, cyano, nitro, C(O)NR 8
R
9 , C(O)ORI 0 , phenyl and pyridinyl, each phenyl and pyridinyl optionally substituted with one or more 5 substituents independently selected from R 1 1
.
; or Q is C(O)NRI 2
RI
3 ,
S(O)
2
NR
1 4
R
15 or RI6; Z is CR 2 ; RI is CI-C 3 alkyl optionally substituted with one or more substituents independently selected from R 1 7 ; 10 each R 2 is independently selected from H, halogen or Cl-C 2 haloalkyl;
R
3 is H or cyano; or CI-C 4 alkyl optionally substituted with one or more substituents selected from halogen;
R
4 and R 5 are independently selected from halogen, CI-C 3 alkyl, CI-C 3 haloalkyl, cyano and nitro; 15 R 6 and R 7 are independently selected from halogen, C I-C 3 alkyl, CI-C 3 haloalkyl, cyano and nitro; or R 6 and R 7 are taken together to form a fused aromatic ring, the fused aromatic ring containing as ring members in addition to the A 3 and A 4 bridgehead atoms, 4 atoms selected from 3 to 4 carbon atoms and 0 to 1 nitrogen atom; 20 each R 8 is independently H, C 1
-C
6 alkyl, C 2
-C
7 alkylcarbonyl or C 2
-C
7 alkoxycarbonyl; each R 9 and RI O is independently H; or CI-C 4 alkyl, C 2
-C
4 alkenyl, C 2
-C
4 alkynyl,
C
3
-C
4 cycloalkyl, C 4
-C
7 alkylcycloalkyl or C 4
-C
7 cycloalkylalkyl, each optionally substituted with one or more substituents selected from R 19 ;
R
12 and R 14 are independently H, C 1
-C
6 alkyl, C 2
-C
7 alkylcarbonyl or C 2
-C
7 25 alkoxycarbonyl;
R
13 and R 15 are independently H; or CI-C 4 alkyl, C 2
-C
4 alkenyl, C 2
-C
4 alkynyl,
C
3
-C
4 cycloalkyl, C 4
-C
7 alkylcycloalkyl or C 4
-C
7 cycloalkylalkyl, each optionally substituted with one or more substituents selected from RI 9 ;
R
16 is halogen, CI-C 3 haloalkyl, C 2
-C
4 dialkylamino, cyano or nitro; 30 each R 19 is independently selected from halogen, CI-C 4 alkyl, CI-C 4 alkoxy, CI-C 4 alkylthio, CI-C 4 alkylsulfonyl, cyano, nitro and QI; each Q 1 is independently selected from phenyl, pyridinyl and thiazolyl, each optionally substituted with one or more substituents independently selected from halogen,
C
1
-C
3 alkyl, CI-C 3 haloalkyl, cyano, phenyl and pyridinyl; and 35 n is 1 or 2; provided that at most 1 of A i , A 2 , A 3 and A 4 is N. Embodiment B. A compound of Embodiment A wherein
R
1 is C 1
-C
3 alkyl substituted with halogen; and WO 2007/123853 PCT/US2007/009181 19 U is C(--O). Embodiment C. A compound of Embodiment B wherein Q is a pyrazolyl ring, a triazolyl ring or an imidazolyl ring, each ring attached through nitrogen and optionally substituted with one or more substituents 5 independently selected from halogen, C 1
-C
4 alkyl, CI-C 4 haloalkyl, C 1
-C
4 alkoxy, CI-C 4 haloalkoxy, cyano, nitro, C(O)NR 8
R
9 and C(O)ORIo; or Q is
C(O)NRI
2
R
13 ;
R
1 is CF 3 ;
R
6 and R 7 are independently selected from H, halogen, CI-C 3 alkyl, CI-C 3 10 haloalkyl, cyano and nitro; or R 6 and R 7 are taken together to form a fused aromatic ring, the fused aromatic ring containing 4 carbon atoms as ring members in addition to the A 3 and A 4 bridgehead atoms; each R 8 is H; each R 9 and RI 0 is independently CI-C 4 alkyl optionally substituted with one Q1 and 15 optionally substituted with one or more substituents selected from halogen, Cl-C 4 alkyl, CI-C 4 alkoxy, C 1
-C
4 alkylthio, CI-C 4 alkylsulfonyl and cyano;
R
12 is H;
R
13 is H; or CI-C 4 alkyl optionally substituted with one or more substituents selected from RI 9 ; and 20 each R 19 is independently selected from halogen and Q 1 . Embodiment D. A compound of Embodiment C wherein each R 2 is independently H, halogen or CF 3 ; and
R
3 is CH 3 , CH 2
CH
3 , or CH 2
CF
3 . Embodiment E. A compound of Embodiment D wherein 25 G is O; and provided that A 1 , A 2 , A 3 and A 4 are each other than N. Specific embodiments include compounds of Formula 1 selected from the group consisting of: 4-[5-(3,5-dichlorophenyl)-2-oxo-5-(trifluoromethyl)-3-oxazolidinyl]-2-methyl N-(2-pyridinylmethyl)benzamide; 4-[5-(3,5-dichlorophenyl)-2-oxo-5-(trifluoromethyl)-3-oxazolidinyl]-2-methyl N-(2,2,2-trifluoroethyl)benzamide; 4-[5-(3,5-dichlorophenyl)-2-oxido-5-(trifluoromethyl)-1,2,3-oxathiazolidin-3-yl] 2-methyl-N-(2-pyridinyimethyl)benzamide; 2-nitro-5-[2-oxo-5-phenyl-5-(trifluoromethyl)-3-oxazolidinyl]benzonitrile; 4-[4-(3,5-dichlorophenyl)-2-oxo-4-(trifluoromethyl)- 1l-imidazolidinyl]-2-methyl N-(2-pyridinylmethyl)benzamide; 4-[4-(3,5-dichlorophenyl)-3-methyl-2-oxo-4-(trifl uoromethyl)- 1-imidazolidinyl]- WO 2007/123853 PCT/US2007/009181 20 2-methyl-N-(2-pyridinylmethyl)benzamide; 4-[5-(3,4-dichlorophenyl)-2-oxo-5-(trifluoromethyl)-3-oxazolidinyl]-2-methyl N-(2-pyridinylmethyl)benzamide; 5-[5-(3,5-dichlorophenyl)-2-oxo-5-(trifluoromethyl)-3-oxazolidinyl] 2-(1H- 1,2,4-triazol- 1-yl)benzonitrile; 4-[5-(3 ,5-dichlorophenyl)-2,2-dioxido-5-(trifluoromethyl)-l,2,3-oxathiazolidin-3-yl] 2-methyl-N-(2-pyridinylmethyl)benzamide; and 4-[5-(3,5-dichlorophenyl)-2-oxo-5-(trifluoromethyl)-3-oxazolidinyl]-2-methyl N-[ I-(2-pyridinyl)ethyl]benzamide. Further specific embodiments include any combination of the compounds of Formula 1 selected from the group immediately above. Of note is that compounds of this invention are characterized by favorable metabolic 5 and/or soil residual patterns and exhibit activity controlling a spectrum of agronomic and nonagronomic invertebrate pests. Of particular note, for reasons of invertebrate pest control spectrum and economic importance, protection of agronomic crops from damage or injury caused by invertebrate pests by controlling invertebrate pests are embodiments of the invention. Compounds of this 10 invention because of their favorable translocation properties or systemicity in plants also protect foliar or other plant parts which are not directly contacted with a compound of Formula 1 or a composition comprising the compound. Also noteworthy as embodiments of the present invention are compositions for controlling an invertebrate pest comprising a biologically effective amount of a compound of 15 any of the preceding Embodiments, as well as any other embodiments described herein, and any combinations thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent. Embodiments of the invention further include methods for 20 controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of any of the preceding Embodiments (e.g., as a composition described herein). Embodiments of the invention also include a composition comprising a compound of any of the preceding Embodiments, in the form of a soil drench liquid formulation. 25 Embodiments of the invention further include methods for controlling an invertebrate pest comprising contacting the soil with a liquid composition as a soil drench comprising a biologically effective amount of a compound of any of the preceding Embodiments. Embodiments of the invention also include a spray composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of any of the WO 2007/123853 PCT/US2007/009181 21 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 humectant. Embodiments of the invention also 5 include a device for controlling an invertebrate pest comprising said bait composition and a housing adapted to receive said bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to said bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known 10 activity for the invertebrate pest. Compounds of Formula 1 can be prepared by one or more of the following methods and variations as described in Schemes 1-14. The definitions of R 1 , R 2 , A 1
A
2 , A 3 , A 4 , G, U, Q, Z, and n in the compounds of Formulae 1-24 below are as defined above in the Summary of the Invention. Formulae la and lb are subsets of Formula 1, and Formula 2a is 15 a subset of Formula 2. As shown in Scheme 1, a compound of Formula 1 can be prepared by treating an amine of Formula 2 with an appropriate reagent of Formula 3 (where L is a suitable nucleophilic reaction leaving group such as halogen or imidazole) in the presence of a base (e.g. triethylamine, N,N-diisopropylethylamine or sodium hydrogen carbonate). Also useful 20 as a base are polymer-supported acid scavengers such as polymer-bound equivalents of N,N diisopropylethylamine and 4-(dimethylamino)pyridine, for example, N-[(4-ethenylphenyl] methyl)]-N-methyl-4-pyridinamine polymer with diethenylbenzene and ethenylbenzene (CAS Registry Number 82942-26-5, hereafter identified as "PS-DMAP"). The method of Scheme 1 can be done with a wide variety of. reagents of Formula 3 such as 25 1,1'-carbonyldiimidazole, phosgene, trichloromethyl chloroformate, triphosgene, (i.e. when U is C(=O)), thiophosgene, 1,1'-thiocarbonyldiimidazole, (i.e. when U is C(=S)), thionyl chloride (i.e. when U is S(=O)), and sulfuryl chloride (i.e. when U is S(0) 2 ). Scheme 1 R1 G-H R GU N A 3 L L baseZ N A 3 2l AL L+ L LI (R ) 'A 2 (R2)n A 2 Q 2 3 1 30 The reaction can be conducted neat or in an solvent such as dichloromethane, chloroform, tetrahydrofuran, acetonitrile or 1,2-dichloroethane. Temperatures for this reaction can range from 0 to 90 *C. The method of Scheme 1 is illustrated in Step F of Example 1, Step D of Example 2, and Example 3.
WO 2007/123853 PCT/US2007/009181 22 Compounds of Formula 2a (Formula 2 wherein G is O) can be made by the ring opening of an appropriate epoxide of Formula 4 by treatment with an amine of Formula 5 in a solvent such as methanol, ethanol, chloroform, tetrahydrofuran, acetonitrile or 1,2-dichloroethane at temperatures ranging from 25 to 90 'C, as depicted in'Scheme 2. The 5 method of Scheme 2 is illustrated in Step E of Example 1 and Step C of Example 2. Scheme 2 RI H
R
1 y (R)R2 (R2 )n 4 5 2a Epoxides of Formula 4 can be prepared from ketones of Formula 6 by treatment with a sulfonium ylide, which is typically generated in situ by reacting a trimethylsulfoxonium 10 halide of Formula 7 with an appropriate base such as sodium hydride, potassium hydride or sodium tert-butoxide, in a suitable solvent such as dimethyl sulfoxide, N,N-dimethylformamide or tert-butanol, as depicted in Scheme 3. The method of Scheme 3 is illustrated in Step D of Example 1. Trimethylsulfoxonium halides of Formula 7 are commercially available. 15 Scheme 3
CH
3 el
H
3 C-S=O E) I Xe CH 3 7 X is halogen base solvent E CH 3
CH
3 R I
H
2 C-S-O - 3
H
2 C-S=0 L I
OCH
3 CH (R2 (R)n 6 4 WO 2007/123853 PCT/US2007/009181 23 As illustrated in Scheme 4, ketones of Formula 6 can be obtained by treating compounds of Formula 8 with lithium metal, an organolithium reagent such as, n-butyllithium, sec-butyllithium or tert-butyllithium, or an alkylmagnesium halide such as ethyl or methyl magnesium bromide or chloride at temperatures typically between -78 'C 5 and room temperature, to form the lithio or Grignard intermediate, respectively. This intermediate is then reacted with a reagent of Formula 9 where L 1 is a leaving group such as CI, Br, OCH 3 or OCOCF 3 to give the ketone of Formula 6. The reaction is run in an organic solvent, preferably tetrahydrofuran or diethyl ether. The method of Scheme 4 is illustrated in Step C of Example 1. 10 Scheme 4 RI Z 1. alkyllithium or alkylmagnesium halide Z (R2)n 0 (R2) 2. I L6 8R1 L16
X
1 is Br, I or CI 9 9 Alternatively, compounds of Formula la (Formula 1 wherein G is O and U is C(=0)) can be prepared from oxazolidinones of Formula 10 by reacting with aromatic halide intermediates of Formula 11 (where L 2 is a leaving group such as F or Cl) as illustrated in 15 Scheme 5. Scheme 5 R L2 A 3 + ~A 4 _____ A 3 A A 2).
N"A
2 kQ A (R )(p2)
A
2 10 11 la In this reaction the oxazolidinone of Formula 10 is contacted with a base, such as sodium hydride or potassium tert-butoxide, and then subsequently treated with a compound 20 of Formula 11 typically in a solvent (e.g., N,N-dimethylformamide or dimethyl sulfoxide). The method of Scheme 5 is illustrated in Step B of Example 4. Alternatively, when Formula 11 is an aryl bromide (i.e. L 2 is Br) the reaction can be conducted with two equivalents of a base such as potassium carbonate and in the presence of a copper(I) catalyst such as WO 2007/123853 PCT/US2007/009181 24 copper(I) iodide (typically 3-5 mol %) and trans-cyclohexanediamine (to solubilize the Cul) using the method described in Organic Letters 2003, 5, 963-965. As depicted in Scheme 6, compounds of Formula la can also be prepared by a copper-mediated N-arylation reaction of an oxazolidinone of Formula 10 with a compound 5 of Formula 12, where M is a group such as boronic acid, boronic ester, biarylbismuthane, trialkylstannane or trialkylsiloxane. The reaction can be run in an solvent such as dichloromethane, chloroform or tetrahydrofuran, and in the presence of a copper salt such as copper (II) acetate and a base (e.g., triethylamine, or pyridine), as depicted in Scheme 6. For :general procedures for this type of reaction, see Ley, S. V.; Thomas, A. W. Angewandte 10 Chemie, International Edition 2003, 42, 5400-5449. Scheme 6 0 R 1 -0 0
R
1 ,0 + I
(R
2 ). (R2 10 12 la Oxazolidinones of Formula 10 can be prepared by the reaction of amino alcohols of Formula 13 with triphosgene or triphosgene substitutes that result in carbonylation (e.g., 15 diphosgene, phosgene, (bis(trichloromethyl) carbonate) or 1,1'-carbonyl-diimidazole). The reaction is run in a suitable organic solvent, such as dichloromethane, 1,2-dichloroethane or tetrahydrofuran in the presence of a base such as triethylamine, sodium hydrogen carbonate or sodium carbonate as depicted in Scheme 7. Scheme 7 R OH 1 C C1 0 C1 z+ CIoKoICN (R2)n (R2)n 20 -13 10 Amino alcohols of Formula 13 can be prepared by the reduction of cyanohydrins of Formula 14 with a reducing agent such as lithium tetrahydroaluminate in a suitable organic solvent such as diethyl ether or tetrahydrofuran as depicted in Scheme 8. The methods of Schemes 7 and 8 are illustrated in Step A of Example 4.
WO 2007/123853 PCT/US2007/009181 25 Scheme 8 RI OH
R
1 OH LiAlH 4
(R
2 )n (R2)n 14 13 Cyanohydrins of the Formula 14 can be prepared from the corresponding ketones (i.e., Formula 6) via one of a variety of cyanation methods well known in the art (see, for 5 example, North, M. Science of Synthesis 2004, 19, 235-284). Compounds of Formula lb (i.e. Formula 1 wherein G is NR 3 and U is C(=O)) can be prepared by reduction of the imide of Formula 15 with sodium borohydride in a suitable solvent such as methanol and then reducing the resulting 5-hydroxy intermediate with sodium borohydride and trifluoroacetic acid. Methods for reduction of ketones and alcohols 10 are well document in the art see, for example, Mehrotra, M. M., et al.; Journal of Medicinal Chemistry 2004, 47, 2037-2061 and Johnson, M. R.; Rickborn, B.; Journal of Organic Chemistry 1970, 35, 1041-1045. The method of Scheme 9 is illustrated in Example 5, Steps E and F as well as Example 6, Steps B and C. Scheme 9
R
3
R
3 0 0 I N O NaBH 4 NaBH 4 1 N Z 5 > A, 4 solvent TFA Z N A 2I I (e.g., MeOH) LA 2A (R )n , Q )R 2 Q 15 15 lb As shown in Scheme 10, compounds of Formula 15 can be prepared from cyclization of ureas of Formula 16 by treatment with aqueous hydrochloric acid according to the general method described by Cook, A. H.; Hunter, G. D.; Journal of the Chemical Society 1952, 3789-3796. For compounds of Formula 15 where R 3 is other than H, then treating the 20 cyclized intermediate (where R 3 is H) with L 3
-R
3 (wherein L 3 is a leaving group) in the presence of a suitable base such as sodium hydride to yield compounds of Formula 15. The second step of the method of Scheme 10 is illustrated in Example 6, Step A.
WO 2007/123853 PCT/US2007/009181 26 Scheme 10
R
3 RIM OH 3 O N- 3 d "CN A 1. cyclization 2. L3-RN A 0'A2<Q (R2 -' 2) (R2)n 2)n 16 15 As shown in Scheme 11, compounds of Formula 16 can be obtained by reacting a-aminonitriles of Formula 17 with isocyanates of Formula 18 according to the general 5 method of Van Dort, M. E.; Jung, Y.-W.; Bioorganic & Medicinal Chemistry Letters 2004, 14(21), 5285-5288. Scheme 11
R
1 NH2
R
1 NH CN OCN A C A (R2)n - 2 (R2)n 17 18 16 Compounds of Formula 17 can be obtained by coverting ketones of Formula 6 to the 10 corresponding imines 20, followed by addition of a cyanide source (e.g., HCN) to the imine intermediates, followed by the addition of cyanide, which are well documented in the art (see, for example, Organic Reactions 2002, 59, 1-714 and Koos, M.; Mosher, H. S.; Tetrahedron 1993, 49, 1541-1546). The method shown in Scheme 12 is particularly useful for the preparation of the 15 imines 20 when R 1 is CF 3 . Scheme 12
R
1
R
1
R
i
Z
O LiN(SiMe 3
)
2 - SiMe 3 MeOH (R2)n (R2)n (R2)n 6 19 20 As shown above, a ketone of Formula 6 is first treated with lithium bis(trimethylsilyl)amide, which results in the formation of an imine intermediate 19, which WO 2007/123853 PCT/US2007/009181 27 is then solvolyzed in methanol to afford a stable imine 20 according to the general method of Gosselin, F. et al Organic Letters 2005, 7, 355-358. Alternatively, compounds of Formula 15 can be prepared by heating compounds of Formula 21 with amines of Formula 5 (see Scheme 13) in the presence of a catalyst such as 5 4-(dimethylamino)pyridine or trifluoroacetic acid. The cyclized hydantoins formed can then be treated with L 3
-R
3 in the presence of a base such as sodium hydride to form compounds of Formula 15. For reference, see Pozzo, A. D. et al.; Tetrahedron 1998, 6019-6028. The method of Scheme 13 is illustrated in Example 5, Step D. Scheme 13 O OCH 2 Ph
R
3 YI \ 0o R I NH H2N. A3 .R S-;2Et A 4 1. cyclization 3
CO
2 Et% NA ~ At ZC2t +Z ,A A4 A./ A'A2J -Q 2. L3-R3 0/,/ Al A (R2)n (R2)n 10 21 5 15 As shown in Scheme 14, compounds of Formula 21 can be obtained by reacting x-ketoesters of Formula 22 with benzyl carbamate, after dehydration to form imines of Formula 23, followed by addition of the Grignard intermediates 24, which can be derived from compounds of Formula 8 as described previously for the method of Scheme 4. For 15 general reference, see Dessipri, E.; Tirrell, D. A.; Macramolecules 1994, 27, 5463-5470. The method of Scheme 14 is illustrated in Example 5, Steps A-C. Scheme 14 MgBr C / ROCH 2 Ph bamte OY OCH 2 Ph
R
1 NH I benzyl ! (R2)n4 R Ocarbamate RI N 24 CO-Et CO2Et CO 2 Et CO 2 Et (R2 )n 22 23 21 One skilled in the art will recognize that compounds of Formula 1 and the 20 intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents. It is also recognized that some reagents and reaction conditions described above for preparing compounds of Formula 1 may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of WO 2007/123853 PCT/US2007/009181 28 protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One 5 skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula 1. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the 10 particular sequence presented to prepare the compounds of Formula 1. Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. 1 H NMR spectra are reported in ppm downfield from tetramethylsilane; 15 19 F NMR spectra are reported in ppm using trichlorofluoromethane as reference; "s" means singlet, "d" means doublet, "t" means triplet, "m" means multiplet, "dd" means doublet of doublet, "dt" means doublet of triplet, "br s" means broad singlet and "br t" means broad triplet. EXAMPLE 1 ' 20 Preparation of 4-[5-(3,5-dichlorophenyl)-2-oxo-5-(trifluoromethyl)-3-oxazolidinyl] 2-methyl-N-(2,2,2-trifluoroethyl)benzamide Step A: Preparation of 4-(acetylamino)-2-methyl-N-(2,2,2-trifluoroethyl)benzamide To a stirred solution of 4-(acetylamino)-2-methylbenzoic acid (Aldrich, 1.9 g, 9.8 mmol) in tetrahydrofuran (9 mL) at room temperature was added 1,1'-carbonyldiimidazole 25 (1.65 g, 10.1 mmol). After 18 h, 2,2,2-trifluoroethanamiine (1.6 g, 16.0 mmol) was added, followed by a catalytic amount of 4-(dimethylamino)pyridine (also known as N,N-dimethyl 4-pyridinamine). After 24 h, water was added to the reaction mixture, and the resulting precipitate was collected by filtration and dried to provide the title compound as a white powder (2.1 g). 30 IH NMIR (DMSO-d 6 ): 8 10.01 (s, IH), 8.80 (t, 1H), 7.46 (d, IH), 7.45 (s, IH), 7.31 (d, 1H), 4.02 (m, 2H), 2.31 (s, 3H), 2.05 (s, 3H). Step B: Preparation of 4-amino-2-methyl-N-(2,2,2-trifluoroethyl)benzamide To 4-(acetylamino)-2-methyl-N-(2,2,2-trifluoroethyl)benzamide (i.e. the product of Step A) was added concentrated hydrochloric acid, and the reaction mixture was heated to 35 100 oC for 2 h. The reaction mixture was cooled using an external ice/water bath, and aqueous sodium hydroxide (50 wt%, 20 mL) was added until the reaction mixture was neutralized, causing a solid to precipitate. The solid was filtered, washed with water and WO 2007/123853 PCT/US2007/009181 29 dried in a vacuum oven at 60 °C overnight to provide the title compound as a white powder (0.89 g). 1 H NMR (DMSO-d 6 ): 8 8.42 (t, 1H), 7.18 (d, 1H), 6.38 (s, IH), 6.39 (d, 2H), 5.43 (br s, 2H), 3.96 (m, 2H), 2.57 (s, 3H). 5 Step C: Preparation of 1-(3,5-dichlorophenyl)-2,2,2-trifluoroethanone To a stirred slurry of 1-bromo-3,5-dichlorobenzene (Aldrich, 15.0 g, 65.1 mmol) in anhydrous ether (300 mL) at -70 oC was added dropwise n-butyllithium (2.5 M in hexane, 26.0 mL, 65.0 mmol) over 30 minutes. After 5 minutes, methyl trifluoroacetate (9.17 g, 71.6 mmol) in ether (7 mL) was added dropwise over 45 minutes. After a further 45 minutes, the 10 reaction mixture was warmed to 0 0 C and then poured into a saturated solution of aqueous potassium dihydrogen phosphate (50 g in 200 mL of water) and stirred for 30 minutes at room temperature. The layers were separated, and the organic layer was washed with saturated sodium chloride (100 mL), dried (MgSO 4 ), and concentrated under reduced pressure to provide the title compound as a yellow oil (13.0 g). 15 IH NMR (CDC1 3 ): 5 7.74 (s, 2H), 7.44 (s, IH). 19 F NMR (CDC1 3 ): 8 -76.82. Step D: Preparation of 2-(3,5-dichlorophenyl)-2-(trifluoromethyl)oxirane Sodium hydride (60%, 0.36 g, 9.0 mmol) was added to a stirred solution of trimethylsulfoxonium iodide (1.88 g, 8.5 mmol) in dimethyl sulfoxide (17 mL) under a nitrogen atmosphere. After stirring for 0.5 h, the solution was added dropwise over 5 20 minutes to a solution of 1-(3,5-dichlorophenyl)-2,2,2-trifluoroethanone (i.e. the product of Step C) (1.7 g, 7.0 mmol) in tetrahydrofuran. The resulting yellow slurry was stirred for 5 minutes, and then the reaction mixture was partitioned between ether (100 mL) and water (50 mL). The organic layer was separated, and the aqueous layer was extracted with ether (70 mL). The combined ether extracts were washed with water (40 mL) and dried (MgSO 4 ). 25 The ether solution was filtered, and the solvent was concentrated under reduced pressure to provide the title compound as an orange oil (1.71 g). The crude product (70-80% by IH NMR) was used without purification. IH NMR (CDCl 3 ):5 7.42 (m, 3H), 3.43 (d, IH), 2.91 (m, 1H). 1 9 F NMIR (CDCI 3 ): 6 -74.57. Step E: 4-[[2-(3,5-dichlorophenyl)-2-hydroxy-3,3,3-trifluoropropyl] amino]-2-methyl 30 N-(2,2,2-trifluoroethyl)benzamide A solution of 2-(3,5-dichlorophenyl)-2-(trifluoromethyl)oxirane (i.e. the product of Step D) (0.82 g) and 4-amino-2-methyl-N-(2,2,2-trifluoroethyl)benzamide (i.e. the product of Step B) (0.42 g, 1.7 mmol) in anhydrous ethanol (8 mL) was heated at 75 oC for 18 h. After cooling, the solvent was concentrated under reduced pressure. The residue was 35 purified by medium pressure silica gel chromatography using ethyl acetate-hexanes (2:3) as eluant to provide the title compound as an off-white glassy solid (0.36 g).
WO 2007/123853 PCT/US2007/009181 30 IH NMR (CDCI 3 ): 8 7.51 (s, 2H), 7.37 (s, 1H), 7.18 (d, 1H), 6.42 (m, 2H), 6.30 (s, IH), 6.29 (d, IH), 5.13 (s, 1H), 3.96 (m, 2H), 3.74 (dd, 1H), 3.62 (dd, IH), 2.00 (s, 3H). 1 9 F NMR (CDCl 3 ): 8 -72.80, -78.47. Step F: 4-[5-(3,5-dichlorophenyl)-2-oxo-5-(trifluoromethyl)-3-oxazolidinyl] 5 2-methyl-N-(2,2,2-trifluoroethyl)benzamide A slurry of 4-[[2-(3,5-dichlorophenyl)-2-hydroxy-3,3,3-trifluoropropyl]aminno] 2-methyl-N-(2,2,2-trifluoroethyl)benzamide (i.e. the product of Step E) (0.28 g, 0.57 mmol), 1,1'-carbonyldiimidazole (0.15 g, 0.93 mmol) and PS-DMAP (Riley Co., 1.4 mmol/g) (0.085 g, 0.12 mmol) in dichloromethane (7 mL) was stirred at room temperature for 5 h. 10 More 1,1'-carbonyldiimidazole (0.05 g, 0.31 mmol) was added. After stirring for 22 h, more 1,1'-carbonyldiimidazole (0.047 g, 0.28 mmol) and PS-DMAP (0.10 g, 0.14 mmol) were added. After stirring for 4 h, the reaction mixture was concentrated under reduced pressure, and the resulting residue was dissolved in ethyl acetate (60 mL), washed with water (3 x 30 mL), filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured 15 by Varian), and concentrated under reduced pressure to give a solid. The crude solid was purified by medium pressure silica gel chromatography using ethyl acetate/hexanes (2:3) as eluant to provide the title product, a compound of the present invention, as an off-white solid (0.20 g). IH NMR (CDCl 3 ): 8 7.48 (m, 3H), 7.41 (d, 1H), 7.37 (d, IH), 7.31 (s, 1H), 6.38 (br s, 1H), 20 4.62 (d, 1H), 4.30 (d, 1H), 4.07 (m, 2H1), 2.43 (s, 3H). 1 9 F NMR (CDCI 3 ): 8 -72.79, -81.57. EXAMPLE 2 Preparation of 4-[5-(3,5-dichlorophenyl)-2-oxo-5-(trifluoromethyl)-3-oxazolidinyl] 2-methyl-N-(2-pyridinylmethyl)benzamide Step A: Preparation of 4-(acetylamnino)-2-methyl-N-(2-pyridinylmethyl)benzamide 25 A mixture of 4-(acetylamino)-2-methylbenzoic acid (5.0 g, 25.9 mmol), 2-pyridinemethanamine (2.94 g, 2.8 mL, 27.2 mmol), and N-(ethylcarbonimidoyl) N,N-dimethyl-1,3-propanediamine, monohydrochloride (5.2 g, 27.1 mmol) in dichloromethane (250 mL) was stirred at room temperature overnight. Then water was added to the reaction mixture, and the resulting two layers were separated. The 30 dichloromethane layer was passed through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian) and concentrated under reduced pressure. The resulting amber oil was triturated with dichloromethane, n-butyl chloride, and hexanes to provide the title compound as a pale yellow solid (5.5 g). IH NMR (CDCI 3 ): 8 8.53 (d, 1H), 7.92 (br s, 1H), 7.69 (m, 1H), 7.42-7.16 (m, 6H), 4.72 (d, 35 2H), 2.42 (s, 3H), 2.15 (s, 3H).
WO 2007/123853 PCT/US2007/009181 31 Step B: Preparation of 4-amino-2-methyl-N-(2-pyridinylmethyl)benzamide A mixture of 4-(acetylamino)-2-methyl-N-(2-pyridinylmethyl)benzamide (i.e. the product of Step A) (5.5 g, 19.4 mmol) and concentrated hydrochloric acid (100 mL) was stirred and heated at reflux for 1 h. After cooling, ice was added and the pH adjusted to 10 5 by adding aqueous sodium hydroxide (50 wt%). The reaction mixture was filtered to collect the solid precipitate, which was washed with water and dried to provide the title compound as a light yellow solid (4.02 g). 1 H NMR (DMSO-d 6 ): 8 8.49 (d, 1H), 8.41 (br s, 1H), 7.76 (m, 1H11), 7.31 (d, 1H), 7.22-7.27 (min, 2H), 6.36-6.40 (m, 2H), 5.36 (s, 2H), 4.47 (s, 2H), 2.28 (s, 3H). 10 Step C: Preparation of 4-[[2-(3,5-dichlorophenyl)-2-hydroxy 3,3,3-trifluoropropyl]amino]-2-methyl-N-(2-pyridinylmethyl)benzamide A solution of 2-(3,5-dichlorophenyl)-2-(trifluoromethyl)oxirane (i.e. the product of Example 1, Step D) (0.75 g) and 4-amino-2-methyl-N-(2-pyridinylmethyl)benzamide (i.e. product of Step B) (0.39 g, 1.7 mmol) in anhydrous ethanol (6 mL) was heated at 65 'C for 15 70 h. The reaction mixture was concentrated under reduced pressure, and the residue was purified by medium pressure silica gel chromatography using ethyl acetate/hexanes (6:8) as eluant to provide the title compound as an off-white glassy solid (0.28 g). IH NMR (CDC13): 8 8.50 (d, IH), 7.70 (t, IH), 7.52 (s, 2H), 7.40 (s, 1H), 7.31 (m, 2H), 7.21 (min, liH), 7.08 (br t, 1H), 6.37 (s, 1H), 6.36 (d, 1H), 5.02 (br s, 1H), 4.68 (d, 2H), 3.88 (t, 1H), 20 3.81 (dd, IH), 3.61 (dd, 1H), 2.39 (s, 3H). 19 F NMR (CDC13): 8 -78.43. Step D: Preparation of 4-[5-(3,5-dichlorophenyl)-2-oxo-5-(trifluoromethyl) 3-oxazolidinyl-2-methyl-N-(2-pyridinylmethyl)benzamide 4-[[2-(3,5-dichlorophenyl)-2-hydroxy-3,3,3-trifluoropropyl]amino-2-methyl N-(2-pyridinylmethyl)benzamide (i.e. the product of Step C) (0.21 g, 0.42 mmol), 25 1,1'-carbonyldiimidazole (0.13 g, 0.79 mmol), PS-DMAP (Riley Co., 0.065 g, 0.12 mmol), and dichloromethane (7 miL) were combined and stirred at room temperature for 5 h. More 1,1'-carbonyldiimidazole (0.05g, 0.31 mmol) was added. After stirring for 22 h, more 1,1'-carbonyldiimidazole (0.15 g, 0.92 mmol) and PS-DMAP (0.31 g, 0.43 mmol) were added. After stirring for 24 h, the reaction mixture was concentrated under reduced pressure 30 and purified by medium pressure silica gel chromatography using ethyl acetate/hexanes (6:8) as eluant to provide the title product, a compound of the present invention, as an off-white glassy solid (0.20 g). IH NMR (CDCl 3 ): 8 8.52 (d, 1H), 7.71 (t, 11), 7.54-7.20 (m, 9H1), 4.73 (d, 2H), 4.63(d, 1H), 4.30 (d, 1H), 2.51 (s, 3H). 1 9 F NMR (CDCl 3 ): 8 -81.52.
WO 2007/123853 PCT/US2007/009181 32 EXAMPLE 3 Preparation of 4-[5-(3,5-dichlorophenyl)-2-oxido-5-(trifluoromethyl)-1,2,3-oxathiazolidin 3-yl]-2-methyl-N-(2-pyridinylmethyl)benzamide To a stirred solution of 4-[[2-(3,5-dichlorophenyl)-2-hydroxy-3,3,3-trifluoro 5 propyl]amino]-2-methyl-N-(2-pyridinylmethyl)benzamide (i.e. the product of Example 2, Step C) (0.11 g, 0.22 mmol), triethylamine (0.096 g, 0.95 mmol), and 4-(dimethylamino)pyridine (0.022 g, 0.018 mmol) in dichloromethane (2 mL) was added dropwise thionyl chloride (0.043 g, 0.36 mmol). After stirring for I h at room temperature, more thionyl chloride (0.026 g, 0.22 mmol) was added. After stirring 1 h more, the reaction 10 mixture was concentrated under reduced pressure, and the crude product was purified by medium pressure silica gel chromatography using ethyl acetate/hexanes (3:6) as eluant to provide the title product (1:1 mixture of diastereoisomers), a compound of the present invention, as an off-white solid (0.04 g). 1 H NMR (CDC13): 5 8.50 (m, 1H), 7.69 (br t, 1H), 7.49 (m, 4H), 7.33 (mn, 1H), 7.22 (m, 2H), 15 6.93 (min, 2H), 4.73 (d, 1H), 4.41 (d, 1H), 4.70 (d, 0.5H), 4.56 (d, 0.5H), 4.38 (d, 0.5H), 4.20 (d, 0.5H), 2.50 (s, 1.5H), 2.47 (s, 1.5H). 19 F NMR (CDCl 3 ): 6 -76.31, -79.67. EXAMPLE 4 Preparation of 2-nitro-5-[2-oxo-5-phenyl-5-(trifluoromethyl)-3-oxazolidinyl]benzonitrile Step A: Preparation of 5-phenyl-5-(trifluoromethyl)-2-oxazolidinone 20 To a cold (below 20 'C) solution of lithium tetrahydroaluminate (10.0 mL, 1.0 M solution in diethyl ether) was added a solution of a-hydroxy a-(trifluoromethyl)benzeneacetonitrile (Aldrich, 2.01 g, 10.0 mmol) in anhydrous diethyl ether (10 mL). The resulting suspension was stirred at ambient temperature for 3 h. To the reaction mixture was sequentially added water (0.38 mL), aqueous sodium hydroxide 25 solution (15 wt%, 0.38 mL), and more water (1.14 mL). The reaction mixture was filtered through a glass frit, and the filtrate was concentrated under reduced pressure to give a white solid (1.89 g). The white solid (1.23 g, 6.0 mmol) was dissolved in dichloromethane (15 mL) and added to a stirred saturated aqueous sodium hydrogen carbonate solution (15 mL). Then a solution of triphosgene bis(trichloromethyl)carbonate, (0.63 g, 2.17 mmol) in 30 dichloromethane (5 mL) was added dropwise over several minutes. The reaction mixture was stirred at ambient temperature for I h. The solvent phases were separated, and the organic phase was washed with water, 1 N aqueous hydrochloric acid, and saturated aqueous sodium chloride solution. The organic extracts were dried (MgSO 4 ), filtered and the solvent was concentrated under reduced pressure to provide the title compound as a white solid (1.35 35 g). IH NMR (CDCI 3 ) 8 7.5 - 7.4 (m, 5H), 5.95 (br s, IH), 4.26 (d, IH), 3.93 (d, 1H).
WO 2007/123853 PCT/US2007/009181 33 Step B: Preparation of 2-nitro-5-[2-oxo-5-phenyl-5-(trifluoromethyl) 3-oxazolidinyl]benzonitrile To a stirred solution of 5-phenyl-5-(trifluoromethyl)-2-oxazolidinone (i.e. the product of Step A) (0.97 g, 4.2 mmol) in N,N-dimethylformamide (20 mL) under a nitrogen 5 atomosphere was added sodium hydride in one portion (60%, 0.21 g, 5.2 mmol). After 0.33 h, 5-chloro-2-nitrobenzonitrile (1.15 g, 6.3 mmol) was added to the reaction mixture. The reaction mixture was stirred for 16 h, diluted with water, extracted with ether (100 mL), and ethyl acetate (100 mL). The combined organic extracts were washed with water (4 x 75 mL), dried (MgSO 4 ), filtered, and concentrated under reduced pressure to give a solid, 10 which was purified by silica gel chromatography and by trituration with 20% ether/hexanes to provide the title product, a compound of the present invention, as a white solid (0.235 g). 1 H NMR (CDCI 3 ) 8 8.4 (m, 1H), 8.1 (m, 1H), 8.07 (s, 1H), 7.6-7.45 (m, 5H), 4.75 (d, 1H), 4.41 (d, 1H). EXAMPLE 5 15 Preparation of 4-[4-(3,5-dichlorophenyl)-2-oxo-4-(trifluoromethyl)-l1-imidazolidinyl] 2-methyl-N-(2-pyridinylmethyl)benzamide Step A: Preparation of 3,3,3-trifluoro-2-hydroxy-N-[(phenylmethoxy)carbonyl]alanine ethyl ester A solution of 3,3,3-trifluoro-2-oxo-propionic acid ethyl ester (Alfa Chem. Co., 12.0 20 g, 70.6 mmol) and benzyl carbamate (9.78 g, 64.8 mmol) in methylene chloride (55 mL) was stirred for 66 h at room temperature under nitrogen. The solvent was removed under reduced pressure. Hexane (100 mL) was added to the crude mixture, and the resulting slurry was allowed to stand overnight. The solid was collected by vacuum filtration, washed with hexane, and air-dried to provide the title compound as a white solid (20.4 g). 25 IH NMR (CDC1 3 ): 8 7.35 (m, 5H), 5.98 (s, IH), 5.35 (s, IH), 5.23 (s, 2H), 4.36 (m, 2H), 1.30 (t, 3H). Step B: Preparation of ethyl 3,3,3-trifluoro 2-[[(phenylmethoxy)carbonyl]imino]propanoate To a solution of 3,3,3-trifluoro-2-hydroxy-N-[(phenylmethoxy)carbonyl]alanine ethyl 30 ester (i.e. the product of Step A) (15.4 g, 48 mmol) and pyridine (7.9 g, 50 mmol) in anhydrous diethyl ether (200 mL) at ice-bath temperature was added dropwise trifluoroacetic anhydride (10.75 g, 51.1 mmol). The resulting slurry was warmed to room temperature and stirred for 1.5 h. The reaction mixture was filtered to remove a white solid. The filtrate was concentrated in vacuo to give a slurry. Hexane (150 mL) was added to the slurry, which was 35 filtered again to remove a white solid. The filtrate was concentrated in vacuo to afford the title product as a colorless oil (14.2 g). 1 H NMR (CDCI 3 ): 8 7.41 (m, 5H), 5.33 (s, 2H), 4.31 (q, 2H), 1.30 (t, 3H).
WO 2007/123853 PCT/US2007/009181 34 Step C: Preparation of ethyl 3,5-dichloro-a-[[(phenylmethoxy)carbonyl]amino] ct-(trifluoromethyl)benzeneacetate To a solution of ethyl 3,3,3-trifluoro-2-[[(phenylmethoxy)carbonyl]imino]propanoate (i.e. the product of Step B) (7.36 g, 24.3 mmol) in anhydrous tetrahydrofuran (10 mL), 5 cooled with a dry-ice bath, was added a solution of 3,5-dichlorophenyl magnesium bromide (Aldrich Chem. Co., 0.5 M in tetrahydrofuran, 50 mL, 25 mmol) over 45 minutes. The cloudy reaction mixture was stirred for 1 h, and then warmed to room temperature. To this yellow solution was added 1N hydrochloric acid (37 mL). The bulk of the tetrahydrofuran was removed in vacuo. The residue was partitioned between ethyl acetate (170 mL) and 10 water (100 mL). The aqueous layer was extracted with ethyl acetate (50 mL). The combined organic layers were filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian), and concentrated under reduced pressure to afford the title compound as a yellow oil (11. 1g). IH NMR (CDCI 3 ): 8 7.34 (min, 8H), 6.10 (s, 1H), 5.07 (s, 2H), 4.28 (min, 2H), 1.21 (t, 3H). 15 19 F NMR (CDCI 3 ): 8 -71.03. Step D: Preparation of 4-[4-(3,5-dichlorophenyl)-2,5-dioxo-4-(trifluoromethyl) 1-imidazolidinyl]-2-methyl-N-(2-pyridinylmethyl)benzamide A solution of ethyl 3,5-dichloro-a- [[(phenylmethoxy)carbonyl]amino] a-(trifluoromethyl)benzeneacetate (i.e. the product of Step C) (1.11 g, 2.5 mmol), 4-amino 20 2-methyl-N-(2-pyridinylmethyl)benzamide (i.e. the product of Step B of Example 2) (0.474 g, 1.95 mmol), 4-(dimethylamino)pyridine (68 mg, 0.55 mmol) in N-methyl-2-pyrrolidinone (NMP) was heated at 200 OC by microwave irradiation for 350 sec. Another run was made with 0.99 g of the product of step C, 0.44 g of the product from Step B of Example 2, and 71 mg of 4-dimethylaminopyridine in NMP (2 mL) under the same conditions. The reaction 25 mixtures from the two runs were combined and diluted with ethyl acetate (100 mL), washed with water (3 X 50 mL), filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian), and concentrated under reduced pressure to give a dark oil. This was purified by medium pressure silica gel chromatography using ethyl acetate/hexanes (45%-85%) as eluant to provide the title compound as a tan solid (0.84 g). 30 1 H NMR (DMSO-d 6 ): 8 10.65 (s, IH), 8.99 (t, 1H), 8.52 (d, 1H), 7.89 (br s, 3H), 7.80 (dt, 1H), 7.54 (d, IH), 7.39 (d, 1H), 7.32-7.27 (min, 3H), 4.54 (d, 2H), 2.39 (s, 3H). Step E: Preparation of 4-[4-(3,5-dichlorophenyl)-5-hydroxy-2-oxo-4-(trifluoromethyl) 1-imidazolidinyl]-2-methyl-N-(2-pyridinylmethyl)benzamide To a slurry of 4-[4-(3,5-dichlorophenyl)-2,5-dioxo-4-(trifluoromethyl) 35 1-imidazolidinyl ]-2-methyl -N-(2-pyridinylmethyl)benzamide (i.e. the product of Step D), (0.66 g, 1.23 inmol) in methanol (18 mL) at ice-bath temperature was added sodium borohydride (0.275 g, 7.3 mmol) in small batches over 3 minutes. The resulting orange solution was stirred at room temperature for 18 h. The solvent was removed in vacuo, and WO 2007/123853 PCT/US2007/009181 35 the residue was partitioned between ethyl acetate (50 mL) and water (50 mL). The aqueous layer was extracted with ethyl acetate (35 mL). The combined organic layers were filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian), and concentrated under reduced pressure to afford the title compound as a tan solid (0.59 g). 5 1 H NMR (DMSO-d 6 ): 89.17 (s, 1H), 8.78 (t, IH), 8.52 (d, IH), 7.79 (dt, IH), 7.75 (t, IH), 7.61 (min, 3H), 7.52 (d, 1H), 7.45 (d, 1H), 7.37 (d, 1H), 7.27 (dd, IH), 6.91 (d, 1H), 6.12 (d, IH), 4.52 (d, 2H), 2.39 (s, 3H). Step F: Preparation of 4-[4-(3,5-dichlorophenyl)-2-oxo-4-(trifluoromethyl) 1-imidazolidinyl]-2-methyl-N-(2-pyridinylmethyl)benzamide 10 To a solution of 4-[4-(3,5-dichlorophenyl)-5-hydroxy-2-oxo-4-(trifluoromethyl) 1-imidazolidinyl]-2-methyl-N-(2-pyridinylmethyl)benzamide (i.e. the product of Step E) (0.18 g, 0.33 mmol) in trifluoroacetic acid (4 mL) at ice-bath temperature was added sodium borohydride (0.10 g, 2.6 mmol) in two batches. After the initial vigorous reaction had subsided, the reaction mixture was stirred at room temperature. An additional batch of 15 sodium borohydride (0.048 g) was added after 2 h. The reaction mixture was stirred for 18 h, and then water (5 mL) was added. The reaction mixture was cooled with an external ice/water bath, and then a solution of sodium hydroxide (4.1 g of 50% aqueous solution and 10 mL of water) was added. The reaction mixture was extracted with ethyl acetate (2 X 25 mL), and the combined organic layers were filtered through a Chem Elut cartridge packed 20 with diatomaceous earth (manufactured by Varian), and concentrated under reduced pressure to give a gummy solid. Another run was conducted using 90 mg of product from Step E, 2 mL of trifluoroacetic acid, and 67 mg of sodium borohydride under similar conditions. The crude products from these two runs were combined and purified by medium pressure silica gel chromatography using ethyl acetate/hexanes (45%-65%) as eluant to provide the title 25 compound, a compound of the present invention, as an off-white solid (0.18 g). 1 H NMR (CDCI 3 ): 8 8.51 (d, 1H), 7.70 (dt, 1H), 7.52-7.30 (min, 8H), 7.23 (dd, 1H), 6.65 (s, 1H), 4.74 (d, 2H), 4.52 (d, IH), 4.13 (d, IH), 2.51 (s, 3H). EXAMPLE 6 Preparation of 4-[4-(3,5-dichlorophenyl)-3-methyl-2-oxo-4-(trifluoromethyl) 30 1-imidazolidinyl]-2-methyl-N-(2-pyridinylmethyl)benzamide Step A: Preparation of 4-[4-(3,5-dichlorophenyl)-3-methyl-2,5-dioxo 4-(trifluoromethyl)-l1-imidazolidinyl]-2-methyl N-(2-pyridinylmethyl)benzamide To a solution of 4-[4-(3,5-dichlorophenyl)-2,5-dioxo-4-(trifluoromethyl) 35 1-imidazolidinyl]-2-methyl-N-(2-pyridinylmethyl)benzamide (i.e. the product of Step D of Example 5) (0.39 g, 0.73 mmol) in N,N-dimethylformamide (4 mL) was added sodium hydride (60% oil dispersion, 0.0335 g, 2.3 mmol). After stirring for 15 min, iodomethane (0.179 g, 1.26 mmol) was added. The reaction mixture was stirred for 45 min and then WO 2007/123853 PCT/US2007/009181 36 partitioned between ethyl acetate (50 mL) and water (25 mL). The organic layer was washed with water (2 X 25 mL) and filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian), and concentrated under reduced pressure to give the title compound as a glassy solid (0.39 g). 5 1 H NMR (DMSO-d 6 ): 8 9.00 (t, 1H), 8.53 (d, IH), 7.93 (s, 1H), 7.80 (dt, 1H), 7.69 (s, 2H), 7.56 (s, 1H), 7.39 (m, 3H), 7.28 (dd, 1H), 4.56 (d, 2H), 3.00 (s, 3H), 2.40 (s, 3H). Step B: Preparation of 4-[4-(3,5-dichlorophenyl)-5-hydroxy-3-methyl-2-oxo 4-(trifluoromethyl)- 1-imidazolidinyl]-2-methyl N-(2-pyridinylmethyl)benzamide 10 To a cloudy solution of 4-[4-(3,5-dichlorophenyl)-3-methyl-2,5-dioxo 4-(trifluoromethyl)-1l-imidazolidinyl]-2-methyl-N-(2-pyridinylmethyl)benzamide (i.e. the product of Step A) (0.37 g, 0.67 mmol) in methanol (10 mL) was added sodium borohydride (0.167 g, 4.42 mmol) in small batches over 5 min. After stirring for 4.5 h, methanol was removed in vacuo, and the residue was partitioned between ethyl acetate (50 mL) and water 15 (50 mL). The aqueous layer was extracted with ethyl acetate (35 mL), and the combined organic layers were filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian), and concentrated under reduced pressure to give the title compound as a tan solid (0.32 g). IH NMR (DMSO-d 6 ): 5 8.75 (t, IH), 8.50 (d, 1H), 7.81 (s, 1H), 7.78 (dt, 1H), 7.56 (d, 1H), 20 7.46-7.31 (m, 6H), 7.26 (dd, 1H), 5.81 (d, 1H), 4.51 (d, 2H), 2.97 (s, 3H), 2.34 (s, 3H). Step C: Preparation of 4-[4-(3,5-dichlorophenyl)-3-methyl-2-oxo-4-(trifluoromethyl) 1-imidazolidinyl]-2-methyl-N-(2-pyridinylmethyl)benzamide To a solution of 4-[4-(3,5-dichlorophenyl)-5-hydroxy-3-methyl-2-oxo 4-(trifluoromethyl)-1-imidazolidinyl]-2-methyl-N-(2-pyridinylmethyl)benzamide (i.e. the 25 product of Step B) (0.25 g, 0.45 mmol) in trifluoroacetic acid (6 mL) was added sodium borohydride (0.14 g, 3.7 mmol) in batches over 3 min. After stirring for 1 h at room temperature, an additional amount of sodium borohydride (0.104 g, 2.7 mmol) was added. After stirring for an additional 18 h, water (10 mL) was added. The reaction mixture was cooled with an external ice/water bath, and then a solution of sodium hydroxide (6 mL g of 30 50% aqueous solution and 20 mL of water) was added. The reaction mixture was extracted with ethyl acetate (1 X 50 mL, 1 X 35 mL), and the combined organic layers were filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian), and concentrated under reduced pressure to give a gummy solid, which was purified by medium pressure silica gel chromatography using ethyl acetate/hexanes (45%-65%) as 35 eluant to provide the title compound, a compound of the present invention, as a white solid (0.20 g).
WO 2007/123853 PCT/US2007/009181 37 1 H NMR (CDCI 3 ): 8 8.53 (d, IH), 7.69 (dt, 1H), 7.51 (d, 1H), 7.45 (m, 2H), 7.34 (m, 4 H), 7.22 (dd, IH), 7.13 (br t, 1H), 4.73 (d, 2H), 4.31 (d, 1H), 3.83 (d, 1H), 2.90 (s, 3H), 2.51 (s, 3H). By the procedures described herein together with methods known in the art, the 5 following compounds of Tables 1 to 15 can be prepared. The following abbreviations are used in the Tables which follow: CN means cyano, NO 2 means nitro, Ph means phenyl, Py means pyridinyl, Me means methyl, Et means ethyl, i-Pr means isopropyl, and OMe means methoxy. (R 2 )m as shown refers to the combination of (R 2
)
n with the instance of Z being
CR
2 as specified for Formula 1. 10 Table 1 O 4 / 6 NRI3 (R)m 5 RS O wherein m is 1, 2, 3, 4 or 5.
(R
2 )m R 5 RI2 RI3 (R 2 )m R 5 R12 RI3 3-Cl H H CH 2
CF
3 3-Cl H H CH 2 -2-Py 3-CI, 4-Cl H H CH 2
CF
3 3-CI, 4-Cl H H CH 2 -2-Py 3-CI, 5-Cl H H CH 2
CF
3 3-CI, 5-CI H H CH 2 -2-Py 3-Cl, 4-F H H CH 2
CF
3 3-CI, 4-F H H CH 2 -2-Py 3-CI, 4-CF 3 H H CH 2
CF
3 3-C1, 4-CF 3 H H CH 2 -2-Py 3-CI, 4-Br H H CH 2
CF
3 3-CI, 4-Br H H CH 2 -2-Py 3-CF 3 H H CH 2
CF
3 3-CF 3 H H CH 2 -2-Py 3-CF 3 , 5-CF 3 H H CH 2
CF
3 3-CF 3 , 5-CF 3 H H CH 2 -2-Py 3-Br H H CH 2
CF
3 3-Br H H CH 2 -2-Py 3-Br, 5-Br H H CH 2
CF
3 3-Br, 5-Br H H CH 2 -2-Py 3-CI NO 2 H CH 2
CF
3 3-Cl NO 2 H CH 2 -2-Py 3-CI, 4-CI NO 2 H CH 2
CF
3 3-Cl, 4-CI NO 2 H CH 2 -2-Py 3-CI, 5-Cl NO 2 H CH 2
CF
3 3-C1, 5-CI NO 2 H CH 2 -2-Py 3-C1, 4-F NO 2 H CH 2
CF
3 3-CI, 4-F NO 2 H CH 2 -2-Py 3-CI, 4-CF 3
NO
2 H CH 2
CF
3 3-C1, 4-CF 3
NO
2 H CH 2 -2-Py 3-Cl, 4-Br NO 2 H CH 2
CF
3 3-C1, 4-Br NO 2 H CH 2 -2-Py 3-CF 3
NO
2 H CH 2
CF
3 3-CF 3
NO
2 H CH 2 -2-Py 3-CF 3 , 5-CF 3
NO
2 H CH 2
CF
3 3-CF 3 , 5-CF 3
NO
2 H CH 2 -2-Py 3-Br NO 2 H CH 2
CF
3 3-Br NO 2 H CH 2 -2-Py WO 2007/123853 PCT/US2007/009181 38
(R
2 )m R 5 RI2 RI3 (R2)m R 5 RI2 R13 3-Br, 5-Br NO 2 H CH 2
CF
3 3-Br, 5-Br NO 2 H CH 2 -2-Py 3-Cl CH 3 H CH 2
CF
3 3-Cl CH 3 H CH 2 -2-Py 3-Cl, 4-Cl CH 3 H CH 2
CF
3 3-Cl, 4-Cl CH 3 H CH 2 -2-Py 3-Cl, 5-Cl CH 3 H CH 2
CF
3 3-Cl, 5-Cl CH 3 H CH 2 -2-Py 3-Cl, 4-F CH 3 H CH 2
CF
3 3-Cl, 4-F CH 3 H CH 2 -2-Py 3-Cl, 4-CF 3
CH
3 H CH 2
CF
3 3-C1, 4-CF 3
CH
3 H CH 2 -2-Py 3-Cl, 4-Br CH 3 H CH 2
CF
3 3-Cl, 4-Br CH 3 H CH 2 -2-Py 3-CF 3
CH
3 H CH 2
CF
3 3-CF 3
CH
3 H CH 2 -2-Py 3-CF 3 , 5-CF 3
CH
3 H CH 2
CF
3 3-CF 3 , 5-CF 3
CH
3 H CH 2 -2-Py 3-Br CH 3 H CH 2
CF
3 3-Br CH 3 H CH 2 -2-Py 3-Br, 5-Br CH 3 H CH 2
CF
3 3-Br, 5-Br CH 3 H CH 2 -2-Py 3-CI Cl H CH 2
CF
3 3-Cl Cl H CH 2 -2-Py 3-Cl, 4-Cl Cl H CH 2
CF
3 3-C1, 4-CI Cl H CH 2 -2-Py 3-CI, 5-Cl Cl H CH 2
CF
3 3-Cl, 5-Cl Cl H CH 2 -2-Py 3-Cl, 4-F Cl H CH 2
CF
3 3-Cl, 4-F Cl H CH 2 -2-Py 3-C1, 4-CF 3 Cl H CH 2
CF
3 3-Cl, 4-CF 3 Cl H CH 2 -2-Py 3-Cl, 4-Br Cl H CH 2
CF
3 3-Ci, 4-Br Cl H CH 2 -2-Py 3-CF 3 Cl H CH 2
CF
3 3-CF 3 Cl H CH 2 -2-Py 3-CF 3 , 5-CF 3 Cl H CH 2
CF
3 3-CF 3 , 5-CF 3 Cl H CH 2 -2-Py 3-Br Cl H CH 2
CF
3 3-Br Cl H CH 2 -2-Py 3-Br, 5-Br Cl H CH 2
CF
3 3-Br, 5-Br Cl H CH 2 -2-Py 3-CI CF 3 H CH 2
CF
3 3-CI CF 3 H CH 2 -2-Py 3-Cl, 4-Cl CF 3 H CH 2
CF
3 3-Cl, 4-Cl CF 3 H CH 2 -2-Py 3-Cl, 5-CI CF 3 H CH 2
CF
3 3-Cl, 5-Cl CF 3 H CH 2 -2-Py 3-Cl, 4-F CF 3 H CH 2
CF
3 3-Cl, 4-F CF 3 H CH 2 -2-Py 3-Cl, 4-CF 3
CF
3 H CH 2
CF
3 3-CI, 4-CF 3
CF
3 H CH 2 -2-Py 3-CI, 4-Br CF 3 H CH 2
CF
3 3-C1, 4-Br CF 3 H CH 2 -2-Py 3-CF 3
CF
3 H CH 2
CF
3 3-CF 3
CF
3 H CH 2 -2-Py 3-CF 3 , 5-CF 3
CF
3 H CH 2
CF
3 3-CF 3 , 5-CF 3
CF
3 H CH 2 -2-Py 3-Br CF 3 H CH 2
CF
3 3-Br CF 3 H CH 2 -2-Py 3-Br, 5-Br CF 3 H CH 2
CF
3 3-Br, 5-Br CF 3 H CH 2 -2-Py 3-CI CN H CH 2
CF
3 3-CI CN H CH 2 -2-Py 3-CI, 4-Cl CN H CH 2
CF
3 3-Cl, 4-CI CN H CH 2 -2-Py 3-CI, 5-Cl CN H CH 2
CF
3 3-Cl, 5-Cl CN H CH 2 -2-Py 3-Cl, 4-F CN H CH 2
CF
3 3-C1, 4-F CN H CH 2 -2-Py 3-CI, 4-CF 3 CN H CH 2
CF
3 3-CI, 4-CF 3 CN H CH 2 -2-Py 3-Cl, 4-Br CN H CH 2
CF
3 3-Cl, 4-Br CN H CH 2 -2-Py WO 2007/123853 PCT/US2007/009181 39
(R
2 )m R5 R12 R13 (R 2 )m R 5
R
1 2 R13 3-CF 3 CN H CH 2
CF
3 3-CF 3 CN H CH 2 -2-Py 3-CF 3 , 5-CF 3 CN H CH 2
CF
3 3-CF 3 , 5-CF 3 CN H CH 2 -2-Py 3-Br CN H CH 2
CF
3 3-Br CN H CH 2 -2-Py 3-Br, 5-Br CN H CH 2
CF
3 3-Br, 5-Br CN H CH 2 -2-Py 3-Cl OMe H CH 2
CF
3 3-Cl OMe H CH 2 -2-Py 3-Cl, 4-Cl OMe H CH 2
CF
3 3-C1, 4-Cl OMe H CH 2 -2-Py 3-Cl. 5-Cl OMe H CH 2
CF
3 3-C1, 5-Cl OMe H CH 2 -2-Py 3-Cl, 4-F OMe H CH 2
CF
3 3-CI, 4-F OMe H CH 2 -2-Py 3-Cl, 4-CF 3 OMe H CH 2
CF
3 3-CI, 4-CF 3 OMe H CH 2 -2-Py 3-Cl, 4-Br OMe H CH 2
CF
3 3-C0, 4-Br OMe H CH 2 -2-Py 3-CF 3 OMe H CH 2
CF
3 3-CF 3 OMe H CH 2 -2-Py 3-CF 3 , 5-CF 3 OMe H CH 2
CF
3 3-CF 3 , 5-CF 3 OMe H CH 2 -2-Py 3-Br OMe H CH 2
CF
3 3-Br OMe H CH 2 -2-Py 3-Br, 5-Br OMe H CH 2
CF
3 3-Br, 5-Br OMe H CH 2 -2-Py 3-Cl H H CH 2
CH
3 3-Cl CF 3 H CH 2
CH
3 3-Cl, 4-Cl H H CH 2
CH
3 3-Cl, 4-CI CF 3 H CH 2
CH
3 3-CI, 5-Cl H H CH 2
CH
3 3-CI, 5-Cl CF 3 H CH 2
CH
3 3-C1, 4-F H H CH 2
CH
3 3-CI, 4-F CF 3 H CH 2
CH
3 3-Cl, 4-CF 3 H H CH 2
CH
3 3-Cl. 4-CF 3
CF
3 H CH 2
CH
3 3-C1, 4-Br H H CH 2
CH
3 3-Cl, 4-Br CF 3 H CH 2
CH
3 3-CF 3 H H CH 2
CH
3 3-CF 3
CF
3 H CH 2
CH
3 3-CF 3 , 5-CF 3 H H CH 2
CH
3 3-CF 3 , 5-CF 3
CF
3 H CH 2
CH
3 3-Br H H CH 2
CH
3 3-Br CF 3 H CH 2
CH
3 3-Br, 5-Br H H CH 2
CH
3 3-Br, 5-Br CF 3 H CH 2
CH
3 3-CI NO2 H CH 2
CH
3 3-Cl CN H CH 2
CH
3 3-Cl, 4-Cl NO 2 H CH 2
CH
3 3-CI, 4-Cl CN H CH 2
CH
3 3-CI, 5-CI NO 2 H CH 2
CH
3 3-Cl, 5-Cl CN H CH 2
CH
3 3-CI, 4-F NO 2 H CH 2
CH
3 3-Cl, 4-F CN H CH 2
CH
3 3-Cl, 4-CF 3
NO
2 H CH 2
CH
3 3-Cl, 4-CF 3 CN H CH 2
CH
3 3-Cl, 4-Br NO 2 H CH 2
CH
3 3-Cl, 4-Br CN H CH 2
CH
3 3-CF 3
NO
2 H CH 2
CH
3 3-CF 3 CN H CH 2
CH
3 3-CF 3 , 5-CF 3
NO
2 H CH 2
CH
3 3-CF 3 , 5-CF 3 CN H CH 2
CH
3 3-Br NO 2 H CH 2
CH
3 3-Br CN H CH 2
CH
3 3-Br, 5-Br NO 2 H CH 2
CH
3 3-Br, 5-Br CN H CH 2
CH
3 3-Cl CH 3 H CH 2
CH
3 3-Cl OMe H CH 2
CH
3 3-C, 4-Cl CH 3 H CH 2
CH
3 3-Cl, 4-CI OMe H CH 2
CH
3 3-CI, 5-Cl CH 3 H CH 2
CH
3 3-CI, 5-Cl OMe H CH 2
CH
3 WO 2007/123853 PCT/US2007/009181 40
(R
2 )m R5 RI2 RI3 (R 2 )m R5 R12 RI3 3-CI, 4-F CH 3 H CH 2
CH
3 3-Cl, 4-F OMe H CH 2
CH
3 3-Cl, 4-CF 3
CH
3 H CH 2
CH
3 3-Cl, 4-CF 3 OMe H CH 2
CH
3 3-Cl, 4-Br CH 3 H CH 2
CH
3 3-CI, 4-Br OMe H CH 2
CH
3 3-CF 3
CH
3 H CH 2
CH
3 3-CF 3 OMe H CH 2
CH
3 3-CF 3 , 5-CF 3
CH
3 H CH 2
CH
3 3-CF 3 , 5-CF 3 OMe H CH 2
CH
3 3-Br CH 3 H CH 2
CH
3 3-Br OMe H CH 2
CH
3 3-Br, 5-Br CH 3 . H CH 2
CH
3 3-Br, 5-Br OMe H CH 2
CH
3 3-Cl Cl H CH 2
CH
3 3-Cl, 4-Br CI H CH 2
CH
3 3-Cl, 4-Cl Cl H CH 2
CH
3 3-CF 3 Cl H CH 2
CH
3 3-Cl, 5-Cl Cl H CH 2
CH
3 3-CF 3 , 5-CF 3 Cl H CH 2
CH
3 3-Cl, 4-F Cl H CH 2
CH
3 3-Br Cl H CH 2
CH
3 3-Cl, 4-CF 3 Cl H CH 2
CH
3 3-Br, 5-Br Cl H CH 2
CH
3 3-C1, 5-Cl CN Me CH 2
CF
3 3-Cl, 5-Cl CN Me CH 2 -2-Py 3-Cl, 5-Cl CN CH 2
OCH
3
CH
2
CF
3 3-Cl, 5-Cl CN CH 2
OCH
3
CH
2 -2-Py 3-Cl, 5-Cl NO 2 Me CH 2
CF
3 3-CI, 5-Cl NO 2 Me CH 2 -2-Py 3-Cl, 5-Cl NO 2
CH
2
OCH
3
CH
2
CF
3 3-Cl, 5-Cl NO 2
CH
2
OCH
3
CH
2 -2-Py 3-Cl, 5-Cl Cl Me CH 2
CF
3 3-Cl, 5-CI Cl Me CH 2 -2-Py 3-Cl, 5-Cl Cl CH 2
OCH
3
CH
2
CF
3 3-Cl, 5-Cl Cl CH 2
OCH
3
CH
2 -2-Py 3-Cl, 5-Cl CH 3 Me CH 2
CF
3 3-Cl, 5-Cl CH 3 Me CH 2 -2-Py 3-Cl, 5-Cl CH 3
CH
2
OCH
3
CH
2
CF
3 3-Cl, 5-Cl CH 3
CH
2
OCH
3
CH
2 -2-Py Table 2
R
3 F3Cl N 2 Cl R 0
R
3
R
5 R12 RI3 R 3
R
5 RI2 R13 H H H CH 2
CF
3 H H H CH 2 -2-Py Me H H CH 2
CF
3 Me H H CH 2 -2-Py
CH
2
CH
3 H H CH 2
CF
3
CH
2
CH
3 H H CH 2 -2-Py
CH
2
CF
3 H H CH 2
CF
3
CH
2
CF
3 H H CH 2 -2-Py CN H H CH 2
CF
3 CN H H CH 2 -2-Py H NO 2 H CH 2
CF
3 H NO 2 H CH 2 -2-Py Me NO 2 H CH 2
CF
3 Me NO 2 H CH 2 -2-Py WO 2007/123853 PCT/US2007/009181 41
R
3
R
5 R12 R1 3
R
3
R
5 R12 RI3
CH
2
CH
3
NO
2 H CH 2
CF
3
CH
2
CH
3
NO
2 H CH 2 -2-Py CH2CF 3
NO
2 H CH 2
CF
3 CH2CF 3 NO2 H CH 2 -2-Py CN NO 2 H CH 2
CF
3 CN NO 2 H CH 2 -2-Py H CH 3 H CH 2
CF
3 H CH 3 H CH 2 -2-Py Me CH 3 H CH 2
CF
3 Me CH 3 H CH 2 -2-Py
CH
2
CH
3
CH
3 H CH 2
CF
3
CH
2
CH
3
CH
3 H CH 2 -2-Py CH2CF 3
CH
3 H CH 2
CF
3 CH2CF 3
CH
3 H CH 2 -2-Py CN CH 3 H CH 2
CF
3 CN CH 3 H CH 2 -2-Py H Cl H CH2CF 3 H Cl H CH2-2-Py Me Cl H CH 2
CF
3 Me Cl H CH 2 -2-Py
CH
2
CH
3 CI H CH 2
CF
3
CH
2
CH
3 CI H CH 2 -2-Py CH2CF 3 Cl H CH2CF 3 CH2CF 3 Cl H CH2-2-Py CN CI H CH 2
CF
3 CN CI H CH 2 -2-Py H CF 3 H CH 2
CF
3 H CF 3 H CH 2 -2-Py Me CF 3 H CH 2
CF
3 Me CF 3 H CH 2 -2-Py
CH
2
CH
3
CF
3 H CH 2
CF
3
CH
2
CH
3
CF
3 H CH 2 -2-Py
CH
2
CF
3
CF
3 H CH 2
CF
3
CH
2
CF
3
CF
3 H CH 2 -2-Py CN CF 3 H CH 2
CF
3 CN CF 3 H CH 2 -2-Py H CN H CH 2
CF
3 H CN H CH 2 -2-Py Me CN H CH 2
CF
3 Me CN H CH 2 -2-Py
CH
2
CH
3 CN H CH 2
CF
3
CH
2
CH
3 CN H CH 2 -2-Py
CH
2
CF
3 CN H CH 2
CF
3
CH
2
CF
3 CN H CH 2 -2-Py CN CN H CH 2
CF
3 CN CN H CH 2 -2-Py H OMe H CH 2
CF
3 H OMe H CH 2 -2-Py Me OMe H CH 2
CF
3 Me OMe H CH 2 -2-Py
CH
2
CH
3 OMe H CH 2
CF
3
CH
2
CH
3 OMe H CH 2 -2-Py
CH
2
CF
3 OMe H CH 2
CF
3
CH
2
CF
3 OMe H CH 2 -2-Py CN OMe H CH 2
CF
3 CN OMe H CH 2 -2-Py H H H CH 2
CH
3 H CF 3 H CH 2
CH
3 Me H H CH 2
CH
3 Me CF 3 H CH 2
CH
3
CH
2
CH
3 H H CH 2
CH
3
CH
2
CH
3
CF
3 H CH 2
CH
3
CH
2
CF
3 H H CH 2
CH
3
CH
2
CF
3
CF
3 H CH 2
CH
3 CN H H CH 2
CH
3 CN CF 3 H CH 2
CH
3 H NO 2 H CH 2
CH
3 H CN H CH 2
CH
3 Me NO 2 H CH 2
CH
3 Me CN H CH 2
CH
3
CH
2
CH
3
NO
2 H CH 2
CH
3
CH
2
CH
3 CN H CH 2
CH
3
CH
2
CF
3
NO
2 H CH 2
CH
3
CH
2
CF
3 CN H CH 2
CH
3 WO 2007/123853 PCT/US2007/009181 42
R
3
R
5 RI2 R13 R 3
R
5 RI2 R13 CN NO 2 H CH 2
CH
3 CN CN H CH 2
CH
3 H CH 3 H CH 2
CH
3 H OMe H CH 2
CH
3 Me CH 3 H CH 2
CH
3 Me OMe H CH 2
CH
3
CH
2
CH
3
CH
3 H CH 2
CH
3
CH
2
CH
3 OMe H CH 2
CH
3
CH
2
CF
3
CH
3 H CH 2
CH
3
CH
2
CF
3 OMe H CH 2
CH
3 CN CH 3 H CH 2
CH
3 CN OMe H CH 2
CH
3 H Cl H CH 2
CH
3
CH
2
CF
3 Cl H CH 2
CH
3 Me Cl H CH 2
CH
3 CN Cl H CH 2
CH
3
CH
2
CH
3 Cl H CH 2
CH
3 H CN Me CH 2
CF
3 H CN Me CH 2 -2-Py Me CN CH 2
OCH
3
CH
2
CF
3 Me CN CH 2
OCH
3
CH
2 -2-Py H NO 2 Me CH 2
CF
3 H NO 2 Me CH 2 -2-Py Me NO 2
CH
2
OCH
3
CH
2
CF
3 Me NO 2
CH
2
OCH
3
CH
2 -2-Py H Cl Me CH 2
CF
3 H Cl Me CH 2 -2-Py Me Cl CH 2
OCH
3
CH
2
CF
3 Me Cl CH 2
OCH
3
CH
2 -2-Py H CH 3 Me CH 2
CF
3 H CH 3 Me CH 2 -2-Py Me CH 3
CH
2
OCH
3
CH
2
CF
3 Me CH 3
CH
2
OCH
3
CH
2 -2-Py Table 3
F
3 C{ 0 3 N 406 W (R2)m 5 R5 N N N W-1 W-2 W-3 W-4 wherein m is 1, 2, 3, 4 or 5.
(R
2 )m R 5 W (R 2 )m R 5 W 3-Cl, 5-Cl CF 3 W-I 3-C1, 5-Cl H W-I 3-CI, 4-F CF 3 W-1 3-Cl, 4-F H W-1 3-CI, 4-Cl CF 3 W-1 3-Cl, 4-CI H W-1 3-CF 3
CF
3 W-1 3-CF 3 . H W-1 3-Br, 5-Br CF 3 W-1 3-Br, 5-Br H W-1 3-Br CF 3 W-1 3-Br H W-1 WO 2007/123853 PCT/US2007/009181 43
(R
2 )m R 5 W (R 2 )m R 5 W 3-Cl CF 3 W-2 3-Cl H W-2 3-C1, 4-Cl CF 3 W-2 3-Ci, 4-Cl H W-2 3-CI, 5-Cl CF 3 W-2 3-CI, 5-Cl H W-2 3-Cl, 4-F CF 3 W-2 3-CI, 4-F H W-2 3-CI, 4-CF 3
CF
3 W-2 3-CI, 4-CF 3 H W-2 3-CI, 4-Br CF 3 W-2 3-CI, 4-Br H W-2 3-CF 3
CF
3 W-2 3-CF 3 H W-2 3-CF 3 , 5-CF 3
CF
3 W-2 3-CF 3 , 5-CF 3 H W-2 3-Br CF 3 W-2 3-Br H W-2 3-Br, 5-Br CF 3 W-2 3-Br, 5-Br H W-2 3-CI, 5-Cl CF 3 W-3 3-Cl, 5-Cl H W-3 3-Cl, 4-F CF 3 W-3 3-Cl, 4-F H W-3 3-CI, 4-Cl CF 3 W-3 3-C1, 4-Cl H W-3 3-CF 3
CF
3 W-3 3-CF 3 H W-3 3-Br, 5-Br CF 3 W-3 3-Br, 5-Br H W-3 3-Br CF 3 W-3 3-Br H W-3 3-CI, 5-Cl CF 3 W-4 3-Cl, 5-Cl H W-4 3-Cl, 4-F CF 3 W-4 3-C1, 4-F H W-4 3-Cl, 4-Cl CF 3 W-4 3-Cl, 4-Cl H W-4 3-CF 3
CF
3 W-4 3-CF 3 H W-4 3-Br, 5-Br CF 3 W-4 3-Br, 5-Br H W-4 3-Br CF 3 W-4 3-Br H W-4 3-Cl, 5-Cl CH 3 W-1 3-Cl, 5-Cl NO 2 W-1 3-CI, 4-F CH 3 W-1 3-CI, 4-F NO 2 W-1 3-CI, 4-CI CH 3 W-1 3-CI, 4-Cl NO 2 W-I 3-CF 3
CH
3 W-1 3-CF 3
NO
2 W-1 3-Br, 5-Br CH 3 W-1 3-Br, 5-Br NO 2 W-1 3-Br CH 3 W-1 3-Br NO 2 W-1 3-Cl CH 3 W-2 3-Cl NO 2 W-2 3-Cl, 4-Cl CH 3 W-2 3-Cl, 4-CI NO 2 W-2 3-Cl, 5-CI CH 3 W-2 3-Cl, 5-Cl NO 2 W-2 3-CI, 4-F CH 3 W-2 3-Cl, 4-F NO 2 W-2 3-CI, 4-CF 3
CH
3 W-2 3-C1, 4-CF 3
NO
2 W-2 3-CI, 4-Br CH 3 W-2 3-Cl, 4-Br NO 2 W-2 3-CF 3
CH
3 W-2 3-CF 3
NO
2 W-2 3-CF 3 , 5-CF 3
CH
3 W-2 3-CF 3 , 5-CF 3
NO
2 W-2 3-Br CH 3 W-2 3-Br NO 2 W-2 WO 2007/123853 PCT/US2007/009181 44
(R
2 )m R 5 W (R 2 )m R S W 3-Br, 5-Br CH 3 W-2 3-Br, 5-Br NO 2 W-2 3-C1, 5-Cl CH 3 W-3 3-C1, 5-Cl NO 2 W-3 3-Cl, 4-F CH 3 W-3 3-Cl, 4-F NO 2 W-3 3-CI, 4-Cl CH 3 W-3 3-Cl, 4-Cl NO 2 W-3 3-CF 3
CH
3 W-3 3-CF 3
NO
2 W-3 3-Br, 5-Br CH 3 W-3 3-Br, 5-Br NO 2 W-3 3-Br CH 3 W-3 3-Br NO 2 W-3 3-C], 5-Cl CH 3 W-4 3-Cl, 5-Cl NO 2 W-4 3-Cl, 4-F CH 3 W-4 3-Cl, 4-F NO 2 W-4 3-CI, 4-Cl CH 3 W-4 3-Cl, 4-Cl NO 2 W-4 3-CF 3
CH
3 W-4 3-CF 3
NO
2 W-4 3-Br, 5-Br CH 3 W-4 3-Br, 5-Br NO 2 W-4 3-Br CH 3 W-4 3-Br NO 2 W-4 3-C1, 5-Cl Cl W-I 3-C1, 5-CI OMe W-I 3-Cl, 4-F Cl W-I 3-C1, 4-F OMe W-I 3-Cl, 4-Cl Cl W-1 3-Cl, 4-Cl .OMe W-1 3-CF 3 Cl W-1 3-CF 3 OMe W-1 3-Br, 5-Br Cl W-1 3-Br, 5-Br OMe W-1 3-Br Cl W-1 3-Br OMe W-1 3-Cl Cl W-2 3-Cl OMe W-2 3-Cl, 4-Cl Cl W-2 3-Cl, 4-Cl OMe W-2 3-CI, 5-Cl Cl W-2 3-Cl, 5-Cl OMe W-2 3-CI, 4-F Cl W-2 3-Cl, 4-F OMe W-2 3-Cl, 4-CF 3 Cl W-2 3-C1, 4-CF 3 OMe W-2 3-CI, 4-Br Cl W-2 3-C1, 4-Br OMe W-2 3-CF 3 CI W-2 3-CF 3 OMe W-2 3-CF 3 , 5-CF 3 Cl W-2 3-CF 3 , 5-CF 3 OMe W-2 3-Br Cl W-2 3-Br OMe W-2 3-Br, 5-Br Cl W-2 3-Br, 5-Br OMe W-2 3-Cl, 5-CI Cl W-3 3-CI, 5-CI OMe W-3 3-Cl, 4-F Cl W-3 3-Cl, 4-F OMe W-3 3-CI, 4-CI Cl W-3 3-C1, 4-CI OMe W-3 3-CF 3 Cl W-3 3-CF 3 OMe W-3 3-Br, 5-Br Cl W-3 3-Br, 5-Br OMe W-3 3-Br Cl W-3 3-Br OMe W-3 3-Cl, 5-CI Cl W-4 3-Cl, 5-Cl OMe W-4 3-CI, 4-F Cl W-4 3-CI, 4-F OMe W-4 WO 2007/123853 PCT/US2007/009181 45
(R
2 )m R 5 W (R 2 )m R 5 W 3-Cl, 4-Cl Cl W-4 3-Cl, 4-Cl OMe W-4 3-CF 3 Cl W-4 3-CF 3 OMe W-4 3-Br, 5-Br Cl W-4 3-Br, 5-Br OMe W-4 3-Br Cl W-4 3-Br OMe W-4 3-Cl, 5-Cl CN W-1 3-Cl1, 5-Cl CN W-3 3-Cl, 4-F CN W-1 3-C1, 4-F CN W-3 3-Cl, 4-Cl CN W-1 3-C1, 4-Cl CN W-3 3-CF 3 CN W-1 3-CF 3 CN W-3 3-Br, 5-Br CN W-1 3-Br, 5-Br CN W-3 3-Br CN W-1 3-Br CN W-3 3-Cl CN W-2 3-C1, 5-Cl CN W-4 3-Cl, 4-Cl CN W-2 3-Cl1, 4-F CN W-4 3-Cl, 5-CI CN W-2 3-C1, 4-Cl CN W-4 3-Cl, 4-F CN W-2 3-CF 3 CN W-4 3-Cl, 4-CF 3 CN W-2 3-Br, 5-Br CN W-4 3-C1, 4-Br CN W-2 3-Br CN W-4 3-CF 3 CN W-2 3-Br CN W-2 3-CF 3 , 5-CF 3 CN W-2 3-Br, 5-Br CN W-2 Table 4
R
3
F
3 C N 4XV 6 4 /6: /f;: W
(R
2 )m 5
R
5 N-N \N N N
N
g N N N N W-1 W-2 W-3 W-4 wherein m is 1, 2, 3, 4 or 5.
(R
2 )m R 3
R
5 W (R 2 )m R 3
R
5 W 3-CI, 5-CI H H W-1 3-C1, 5-Cl H H W-2 3-CI, 5-Cl Me H W-1 3-CI, 5-CI Me H W-2 3-CI, 5-Cl CH 2
CH
3 H W-1 3-Cl, 5-Cl CH 2
CH
3 H W-2 3-C1, 5-Cl CH 2
CF
3 H W-1 3-CI, 5-Cl CH 2
CF
3 H W-2 WO 2007/123853 PCT/US2007/009181 46
(R
2 )m R 3
R
5 W (R 2 )m R 3
R
5 W 3-Cl, 5-Cl CN H W-1 3-Cl, 5-Cl CN H W-2 3-C1, 5-Cl H NO 2 W-1 3-Cl, 5-Cl H NO 2 W-2 3-CI, 5-Cl Me NO 2 W-1 3-Cl, 5-Cl Me NO 2 W-2 3-C1, 5-Cl CH 2
CH
3
NO
2 W-1 3-CI, 5-Cl CH 2
CH
3
NO
2 W-2 3-Cl, 5-Cl CH 2
CF
3
NO
2 W-1 3-Cl, 5-Cl CH 2
CF
3
NO
2 W-2 3-C1, 5-Cl CN NO 2 W-1 3-Cl, 5-Cl CN NO 2 W-2 3-Cl, 5-CI H CH 3 W-1 3-Cl, 5-Cl H CH 3 W-2 3-Cl, 5-Cl Me CH 3 W-1 3-C1, 5-Cl Me CH 3 W-2 3-Cl, 5-CI CH 2
CH
3
CH
3 W-1 3-C1, 5-Cl CH 2
CH
3
CH
3 W-2 3-Cl, 5-CI CH 2
CF
3
CH
3 W-1 3-CI, 5-CI CH 2
CF
3
CH
3 W-2 3-CI, 5-Cl CN CH 3 W-1 3-Cl, 5-Cl CN CH 3 W-2 3-Cl, 5-Cl H CI W-1 3-CI, 5-Cl H Cl W-2 3-CI, 5-Cl Me Cl W-1 3-C, 5-Cl Me Cl W-2 3-CI, 5-Cl CH 2
CH
3 Cl W-1 3-Cl, 5-Cl CH 2
CH
3 Cl W-2 3-Cl, 5-Cl CH 2
CF
3 Cl W-1 3-Cl, 5-Cl CH 2
CF
3 Cl W-2 3-Cl, 5-Cl CN Cl W-1 3-C1, 5-Cl CN Cl W-2 3-C1, 5-CI H CF 3 W-1 3-Cl, 5-CI H CF 3 W-2 3-C1, 5-Cl Me CF 3 W-1 3-Cl, 5-Cl Me CF 3 W-2 3-Cl, 5-Cl CH 2
CH
3
CF
3 W-1 3-CI, 5-Cl CH 2
CH
3
CF
3 W-2 3-Cl, 5-CI CH 2
CF
3
CF
3 W-1 3-Cl, 5-Cl CH 2
CF
3
CF
3 W-2 3-CI, 5-Cl CN CF 3 W-1 3-CI, 5-Cl CN CF 3 W-2 3-Cl, 5-Ci H CN W-1 3-Cl, 5-Cl H CN W-2 3-C1, 5-Cl Me CN W-1 3-C1, 5-Cl Me CN W-2 3-Cl, 5-Cl CH 2
CH
3 CN W-1 3-Cl, 5-Cl CH 2
CH
3 CN W-2 3-Cl, 5-CI CH 2
CF
3 CN W-1 3-Cl, 5-CI CH 2
CF
3 CN W-2 3-Cl, 5-Cl CN CN W-1 3-C1, 5-CI CN CN W-2 3-C1, 5-Cl H OMe W-1 3-CI, 5-Cl H OMe W-2 3-CI, S-CI Me OMe W-1 3-Cl, 5-CI Me OMe W-2 3-Cl, 5-Cl CH 2
CH
3 OMe W-1 3-CI, 5-Cl CH 2
CH
3 OMe W-2 3-C1, 5-Cl CH 2
CF
3 OMe W-1 3-Cl, 5-Cl CH 2
CF
3 OMe W-2 3-CI, 5-Cl CN OMe W-1 3-Cl, 5-Cl CN OMe W-2 3-CI, 5-Cl H H W-3 3-Cl, 5-Cl H H W-4 3-CI, 5-CI Me H W-3 3-Cl, 5-Cl Me H W-4 3-Cl, 5-Cl CH 2
CH
3 H W-3 3-CI, 5-Cl CH 2
CH
3 H W-4 3-CI, S-CI CH 2
CF
3 H W-3 3-CI, 5-CI CH 2
CF
3 H W-4 3-CI, 5-Cl CN H W-3 3-CI, 5-Cl CN H W-4 3-Cl, 5-CI H NO 2 W-3 3-Cl, 5-Cl H NO 2 W-4 WO 2007/123853 PCT/US2007/009181 47
(R
2 )m R 3
R
5 W (R 2 )m R 3
R
5 W 3-Cl, 5-Cl Me NO 2 W-3 3-Cl, 5-Cl Me NO 2 W-4 3-Ci, 5-Cl CH 2
CH
3
NO
2 W-3 3-CI, 5-Cl CH 2
CH
3
NO
2 W-4 3-Cl, 5-Cl CH 2
CF
3
NO
2 W-3 3-Cl, 5-Cl CH 2
CF
3
NO
2 W-4 3-Cl, 5-Cl CN NO 2 W-3 3-Cl, 5-Cl CN NO 2 W-4 3-CI, 5-Cl H CH 3 W-3 3-C0, 5-Cl H CH 3 W-4 3-Cl, 5-Cl Me CH 3 W-3 3-Cl, 5-CI Me CH 3 W-4 3-Cl, 5-Cl CH 2
CH
3
CH
3 W-3 3-Cl, 5-CI CH 2
CH
3
CH
3 W-4 3-Cl, 5-Cl CH 2
CF
3
CH
3 W-3 3-Cl, 5-Cl CH 2
CF
3
CH
3 W-4 3-C0, 5-Cl CN CH 3 W-3 3-CI, 5-CI CN CH 3 W-4 3-Cl, 5-Cl H Cl W-3 3-CI, 5-Cl H Cl W-4 3-Cl, 5-Cl Me Cl W-3 3-Cl, 5-Cl Me Cl W-4 3-Cl, 5-Cl CH 2
CH
3 Cl W-3 3-CI, 5-Cl CH 2
CH
3 Cl W-4 3-Cl, 5-Cl CH 2
CF
3 Cl W-3 3-Cl, 5-Cl CH 2
CF
3 Cl W-4 3-CI, 5-CI CN Cl W-3 3-Cl, 5-Cl CN CI W-4 3-Cl, 5-Cl H CF 3 W-3 3-CI, 5-Cl H CF 3 W-4 3-Cl, 5-CI Me CF 3 W-3 3-CI, 5-Cl Me CF 3 W-4 3-Cl, 5-Cl CH 2
CH
3
CF
3 W-3 3-CI, 5-Cl CH 2
CH
3
CF
3 W-4 3-CI, 5-Cl CH 2
CF
3
CF
3 W-3 3-CI, 5-Cl CH 2
CF
3
CF
3 W-4 3-Cl, 5-Cl CN CF 3 W-3 3-Cl, 5-Cl CN CF 3 W-4 3-Cl, 5-Cl H CN W-3 3-Cl, 5-Cl H CN W-4 3-CI, 5-CI Me CN W-3 3-Cl, 5-Cl Me CN W-4 3-Cl, 5-Cl CH 2
CH
3 CN W-3 3-CI, 5-CI CH 2
CH
3 CN W-4 3-Cl, 5-CI CH 2
CF
3 CN W-3 3-Cl, 5-Cl CH 2
CF
3 CN W-4 3-Cl, 5-CI CN CN W-3 3-CI, 5-Cl CN CN W-4 3-Cl, 5-CI H OMe W-3 3-Cl, 5-Cl H OMe W-4 3-Cl, 5-CI Me OMe W-3 3-Cl, 5-Cl Me OMe W-4 3-Cl, 5-Cl CH 2
CH
3 OMe W-3 3-CI, 5-Cl CH 2
CH
3 OMe W-4 3-Cl, 5-Cl CH 2
CF
3 OMe W-3 3-CI, 5-Cl CH 2
CF
3 OMe W-4 3-Cl. 5-Cl CN OMe W-3 3-C1, 5-Cl CN OMe W-4 3-Br H H W-2 3-Br H CF 3 W-2 3-Br Me H W-2 3-Br Me CF 3 W-2 3-Br CH 2
CH
3 H W-2 3-Br CH 2
CH
3
CF
3 W-2 3-Br CH 2
CF
3 H W-2 3-Br CH 2
CF
3
CF
3 W-2 3-Br CN H W-2 3-Br CN CF 3 W-2 3-Br H NO 2 W-2 3-Br H CN W-2 3-Br Me NO 2 W-2 3-Br Me CN W-2 3-Br CH 2
CH
3
NO
2 W-2 3-Br CH 2
CH
3 CN W-2 WO 2007/123853 PCT/US2007/009181 48
(R
2 )m R 3
R
5 W (R 2 )m R 3
R
5 W 3-Br CH 2
CF
3
NO
2 W-2 3-Br CH 2
CF
3 CN W-2 3-Br CN NO 2 W-2 3-Br CN CN W-2 3-Br H CH 3 W-2 3-Br H OMe W-2 3-Br Me CH 3 W-2 3-Br Me OMe W-2 3-Br CH 2
CH
3
CH
3 W-2 3-Br CH 2
CH
3 OMe W-2 3-Br CH 2
CF
3
CH
3 W-2 3-Br CH 2
CF
3 OMe W-2 3-Br CN CH 3 W-2 3-Br CN OMe W-2 3-Br H CI W-2 3-Br CH 2
CF
3 Cl W-2 3-Br Me Cl W-2 3-Br CN CI W-2 3-Br CH 2
CH
3 CI W-2 Table 5 O
F
3 C N - 1 w R2 Zl R5 N \ H H yN N N N N
CF
3 z:z7N IIY 0 0 W-2 W-4 W-5 W-6
R
2
R
5 ZI Z 2 W R 2
R
5 Zl Z 2 W Br CI CH N W-2 Br Cl CH N W-4 Br H CH N W-2 Br H CH N W-4 Br Me CH N W-2 Br Me CH N W-4
CF
3 CI CH N W-2 CF 3 CI CH N W-4
CF
3 H CH N W-2 CF 3 H CH N W-4
CF
3 Me CH N W-2 CF 3 Me CH N W-4 Cl CI CH N W-2 Cl CI CH N W-4 CI H CH N W-2 Cl H CH N W-4 CI Me CH N W-2 Cl Me CH N W-4
CF
3 Cl N CCI W-2 CF 3 CI N CCI W-4
CF
3 H N CCI W-2 CF 3 H N CCI W-4
CF
3 Me N CCI W-2 CF 3 Me N CCI W-4 CI CI N CCI W-2 CI CI N CCI W-4 WO 2007/123853 PCT/US2007/009181 49
R
2
R
S ZW Z 2 W R 2
R
5 ZI Z 2 W CI H N CCI W-2 CI H N CCI W-4 Cl Me N CCI W-2 Cl Me N CCI W-4 Br CI CH N W-5 Br Cl CH N W-6 Br H CH N W-5 Br H CH N W-6 Br Me CH N W-5 Br Me CH N W-6
CF
3 Cl CH N W-5 CF 3 Cl CH N W-6
CF
3 H CH N W-5 CF 3 H CH N W-6
CF
3 Me CH N W-5 CF 3 Me CH N W-6 Cl Cl CH N W-5 CI Cl CH N W-6 CI H CH N W-5 CI H CH N W-6 CI Me CH N W-5 Cl Me CH N W-6
CF
3 CI N CCI W-5 CF 3 CI N CCI W-6
CF
3 H N CCI W-5 CF 3 H N CCI W-6
CF
3 Me N CCI W-5 CF 3 Me N CCI W-6 Cl CI N CCI W-5 Cl CI N CCI W-6 CI H N CCI W-5 CI H N CCI W-6 CI Me N CCI W-5 CI Me N CCI W-6 Table 6
R
3 N
F
3 C N - II R 5 -N H H N N N N \N N CF3 0 0 W-2 W-4 W-5 W-6 R2 R3 R5 Z 1
Z
2 Q R2 R3 R5 Zl Z 2 Q Br H H CH N W-2 Br H H CH N W-4 Br Me H CH N W-2 Br Me H CH N W-4 Br H Me CH N W-2 Br H Me CH N W-4 Br Me Me CH N W-2 Br Me Me CH N W-4 Br H CI CH N W-2 Br H CI CH N W-4 Br Me CI CH N W-2 Br Me CI CH N W-4 WO 2007/123853 PCT/US2007/009181 50 R2 R3 R5 Z 1
Z
2 Q R2 R3 R5 ZI Z2 Q CI H H CH N W-2 Cl H H CH N W-4 CI Me H CH N W-2 Cl Me H CH N W-4 CI H Me CH N W-2 CI H Me CH N W-4 CI Me Me CH N W-2 CI Me Me CH N W-4 CI H CI CH N W-2 CI H CI CH N W-4 Cl Me CI CH N W-2 Cl Me CI CH N W-4 CI H H N CCI W-2 CI H H N CCI W-4 CI Me H N CCI W-2 CI Me H N CCI W-4 CI H Me N CCI W-2 Cl H Me N CCI W-4 Cl Me Me N CCI W-2 CI Me Me N CCI W-4 Cl H Cl N CCI W-2 CI H Cl N CCI W-4 CI Me Cl N CCI W-2 CI Me Cl N CCI W-4 Br H H CH N W-5 Br H H CH N W-6 Br Me H CH N W-5 Br Me H CH N W-6 Br H Me CH N W-5 Br H Me CH N W-6 Br Me Me CH N W-5 Br Me Me CH N W-6 Br H CI CH N W-5 Br H Cl CH N W-6 Br Me Cl CH N W-5 Br Me Cl CH N W-6 Cl H H CH N W-5 CI H H CH N W-6 CI Me H CH N W-5 Cl Me H CH N W-6 CI H Me CH N W-5 CI H Me CH N W-6 CI Me Me CH N W-5 Cl Me Me CH N W-6 CI H Cl CH N W-5 Cl H CI CH N W-6 CI Me CI CH N W-5 CI Me Cl CH N W-6 CI H H N CCI W-5 CI H H N CCI W-6 CI Me H N CCI W-5 Cl Me H N CCI W-6 Cl H Me N CCI W-5 CI H Me N CCI W-6 CI Me Me N CCI W-5 Cl Me Me N CCI W-6 CI H CI N CCI W-5 CI H Cl N CCl W-6 CI Me CI N CCI W-5 CI Me Cl N CCI W-6 WO 2007/123853 PCT/US2007/009181 51 Table 7 O
F
3 C N - I Cl (: Q
R
5 Cl
R
5 Q R5 Q Cl SO 2 NHMe Me SO 2 NHMe Cl SO 2 NMe 2 Me SO 2 NMe 2 Cl SO 2
NHCH
2
CH
2
=CH
2 Me SO 2
NHCH
2
CH
2 -- CH 2 Cl SO 2
N(CH
3
)CH
2
CH
2
-CH
2 Me SO 2
N(CH
3
)CH
2
CH
2
-CH
2 Cl SO 2
NHCH
2
CF
3 Me SO 2
NHCH
2
CF
3 Cl SO 2
N(CH
3
)CH
2
CF
3 Me SO 2
N(CH
3
)CH
2
CF
3 Cl SO 2
NHCH
2 C-CH Me SO 2
NHCH
2 C CH Cl SO 2
N(CH
3
)CH
2 C-CH Me SO 2
N(CH
3
)CH
2 C-CH Cl SO 2
NHCH
2 -2-Py Me SO 2
NHCH
2 -2-Py Cl SO 2
N(CH
3
)CH
2 -2-Py Me SO 2
N(CH
3
)CH
2 -2-Py Cl C(=S)NHMe Me C(=S)NHMe Cl C(=S)NMe 2 Me C(-S)NMe 2 Cl C(=S)NHCH 2
CH
2
=CH
2 Me C(-S)NHCH 2
CH
2
=CH
2 Cl C(=S)N(CH 3
)CH
2
CH
2
-CH
2 Me C(=S)N(CH 3
)CH
2
CH
2
=CH
2 Cl C(=S)NHCH 2
CF
3 Me C(=S)NHCH 2
CF
3 Cl C(=S)N(CH 3
)CH
2
CF
3 Me C(=S)N(CH 3
)CH
2
CF
3 Cl C(=S)NHCH 2 C=CH Me C(=S)NHCH 2 C=CH Cl C(=S)N(CH 3
)CH
2 C-CH Me C(=S)NMeCH 2 C=-CH Cl C(=S)NHCH 2 -2-Py Me C(=S)NHCH 2 -2-Py Cl C(=S)N(CH 3
)CH
2 -2-Py Me C(=S)N(CH 3
)CH
2 -2-Py Cl F Me F Cl Cl Me Cl Cl CN Me CN Cl NO 2 Me NO 2 Cl 4-morpholinyl Me 4-morpholinyl CN SO 2 NHMe NO 2
SO
2 NHMe CN SO 2 NMe 2
NO
2
SO
2 NMe 2 CN SO 2
NHCH
2
CH
2
-CH
2
NO
2
SO
2
NHCH
2
CH
2
=CH
2 CN SO 2
N(CH
3
)CH
2
CH
2
-CH
2
NO
2
SO
2
N(CH
3
)CH
2
CH
2
=CH
2 WO 2007/123853 PCT/US2007/009181 52
R
5 Q R 5 Q CN SO 2
NHCH
2
CF
3
NO
2
SO
2
NHCH
2
CF
3 CN SO 2
N(CH
3
)CH
2
CF
3
NO
2
SO
2
NCCH
3
)CH
2
CF
3 CN SO 2
NHCH
2 C -CH N0 2
SO
2
NHCH
2 C=-CH CN SO 2
N(CH
3
)CH
2 C=-CH NO 2
SO
2
N(CH
3
)CH
2 C-=CH CN SO 2
NHCH
2 -2-PY NO 2
SO
2
NH-CH
2 -2-Py CN SO 2
N(CH
3
)CH
2 -2-Py NO 2
SO
2
N(CH
3
)CH
2 -2-Py CN C(--S)N-1Me NO 2 C(=S)NHMe CN C(--S)NMe 2
NO
2 C(--S)NMe 2 CN C(=S)NHCH 2
CH
2 -- CH 2
NO
2
C(=S)NHCH
2
CH
2 -- CH 2 CN C(=S)N(CH 3
)CH
2
CH
2
=-CH
2
NO
2
C(=S)N(CH
3
)CH
2
CH
2 -- CH 2 CN C(=S)NIICH 2
CF
3
NO
2
C(=S)NHCH
2
CF
3 CN C(=S)N(CH 3
)CH
2
CF
3
NO
2
C(=S)N(CH
3
)CH
2
CF
3 CN C(=S)NI-1CH 2 C.=-CH N0 2
C(=S)NHCH
2 C--CH CN C(=S)N(CH 3
)CH
2 C--CH NO 2
C(=S)N(CH
3
)CH
2 C-=CH CN C(=S)NHCH 2 -2-Py NO 2
C(=S)NHCH
2 -2-Py CN G(=S)N(CH 3
)CH
2 -2-Py NO 2
C(=S)N(CH
3
)CH
2 -2-Py CN F NO 2 F CN cI NO 2 CI CN CN NO 2 CN CN NO 2
NO
2
NO
2 CN 4-morpholinyl NO 2 4-morpholinyl Table 8 R3
F
3 C N cI R3 R 5 Q R3__ R 5 Q H cI S0 2 NHMe H Me S0 2 NHMe Me CI S0 2 NHMe Me Me S0 2 NHMe H CI S0 2 NMe 2 H Me SO 2 NMe 2 Me CI SO 2 NMe 2 Me Me S0 2 NMe 2 H CI S0 2
NHCH
2
CH
2 -- CH 2 H Me S0 2
NHCH
2
CH
2
=CH
2 Me CI SO 2
NHCH
2
CH
2
=CH
2 Me Me S0 2
NHCH
2
CH
2
=CH
2 WO 2007/123853 PCT/US2007/009181 53 R3__ R5_ Q R3__ R5__ Q H CI SO 2
NI{CH
2
CF
3 H Me SO 2
NHCH
2
CF
3 Me CI SO 2
NHCH
2
CF
3 Me Me SO 2
NH-CH
2
CF
3 H CI SO 2
N(CH
3
)CH
2
CF
3 H Me SO 2
N(CH
3
)CH
2
CF
3 Me CI SO 2
N(CH
3
)CH
2
CF
3 Me Me SQ 2
N(CH
3
)CH
2
CF
3 H CI SO 2
NH-CH
2 C--CH H Me SO 2
NHCH
2 C -CH Me CI SO 2
NHCH
2 C-=CH Me Me SO 2
NHCH
2 C--CH H Cl SQ 2
NCH
2 -2-Py H Me SO 2
NHCH
2 -2-Py Me CI SO 2
NHCH
2 -2-Py Me Me SO 2
NHCH
2 -2-Py H CI SO 2
N(CH
3
)CH
2 -2-Py H Me SO 2
N(CH
3
)CH
2 -2-Py Me CI SO 2
N(CH
3
)CH
2 -2-Py Me Me SO 2
N(CH
3
)CH
2 -2-Py H CI C(=S)NHMe H Me C(=S)NIJMe me CI C(=S)NHMe Me. Me C(=S)NHMe H CI C(=S)NMe 2 H Me C(=S)NMe 2 Me CI C(=S)NMe 2 Me Me C(=S)NMe 2 H CI C(=S)NHCH 2
CH
2 -- CH 2 H Me C(=S)NHCH 2
CH
2
=CH
2 Me C! C(=S)NHCH 2
CH
2
=CH
2 Me Me C(=S)NHCH 2
CH
2
=CH
2 H CI C(=S)NHCH 2
CF
3 H Me C(=S)NIICH 2
CF
3 Me CI C(=S)NHCH 2
CF
3 Me Me C(=S)NHCH 2
CF
3 H CI C(=S)N(CH 3
)CH
2
CF
3 H Me C(=S)N(CH 3
)CH
2
CF
3 Me CI C(=S)N(CH 3
)CH
2
CF
3 Me Me C(=S)N(CH 3
)CH
2
CF
3 H CI C(=S)NHCH 2 C3ECH H Me C(=S)N1{CH 2 C=-CH Me Cl C(=S)NHCH 2 C-=CH Me Me C(=S)NHCH 2 C5=CH H Cl C(=S)N(CH 3
)CH
2 C-=CH H Me C(--S)N(CH 3
)CH
2 C CH Me Cl C(=S)N(CH 3
)CH
2 C--CH Me Me C(=S)N(CH 3
)CH
2 C--CH H CI C(=S)NHCH 2 -2-Py H Me C(=S)NHCH 2 -2-Py Me CI C(=S)NHCH 2 -2-Py Me Me C(=S)NIICH 2 -2-Py H CI C(=S)N(CH 3 ) CH 2 -2-Py H Me C(=S)N(CH 3
)CH
2 -2-Py Me CI C(=S)N(CH 3
)CH
2 -2-Py Me Me C(=S)N(CH 3 )CH4 2 -2-Py H CI F H Me F Me CI F Me Me F H CI CI H Me CI Me CI CI Me Me CI H CI CN H Me CN Me CI CN Me Me CN H CI NO 2 H Me NO 2 Me CI NO 2 Me Me NO 2 H CI 4-morpholinyl H Me 4-morpholinyl WO 2007/123853 PCT/US2007/009181 54
R
3
R
5 Q R 3
R
5 Q Me CI 4-morpholinyl Me Me 4-morpholinyl H CN SO 2 NHMe H NO 2
SO
2 NHMe Me CN SO 2 NHMe Me NO2 SO 2 NHMe H CN SO 2 NMe 2 H NO 2
SO
2 NMe 2 Me CN SO 2 NMe 2 Me NO 2
SO
2 NMe 2 H CN SO 2
NHCH
2
CH
2
--CH
2 H NO 2
SO
2
NHCH
2
CH
2
--CH
2 Me CN SO 2
NHCH
2
CH
2
=CH
2 Me NO 2 SO2NHCH 2
CH
2
--CH
2 H CN SO 2
NHCH
2
CF
3 H NO 2
SO
2
NHCH
2
CF
3 Me CN SO 2
NHCH
2
CF
3 Me NO 2 SO2NHCH 2
CF
3 H CN SO 2
N(CH
3
)CH
2
CF
3 H NO 2
SO
2
N(CH
3
)CH
2
CF
3 Me CN SO2N(CH 3
)CH
2
CF
3 Me NO 2
SO
2
N(CH
3
)CH
2
CF
3 H CN SO 2
NHCH
2 C-CH H NO 2
SO
2
NHCH
2 C=CH Me CN SO 2
NHCH
2 C-CH Me NO 2
SO
2
NHCH
2 C=CH H CN SO 2
NHCH
2 -2-Py H NO 2
SO
2
NHCH
2 -2-Py Me CN SO 2
NHCH
2 -2-Py Me NO 2
SO
2
NHCH
2 -2-Py H CN SO 2
N(CH
3
)CH
2 -2-Py H NO 2
SO
2
N(CH
3
)CH
2 -2-Py Me CN SO 2
N(CH
3
)CH
2 -2-Py Me NO 2
SO
2
N(CH
3
)CH
2 -2-Py H CN C(=S)NHMe H NO 2 C(=S)NHMe Me CN C(=S)NHMe Me NO 2 C(=S)NHMe H CN C(=S)NMe 2 H NO 2 C(=S)NMe 2 Me CN C(=S)NMe 2 Me NO 2 C(=S)NMe 2 H CN C(=S)NHCH 2
CH
2
--CH
2 H NO 2
C(=S)NCH
2
CH
2
=CH
2 Me CN C(=S)NHCH 2
CH
2
=CH
2 Me NO2 C(-=S)NHCH 2
CH
2
--CH
2 H CN C(=S)NHCH 2
CF
3 H NO 2
C(=S)NHCH
2
CF
3 Me CN C(=S)NHCH 2
CF
3 Me NO 2
C(=S)NHCH
2
CF
3 H CN C(=S)N(CH 3
)CH
2
CF
3 H NO 2
C(=S)N(CH
3
)CH
2
CF
3 Me CN C(=S)N(CH 3
)CH
2
CF
3 Me NO 2
C(=S)N(CH
3
)CH
2
CF
3 H CN C(=S)NHCH 2 C-CH H NO 2
C(=S)NHCH
2 C-CH Me CN C(=S)NHCH 2 C-CH Me NO 2
C(=S)NHCH
2 C-CH H CN C(=S)N(CH 3
)CH
2 C=CH H NO 2
C(=S)N(CH
3
)CH
2 C-CH Me CN C(=S)N(CH 3
)CH
2 C-CH Me NO 2
C(=S)N(CH
3
)CH
2 C-CH H CN C(=S)NHCH 2 -2-Py H NO 2
C(=S)NHCH
2 -2-Py Me CN C(=S)NHCH 2 -2-Py Me NO 2
C(=S)NHCH
2 -2-Py H CN C(=S)N(CH 3
)CH
2 -2-Py H NO 2
C(=S)N(CH
3
)CH
2 -2-Py Me CN C(=S)N(CH 3
)CH
2 -2-Py Me NO 2
C(=S)N(CH
3
)CH
2 -2-Py H CN F H NO 2 F Me CN F Me NO 2
F
WO 2007/123853 PCT/US2007/009181 55 R3__ R5_ Q R 3
R
5 Q H CM CI H N0 2 CI Me CM CI Me NO 2 CI H CN CN H NO 2 CN Me CN CN *Me NO 2 CN H CN N0 2 H N0 2
NO
2 Me CN N02 Me N0 2
NO
2 H CM 4-morpholinyl H N02 4-morpholinyl Me CM 4-moi-pholinyl Me N02 4-morpholinyl Table 9
F
3 C r N ':: Q
R
5 CI R5_____ Q R5______ Q Cl C(O)NHEt Me S0 2
NHCH
2 -2-Py CI C(O)NIICH 2
CF
3 Me 1-imidazoyl CI C(O)NHCH 2 -2-Py Me 1H-1,2,4-triazol-1-yi CI S0 2
NHCH
2
CF
3 Me 4-morpholinyl CI S0 2
NHCH
2 -2-Py N0 2 C(O)NHEt CI I-imidazoyl NO 2
C(O)NHCH
2
CF
3 CI I H-I,2,4-triazol- l-yI NO 2
C(O)NHCH
2 -2-Py CI 4-morpholinyl NO 2
SO
2
NHCH
2
CF
3 CM C(O)NHEt N0 2 S0 2
NHCH
2 -2-Py CM C(O)NHCH 2
CF
3 N0 2 1-imidazoyl CN C(O)NHCH 2 -2-Py NO 2 IH-1 ,2,4-triazol-1-yl CN S0 2
NHCH
2
CF
3 N0 2 4-morpholinyl CN SO 2
NHCH
2 -2-Py H C(O)NHEt CN 1-imidazoyl H C(O)NHCH 2
CF
3 CN I H-i 2,4-triazol- l-yi H C(O)NHCH 2 -2-Py CN 4-morpholinyl H SO 2
NHCH
2
CF
3 Me C(O)NHEt H SO 2
NHCH
2 -2-Py Me C(O)NHCH 2
CF
3 H I-imidazoyl Me C(O)NHCH 2 -2-Py H 1 H-I ,2,4-triazol- l-yi WO 2007/123853 PCT/US2007/009181 56 R5____ Q R 5 Q Me SO 2
NHCH
2
CF
3 H 4-morpholinyl Table 10
F
3 CI N
R
5 CI
R
5 U Q R 5 U Q
CF
3 S(=O) IH-1,2,4-triazol-1-yl H S(=O) IH-I,2,4-triazol-1-yI
CF
3 S(0) 2 IH-1,2,4-triazol-1-yi H S02 IH-1,2,4-triazol-1-yi
CF
3 S(=O) C(O)NHCH 2 -2-Py H S(=O) C(O)NHCH 2 -2-Py
CF
3 S(0) 2
C(O)NHCH
2 -2-Py H S02 C(O)NHCH 2 -2-Py
CF
3 S(=O) C(O)NHCH 2
CF
3 H S(=O) C(O)NHCH 2
CF
3
CF
3 S(0) 2
C(O)NHCH
2
CF
3 H S(0) 2
C(O)NHCH
2
CF
3
CF
3 S(=O) C(O)NIIEt H S(=-O) C(O)NHEt
CF
3 S02C(O)NHEt H S02C(O)NHEt CI S(=O) IH-1,2,4-triazol-1-yi Me S(=O) IH-I,2,4-t-iazol-1-yi CI S(0) 2 IH-1,2,4-triazol-1-yl Me S(0) 2 IH-I.2,4-triazol-1-yi CI S(=O) C(O)NHCH 2 -2-Py Me S(=O) C(O)NHCH 2 -2-Py Cl S(0) 2
C(O)NHCH
2 -2-Py Me S(0) 2
C(O)NHCH
2 -2-Py Cl S(=-O) C(O)NHCH 2
CF
3 Me S(=O) C(O)NHCH 2
CF
3 Cl S(0) 2
C(O)NHCH
2
CF
3 Me S02 C(O)NHCH 2
CF
3 CI S(=O) C(O)NHEt Me S(=O) C(O)NHEt CI S(0) 2 C(O)NHEt Me S02C(O)NHEt CN S(=O) IH-1,2;4-triazol-1-yi NO 2 S(=O) IH-1,2,4-triazol-1-yI CN S(0) 2 IH-1,2.4-triazol-1-yi NO 2 S(0) 2 IH-1,2,4-triazol-I-yi CN S(=O) C(O)NHCH 2 -2-Py NO 2 S(=O) C(O)NIICH 2 -2-Py CN S(0) 2
C(O)NHCH
2 -2-Py NO 2 S(0) 2
C(O)NHCH
2 -2-Py CN S(=O) C(O)NHCH 2
CF
3
NO
2 S(=O) C(O)NIHCH 2
CF
3 CN S02 C(O)NHCH 2
CF
3 NO2 0 2
C(O)NHCH
2
CF
3 CN S(=O) C(O)NHEt NO 2 S(=O) C(O)NHEt CN S(0) 2 C(O)NHEt NO2 0 2 C(O)NHEt WO 2007/123853 PCT/US2007/009181 57 Table I11 R3
F
3 C N
R
3 R5___ Q R 3 R5___ Q Me CF 3 C(O)NUEt Me H C(O)NIIEt Me CF 3
C(O)NHCH
2
CF
3 Me H C(O)NHCH 2
CF
3 Me CF 3
C(O)NHCH
2 -2-Py Me H C(O)NHCH 2 -2-Py Me CF 3 IH-1,2,4-triazol-i-yi Me H IH-I,2,4-triazol-i-yi H CF 3 C(O)NTIEt H H C(O)NHEt H CF 3
C(O)NHCH
2
CF
3 H H C(O)NIICH 2
CF
3 H CF 3
C(O)NHCH
2 -2-Py H H C(O)NHCH 2 -2-Py H CF 3 IH-1,2,4-triazol-1-yi H H JH-L,2,4-triazol-1-yl Me CI C(O)NHEt Me Me C(O)NHEt Me CI C(O)NHCH 2
CF
3 Me Me C(O)N1HCH 2
CF
3 Me CI C(O)NHCH 2 -2-Py Me Me C(O)NHCH 2 -2-Py Me CI )H-1,2,4-tfiazol-1-yI Me Me lH-1,2,4-triazol-1-yI H CI C(O)NHEt H Me C(O)NHEt H CI C(O)NHCH 2
CF
3 H Me C(O)NHCH 2
CF
3 H CI C(O)NHCH 2 -2-Py H Me C(O)NHCH 2 -2-Py H CI IH-1,2,4-triazol-1-yl H Me IH-1,2,4-triazol-1-yl Me CN C(O)NHEt Me NO 2 C(O)NHEt Me CN C(O)NHCH 2
CF
3 Me NO 2
C(O)NHCH
2
CF
3 Me CN C(O)NIHCH 2 -2-Py Me NO 2
C(O)NHCH
2 -2-Py Me CNIH-1,2,4-triazol-1-yi Me NO 2 IH-1,2,4-triazol-1-yi H CN C(O)NHEt H NO 2 C(O)NHEt H CN C(O)NHCH 2
CF
3 H NO 2
C(O)NHCH
2
CF
3 H CN C(O)NHCH 2 -2-Py H N02 C(O)NHCH 2 -2-Py H CN IH-1,2,4-triazol-i-yl H N02 )H-1,2,4-triazol-i-yI WO 2007/123853 PCT/US2007/009181 58 Table 12
F
3 C N CI - A -A 2 Q At A 2 Q A' A 2 Q CH CHI C(0) N HEt CH N C(O)NHCH 2 -2-Py N CH C(O)NHEt N N C(O)NIICH 2 -2-Py CH N C(O)NBEt C H CII I-imidazoyl N N C(O)NHEt N CHI 1-imidazoyl CH CH C(O)NHCH 2
CF
3 CHI N I-imidazoyl N CH C(O)NHCH 2
CF
3 N N 1-imidazoyl CH N C(O)NHCH 2
CF
3 CH CH IH-1,2,4-triazol-i-yi N N C(O)NHCH 2
CF
3 N CH IH-I,2,4-triazol-i-yi CH CH C(O)NHCH 2 -2-Py CHI N IH-1,2,4-triazol-i-yi N CHI C(O)NHCH 2 -2-Py N N I-1,2,4-triazol-I-yi Table 13
F
3 C R Q N, Cll R3AI Q R3_____ A I Q H CHI C(O)NHEt Me N C(O)NHCII 2 -2-Py H N C(O)NHEt Me CHI I-imidazoyl HI CII C(O)NIICH 2
CF
3 Me N 1-imidazoyl HI N C(O)NHCII 2
CF
3 Me CH IH-1,2,4-triazol-1-yi HI CH C(O)NHCH 2 -2-Py Me N IH-1,2,4-triazol-I-yI H N C(O)NHCH 2 -2-Py CII 2
CF
3 CH C(O)NHEt H CH 1-imidazoyl CH 2
CF
3 N C(O)NHEt H N 1-imidazoyl CH 2
CF
3 CH C(O)NIICH 2
CF
3 H CH )H-I,2,4-triazol-i-yl CH 2
CF
3 N C(O)NHCH 2
CF
3 WO 2007/123853 PCT/US2007/009181 59
R
3 Al Q R 3 Al Q H N IH-1,2,4-triazol-1-yl CH 2
CF
3 CH C(O)NHCH 2 -2-Py Me CH C(O)NHEt CH 2
CF
3 N C(O)NHCH 2 -2-Py Me N C(O)NHEt CH 2
CF
3 CH 1-imidazoyl Me CH C(O)NHCH 2
CF
3
CH
2
CF
3 N 1-imidazoyl Me N C(O)NHCH 2
CF
3
CH
2
CF
3 CH 1H-1,2,4-triazol-1-yl Me CH C(O)NHCH 2 -2-Py CH 2
CF
3 N IH-1,2,4-triazol-1-yl Table 14 0 F30OO{ 2 N A 3 4 / 6 AlQ
(R
2 )m 5 R 5 wherein m is 1, 2, 3, 4 or 5.
(R
2 )m Al A 3
R
5 Q R 2
A
1
A
3
R
5 Q 3-C1, 4-Cl N N H C(O)NHEt 3-CI, 4-Cl N N H C(O)NHCH 2 -2-Py 3-Cl, 4-Cl N CH H C(0)NHEt 3-Cl, 4-Cl N CH H C(O)NHCH 2 -2-Py 3-Cl, 4-Cl CH N H C(0)NHEt 3-CI, 4-Cl CH N H C(O)NHCH 2 -2-Py 3-Cl, 5-Cl N N H C(O)NHEt 3-CI, 5-Cl N N H C(O)NHCH 2 -2-Py 3-CI, 5-Cl N CH H C(O)NHEt 3-C1, 5-Cl N CH H C(O)NHCH 2 -2-Py 3-CI, 5-Cl CH N H C(O)NHEt 3-C1, 5-Cl CH N H C(O)NHCH 2 -2-Py 3-CI, 4-Cl N N Me C(O)NHEt 3-CI, 4-Cl N N Me C(O)NHCH 2 -2-Py 3-Cl, 4-Cl N CH Me C(O)NHEt 3-C, 4-Cl N CH Me C(O)NHCH 2 -2-Py 3-Cl, 4-Cl CH N Me C(O)NHEt 3-CI, 4-Cl CH N Me C(O)NHCH 2 -2-Py 3-Cl, 5-CI N N Me C(O)NHEt 3-Cl, 5-Cl N N Me C(O)NHCH 2 -2-Py 3-Cl, 5-Cl N CH Me C(O)NHEt 3-Cl, 5-CI N CH Me C(O)NHCH 2 -2-Py 3-CI, 5-Cl CH N Me C(O)NHEt 3-Cl, 5-Cl CH N Me C(O)NHCH 2 -2-Py 3-Cl, 4-Cl N N CF 3 C(O)NHEt 3-Cl, 4-Cl N N CF 3
C(O)NHCH
2 -2-Py 3-CI, 4-Cl N CH CF 3 C(O)NHEt 3-C1, 4-Cl N CH CF 3
C(O)NHCH
2 -2-Py 3-C1, 4-Cl CH N CF 3 C(O)NHEt 3-C1, 4-Cl CH N CF 3
C(O)NHCH
2 -2-Py 3-Cl, 5-Cl N N CF 3 C(O)NHEt 3-Cl, 5-Cl N N CF 3
C(O)NHCH
2 -2-Py 3-Cl, 5-CI N CH CF 3 C(O)NHEt 3-Cl, 5-Cl N CH CF 3
C(O)NHCH
2 -2-Py 3-Cl, 5-CI CH N CF 3 C(O)NHEt 3-Cl, 5-Cl CH N CF 3
C(O)NHCH
2 -2-Py 3-CI, 4-Cl N N H C(O)NHCH 2
CF
3 3-Cl, 4-Cl N N H IH- 1,2,4-triazol- l-yl 3-Cl, 4-Cl N CH H C(O)NHCH 2
CF
3 3-Cl, 4-CI N CH H IH-l,2,4-triazol-1l-yl 3-Cl, 4-Cl CH N H C(O)NHCH 2
CF
3 3-Cl, 4-Cl CH N H IH-l,2,4-triazol-1-yl WO 2007/123853 PCT/US2007/009181 60
(R
2 )m A' A 3
R
5 Q R 2 A' A 3
R
5 Q 3-C1, 5-Cl N N H C(O)NHCH 2
CF
3 3-Cl, 5-CI N N H IH-1,2,4-triazol-1-yl 3-Cl, 5-CI N CH H C(O)NHCH 2
CF
3 3-Cl, 5-CI N CH H 1H-1,2,4-triazol-1-yl 3-CI, 5-CI CH N H C(O)NHCH 2
CF
3 3-Cl, 5-Cl CH N H 1H-1,2,4-triazol-1-yl 3-CI, 4-Cl N N Me C(O)NHCH 2
CF
3 3-Cl, 4-Cl N N Me IH-1,2,4-triazol-1-yl 3-CI, 4-Cl N CH Me C(O)NHCH 2
CF
3 3-Cl, 4-Cl N CH Me 1H-1,2,4-triazol-1-yl 3-Cl, 4-CI CH N Me C(O)NHCH 2
CF
3 3-Cl, 4-Cl CH N Me IH-1,2,4-triazol-1-yl 3-Cl, 5-CI N N Me C(O)NHCH 2
CF
3 3-CI, 5-Cl N N Me 1H-1,2,4-triazol-1-yl 3-CI, 5-Cl N CH Me C(O)NHCH 2
CF
3 3-Cl, 5-Cl N CH Me IH-1,2,4-triazol-1-yl 3-Cl, 5-Cl CH N Me C(O)NHCH 2
CF
3 3-Cl, 5-Cl CH N Me IH-1,2,4-triazol-i-yl 3-Cl, 4-Cl N N CF 3
C(O)NHCH
2
CF
3 3-Cl, 4-Cl N N CF 3 IH-1,2,4-triazol-1-yl 3-Cl, 4-CI N CH CF 3
C(O)NHCH
2
CF
3 3-Cl, 4-Cl N CH CF 3 1H-1,2,4-triazol-1-yl 3-CI, 4-CI CH N CF 3
C(O)NHCH
2
CF
3 3-Cl, 4-Cl CH N CF 3 IH-1,2,4-triazol-1-yl 3-Cl, 5-Cl N N CF 3
C(O)NHCH
2
CF
3 3-CI, 5-Cl N N CF 3 1H-1,2,4-triazol-1-yl 3-Cl, 5-CI N CH CF 3
C(O)NHCH
2
CF
3 3-Cl, 5-Cl N CH CF 3 IH-1,2,4-triazol-1-yl 3-Cl, 5-Cl CH N CF 3
C(O)NHCH
2
CF
3 3-Cl, 5-Cl CH N CF 3 1H-1,2,4-triazol-1-yl Table 15
R
3
F
3 C N Cl N A Q Cl R5
R
3 A A 3
R
5 Q R 3
A
1
A
3
R
5 Q H CH N Me C(O)NHEt H N N H C(O)NHEt H CH N Me C(O)NHEt H N N H C(O)NHEt H CH N Me C(O)NHCH 2
CF
3 H N N H C(O)NHCH 2
CF
3 H CH N Me C(O)NHCH 2
CF
3 H N N H C(O)NHCH 2
CF
3 H CH N Me C(O)NHCH 2 -2-Py H N N H C(O)NHCH 2 -2-Py H CH N Me C(O)NHCH 2 -2-Py H N N H C(O)NHCH 2 -2-Py H CH N Me 1H-1,2,4-triazol-1-yl H N N H 1H-1,2,4-triazol-1-yl H CH N Me 1H-1,2,4-triazol-i-yl H N N H 1IH-1,2,4-triazol-1-yl Me CH N Me C(O)NHEt Me N N H C(O)NHEt Me CH N Me C(O)NHEt Me N N H C(O)NHEt Me CH N Me C(O)NHCH 2
CF
3 Me N N H C(O)NHCH 2
CF
3 Me CH N Me C(O)NHCH 2
CF
3 Me N N H C(O)NHCH 2
CF
3 WO 2007/123853 PCT/US2007/009181 61
R
3 Al A 3
R
5 Q R 3 Al A 3
R
5 Q Me CH N Me C(O)NHCH 2 -2-Py Me N N H C(O)NHCH 2 -2-Py Me. CH N Me C(O)NHCH 2 -2-Py Me N N H C(O)NHCH 2 -2-Py Me CH N Me 1IH-1,2,4-triazol-1-yi Me N N H 1IH-1,2,4-triazol-1-yl Me CH N Me 1IH-1,2,4-triazol-1-yl Me N N H IH-1,2,4-triazol-1-yl H N CH Me C(O)NHEt H CH N CF 3 C(O)NHEt H N CH Me C(O)NHEt H CH N CF 3 C(O)NHEt H N CH Me C(O)NHCH 2
CF
3 H CH N CF 3
C(O)NHCH
2
CF
3 H N CH Me C(O)NHCH 2
CF
3 H CH N CF 3
C(O)NHCH
2
CF
3 H N CH Me C(O)NHCH 2 -2-Py H CH N CF 3
C(O)NHCH
2 -2-Py H N CH Me C(O)NHCH 2 -2-Py H CH N CF 3
C(O)NHCH
2 -2-Py H N CH Me 1H-1,2,4-triazol-1-yl H CH N CF 3 1H-1,2,4-triazol-1-yl H N CH Me 1H-1,2,4-triazol-1-yl H CH N CF 3 1H-1,2,4-triazol-i1-yl Me N CH Me C(O)NHEt Me CH N CF 3 C(O)NHEt Me N CH Me C(O)NHEt Me CH N CF 3 C(O)NHEt Me N CH Me C(O)NHCH 2
CF
3 Me CH N CF 3
C(O)NHCH
2
CF
3 Me N CH Me C(O)NHCH 2
CF
3 Me CH N CF 3
C(O)NHCH
2
CF
3 Me N CH Me C(O)NHCH 2 -2-Py Me CH N CF 3
C(O)NHCH
2 -2-Py Me N CH Me C(O)NHCH 2 -2-Py Me CH N CF 3
C(O)NHCH
2 -2-Py Me N CH Me 1H-1,2,4-triazol-1-yl Me CH N CF 3 1H-1,2,4-triazol-1-yl Me N CH Me 1IH-1,2,4-triazol-1-yl Me CH N CF 3 IH-1,2,4-triazol-1-yl H N N Me C(O)NHEt H N CH CF 3 C(O)NHEt H N N Me C(O)NHEt H N CH CF 3 C(O)NHEt H N N Me C(O)NHCH 2
CF
3 H N CH CF 3
C(O)NHCH
2
CF
3 H N N Me C(O)NHCH 2
CF
3 H N CH CF 3
C(O)NHCH
2
CF
3 H N N Me C(O)NHCH 2 -2-Py H N CH CF 3
C(O)NHCH
2 -2-Py H N N Me C(O)NHCH 2 -2-Py H N CH CF 3
C(O)NHCH
2 -2-Py H N N Me 1IH-1,2,4-triazol-1-yl H N CH CF 3 1IH-1,2,4-triazol-1-yl H N N Me 1IH-1,2,4-triazol-i-yl H N CH CF 3 1IH-1,2,4-triazol-1-yl Me N N Me C(O)NHEt Me N CH CF 3 C(O)NHEt Me N N Me C(O)NHEt Me N CH CF 3 C(O)NHEt Me N N Me C(O)NHCH 2
CF
3 Me N CH CF 3
C(O)NHCH
2
CF
3 Me N N Me C(O)NHCH 2
CF
3 Me N CH CF 3
C(O)NHCH
2
CF
3 Me N N Me C(O)NHCH 2 -2-Py Me N CH CF 3
C(O)NHCH
2 -2-Py Me N N Me C(O)NHCH 2 -2-Py Me N CH CF 3
C(O)NHCH
2 -2-Py Me N N Me 1IH-1,2,4-triazol-1-yl Me N CH CF 3 1H-1,2,4-triazol-1-yi Me N N Me 1IH-1,2,4-triazol-i-yl Me N CH CF 3 1IH-1,2,4-triazol-1-yl H CH N H C(O)NHEt H N N CF 3 C(O)NHEt WO 2007/123853 PCT/US2007/009181 62
R
3 Al A 3
R
5 Q R 3 Al A 3
R
5 Q H CH N H C(O)NHEt H N N CF 3 C(O)NHEt H CH N H C(O)NHCH 2
CF
3 H N N CF 3
C(O)NHCH
2
CF
3 H CH N H C(O)NHCH 2
CF
3 H N N CF 3
C(O)NHCH
2
CF
3 H CH N H C(O)NHCH 2 -2-Py H N N CF 3
C(O)NHCH
2 -2-Py H CH N H C(O)NHCH 2 -2-Py H N N CF 3
C(O)NHCH
2 -2-Py H CH N H IH-1,2,4-triazol-1-yl H N N CF 3 1H-1,2,4-triazol-1-yl H CH N H IH-1,2,4-triazol-1-yl H N N CF 3 IH-1,2,4-triazol-1-yl Me CH N H C(O)NHEt Me N N CF 3 C(O)NHEt Me CH N H C(O)NHEt Me N N CF 3 C(O)NHEt Me CH N H C(O)NHCH 2
CF
3 Me N N CF 3
C(O)NHCH
2
CF
3 Me CH N H C(O)NHCH 2
CF
3 Me N N CF 3
C(O)NHCH
2
CF
3 Me CH N H C(O)NHCH 2 -2-Py Me N N CF 3
C(O)NHCH
2 -2-Py Me CH N H C(O)NHCH 2 -2-Py Me N N CF 3
C(O)NHCH
2 -2-Py Me CH N H 1IH-1,2,4-triazol-1-yl Me N N CF 3 1H-1,2,4-triazol-1-yl Me CH N H 1IH-1,2,4-triazol-1-yl Me N N CF 3 1H-1,2,4-triazol-1-yl Formulation/Utility Compounds of this invention can generally be used as an invertebrate pest control active ingredient in a composition, i.e. formulation, with a carrier suitable for agronomic or 5 nonagronomic uses comprising at least one of a liquid diluent, a solid diluent or a surfactant. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable 10 concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. The general types of aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion and suspo-emulsion. The general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable 15 concentrate, dispersible concentrate and oil dispersion. The general types of solid compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like which can be water-dispersible ("wettable") or water-soluble. Films and coatings formed from film forming solutions or flowable suspensions are particularly useful for seed treatment. Active 20 ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or WO 2007/123853 PCT/US2007/009181 63 "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. 5 Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water. Spray volumes can range from about one to several thousand liters per hectare, but more typically.are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium 10 for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into the furrow during planting. Liquid and solid formulations can be applied onto seeds of crops and other desirable vegetation as seed treatments before planting to protect developing roots and other subterranean plant parts and/or foliage through systemic 15 uptake. The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight. Weight Percent ActiveIngredient Diluent Surfactant Water-Dispersible and Water-soluble 0.001-90 0-99.999 0-15 Granules, Tablets and Powders. Oil Dispersions, Suspensions, 1-50 40-99 0-50 Emulsions, Solutions (including Emulsifiable Concentrates) Dusts 1-25 70-99 0-5 Granules and Pellets 0.001-99 5-99.999 0-15 High Strength Compositions 90-99 0-10 0-2 20 Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland 25 Books, Caldwell, New Jersey. Liquid diluents include, for example, water, N,N-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), ethylene glycol, triethylene glycol, propylene glycol, dipropylene WO 2007/123853 PCT/US2007/009181 64 glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, triacetin, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone 5 and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactate esters, dibasic esters and y-butyrolactone, and alcohols, which can be linear, branched, saturated or unsaturated, such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl 10 alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzyl alcohol. Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically
C
6
--C
22 ), such as plant seed and fruit oils (e.g, oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut 15 and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 20 1950. McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. 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") 25 generally modify, most often reduce, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in a surfactant molecule, surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents. Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such 30 as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol 35 ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; WO 2007/123853 PCT/US2007/009181 65 ethoxylated methyl esters; ethoxylated tristyrylphenol (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters and polyethoxylated 5 glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, graft or comb polymers and star polymers; polyethylene glycols (pegs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar-derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides. 10 Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl 15 phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides such as N,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes; sulfonates of 20 naphthalene and alkyl naphthalene; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their derivatives such as dialkyl sulfosuccinate salts. Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylene tetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines 25 (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides. Also useful for the present compositions are mixtures of nonionic and anionic 30 surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon's Emulsifiers and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., 35 New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987. Compositions of this invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to WO 2007/123853 PCT/US2007/009181 66 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 5 (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes. Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of formulation auxiliaries and additives include those listed in McCutcheon's Volume 2: 10 Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222. The compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or 15 by grinding in a liquid or dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water. Active ingredient slurries, with particle diameters of up to 2,000 pm can be wet milled using media mills to 20 obtain particles with average diameters below 3 p.m. Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 pm range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill 25 or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. 30 Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566. For further information regarding the art of formulation, see T. S. Woods, "The 35 Formulator's Toolbox - Product Forms for Modern Agriculture" in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361, Col. 6, line 16 through WO 2007/123853 PCT/US2007/009181 67 Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; Hance et al., 5 Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000. In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Tables A D. Without further elaboration, it is believed that one skilled in the art using the preceding 10 description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be constructed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except where otherwise indicated. Example A High Strength Concentrate Compound 2 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0% 15 Example B Wettable Powder Compound 12 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 18 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0% WO 2007/123853 PCT/US2007/009181 68 Example E Emulsifiable Concentrate Compound 19 10.0% polyoxyethylene sorbitol hexoleate 20.0%
C
6
-C
10 fatty acid methyl ester 70.0% Example F Microemulsion Compound 2 5.0% polyvinylpyrrolidone-vinyl acetate copolymer 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water 20.0% Example G Seed Treatment Compound 18 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 19 2.5% pyrrolidone-styrene copolymer 4.8% tristyrylphenyl 16-ethoxylate 2.3% talc 0.8% corn starch 5.0% Nitrophoska® Permanent 15-9-15 slow-release fertilizer 36.0% (BASF) kaolin 38.0% water 10.6% 5 Compounds of this invention exhibit activity against a wide spectrum of invertebrate pests. These pests include invertebrates inhabiting a variety of environments such as, for example, plant foliage, roots, soil, harvested crops or other foodstuffs, building structures or animal integuments. These pests include, for example, invertebrates feeding on foliage WO 2007/123853 PCT/US2007/009181 69 (including leaves, stems, flowers and fruits), seeds, wood, textile fibers or animal blood or tissues, and thereby causing injury or damage to, for example, growing or stored agronomic crops, forests, greenhouse crops, ornamentals, nursery crops, stored foodstuffs or fiber products, or houses or other structures or their contents, or being harmful to animal health or 5 public health. Those skilled in the art will appreciate that not all compounds are equally effective against all growth stages of all pests. These present compounds and compositions are thus useful agronomically for protecting field crops from phytophagous invertebrate pests, and also nonagronomically for protecting other horticultural crops and plants from phytophagous invertebrate pests. This 10 utility includes protecting crops and other plants (i.e. both agronomic and nonagronomic) that contain genetic material introduced by genetic engineering (i.e. transgenic) or modified by mutagenesis to provide advantageous traits. Examples of such traits include tolerance to herbicides, resistance to phytophagous pests (e.g., insects, mites, aphids, spiders, nematodes, snails, plant-pathogenic fungi, bacteria and viruses), improved plant growth, increased 15 tolerance of adverse growing conditions such as high or low temperatures, low or high soil moisture, and high salinity, increased flowering or fruiting, greater harvest yields, more rapid maturation, higher quality and/or nutritional value of the harvested product, or improved storage or process properties of the harvested products. Transgenic plants can be modified to express multiple traits. Examples of plants containing traits provided by genetic 20 engineering or mutagenesis include varieties of corn, cotton, soybean and potato expressing an insecticidal Bacillus thuringiensis toxin such as YIELD GARD®, KNOCKOUT®, STARLINK®, BOLLGARD®, NuCOTN® and NEWLEAF®, and herbicide-tolerant varieties of corn, cotton, soybean and rapeseed such as ROUNDUP READY®, LIBERTY LINK®, IMI®, STS® and CLEARFIELD®, as well as crops expressing N-acetyltransferase (GAT) to 25 provide resistance to glyphosate herbicide, or crops containing the HRA gene providing resistance to herbicides inhibiting acetolactate synthase (ALS). The present compounds and compositions may interact synergistically with traits introduced by genetic engineering or modified by mutagenesis, thus enhancing phenotypic expression or effectiveness of the traits or increasing the invertebrate pest control effectiveness of the present compounds and 30 compositions. In particular, the present compounds and compositions may interact synergistically with the phenotypic expression of proteins or other natural products toxic to invertebrate pests to provide greater-than-additive control of these pests. Compositions of this invention can also optionally comprise plant nutrients, e.g., a fertilizer composition comprising at least one plant nutrient selected from nitrogen, 35 phosphorus, potassium, sulfur, calcium, magnesium, iron, copper, boron, manganese, zinc, and molybdenum. Of note are compositions comprising at least one fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium and magnesium. Compositions of the present invention which further comprise at WO 2007/123853 PCT/US2007/009181 70 least one plant nutrient can be in the form of liquids or solids. Of note are solid formulations in the form of granules, small sticks or tablets. Solid formulations comprising a fertilizer composition can be prepared by mixing the compound or composition of the present invention with the fertilizer composition together with formulating ingredients and then 5 preparing the formulation by methods such as granulation or extrusion. Alternatively solid formulations can be prepared by spraying a solution or suspension of a compound or composition of the present invention in a volatile solvent onto a previous prepared fertilizer composition in the form of dimensionally stable mixtures, e.g., granules, small sticks or tablets, and then evaporating the solvent. 10 Nonagronomic uses refer to invertebrate pest control in the areas other than fields of crop plants. Nonagronomic uses of the present compounds and compositions include control of invertebrate pests in stored grains, beans and other foodstuffs, and in textiles such as clothing and carpets. Nonagronomic uses of the present compounds and compositions also include invertebrate pest control in ornamental plants, forests, in yards, along roadsides and 15 railroad rights of way, and on turf such as lawns, golf courses and pastures. Nonagronomic uses of the present compounds and compositions also include invertebrate pest control in houses and other buildings which may be occupied by humans and/or companion, farm, ranch, zoo or other animals. Nonagronomic uses of the present compounds and compositions also include the control of pests such as termites that can damage wood or 20 other structural materials used in buildings. Nonagronomic uses of the present compounds and compositions also include protecting human and animal health by controlling invertebrate pests that are parasitic or transmit infectious diseases. The controlling of animal parasites includes controlling external parasites that are parasitic to the surface of the body of the host animal (e.g., 25 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 parasites include heartworms, hookworms and helminths. Compounds and compositions of the present 30 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. Compounds 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, 35 buffalos, rabbits, hens, turkeys, ducks, geese and bees; pet animals and domestic animals such as dogs, cats, pet birds and aquarium fish; as well as so-called experimental animals, such as hamsters, guinea pigs, rats and mice. By combating these parasites, fatalities and performance reduction (in terms of meat, milk, wool, skins, eggs, honey, etc.) are reduced, WO 2007/123853 PCT/US2007/009181 71 so that applying a composition comprising a compound of the present invention allows more economic and simple husbandry of animals. Examples of agronomic or nonagronomnic invertebrate pests include eggs, larvae and adults of the order Lepidoptera, such as armyworms, cutworms, loopers, and heliothines in 5 the family Noctuidae (e.g., pink stem borer (Sesamia inferens Walker), corn stalk borer (Sesamia nonagrioides Lefebvre), southern armyworm (Spodoptera eridania Cramer), fall armyworm (Spodoptera fugiperda J. E. Smith), beet armyworm (Spodoptera exigua Huibner), cotton leafworm (Spodoptera littoralis Boisduval), yellowstriped armyworm (Spodoptera ornithogalli Guenie), black cutworm (Agrotis ipsilon Hufnagel), velvetbean 10 caterpillar (Anticarsia gemmatalis Hilbner), green fruitworm (Lithophane antennata Walker), cabbage armyworm (Barathra brassicae Linnaeus), soybean looper (Pseudoplusia includens Walker), cabbage looper (Trichoplusia ni HUibner), tobacco budworm (Heliothis virescens Fabricius)); borers, casebearers, webworms, coneworms, cabbageworms and skeletonizers from the family Pyralidae (e.g., European corn borer (Ostrinia nubilalis 15 HUibner), navel orangeworm (Amyelois transitella Walker), corn root webworm (Crambus caliginosellus Clemens), sod webworms (Pyralidae: Crambinae) such as sod worm (Herpetogramma licarsisalis Walker), sugarcane stem borer (Chilo infuscatellus Snellen), tomato small borer (Neoleucinodes elegantalis Guen6e), green leafroller (Cnaphalocerus medinalis), grape leaffolder (Desmia funeralis HUibner), melon worm (Diaphania nitidalis 20 Stoll), cabbage center grub (Helluala hydralis Guenre), yellow stem borer (Scirpophaga incertulas Walker), early shoot borer (Scirpophaga infuscatellus Snellen), white stem borer (Scirpophaga innotata Walker), top shoot borer (Scirpophaga nivella Fabricius), dark headed rice borer (Chilo polychrysus Meyrick), cabbage cluster caterpillar (Crocidolomia binotalis English)); leafrollers, budworms, seed worms, and fruit worms in the family 25 Tortricidae (e.g., codling moth (Cydia pomonella Linnaeus), grape berry moth (Endopiza viteana Clemens), oriental fruit moth (Grapholita molesta Busck), citrus false codling moth (Cryptophlebia leucotreta Meyrick), citrus borer (Ecdytolopha aurantiana Lima), redbanded leafroller (Argyrotaenia velutinana Walker), obliquebanded leafroller (Choristoneura rosaceana Harris), light brown apple moth (Epiphyas postvittana Walker), European grape 30 berry moth (Eupoecilia ambiguella Hibner), apple bud moth (Pandemis pyrusana Kearfott), omnivorous leafroller (Platynota stultana Walsingham), barred fruit-tree tortrix (Pandemis cerasana HUibner), apple brown tortrix (Pandemis heparana Denis & Schiffermilller)); and many other economically important lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth (Lymantria 35 dispar Linnaeus), peach fruit borer (Carposina niponensis Walsingham), peach twig borer (Anarsia lineatella Zeller), potato tuberworm (Phthorimaea operculella Zeller), spotted teniform leafminer (Lithocolletis blancardella Fabricius), Asiatic apple leafminer (Lithocolletis ringoniella Matsumura), rice leaffolder (Lerodea eufala Edwards), apple WO 2007/123853 PCT/US2007/009181 72 leafminer (Leucoptera scitella Zeller)); eggs, nymphs and adults of the order Blattodea including cockroaches from the families Blattellidae and Blattidae (e.g., oriental cockroach (Blatta orientalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo), German cockroach (Blattella germanica Linnaeus), brownbanded cockroach (Supella longipalpa 5 Fabricius), American cockroach (Periplaneta americana Linnaeus), brown cockroach (Periplaneta brunnea Burmeister), Madeira cockroach (Leucophaea maderae Fabricius)), smoky brown cockroach (Periplaneta fuliginosa Service), Australian Cockroach (Periplaneta australasiae Fabr.), lobster cockroach (Nauphoeta cinerea Olivier) and smooth cockroach (Symploce pallens Stephens)); eggs, foliar feeding, fruit feeding, root feeding, 10 seed feeding and vesicular tissue feeding larvae and adults of the order Coleoptera including weevils from the families Anthribidae, Bruchidae, and Curculionidae (e.g., boll weevil (Anthonomus grandis Boheman), rice water weevil (Lissorhoptrus oryzophilus Kuschel), granary weevil (Sitophilus granarius Linnaeus), rice weevil (Sitophilus oryzae Linnaeus)), annual bluegrass weevil (Listronotus maculicollis Dietz), bluegrass billbug (Sphenophorus 15 parvulus Gyllenhal), hunting billbug (Sphenophorus venatus vestitus), Denver billbug (Sphenophorus cicatristriatus Fahraeus)); flea beetles, cucumber beetles, rootworms, leaf beetles, potato beetles, and leafminers in the family Chrysomelidae (e.g., Colorado potato beetle (Leptinotarsa decemlineata Say), western corn rootworm (Diabrotica virgifera virgifera LeConte)); chafers and other beetles from the family Scarabaeidae (e.g., Japanese 20 beetle (Popillia japonica Newman), oriental beetle (Anomala orientalis Waterhouse, Exomala orientalis (Waterhouse) Baraud), northern masked chafer (Cyclocephala borealis Arrow), southern masked chafer (Cyclocephala immaculata Olivier or C. lurida Bland), dung beetle and white grub (Aphodius spp.), black turfgrass ataenius (Ataenius spretulus Haldeman), green June beetle (Cotinis nitida Linnaeus), Asiatic garden beetle (Maladera 25 castanea Arrow), May/June beetles (Phyllophaga spp.) and European chafer (Rhizotrogus majalis Razoumowsky)); carpet beetles from the family Dermestidae; wireworms from the family Elateridae; bark beetles from the family Scolytidae and flour beetles from the family Tenebrionidae. In addition, agronomic and nonagronomic pests include: eggs, adults and larvae of the order Dermaptera including earwigs from the family Forficulidae (e.g., 30 European earwig (Forficula auricularia Linnaeus), black earwig (Chelisoches morio Fabricius)); eggs, immatures, adults and nymphs of the orders Hemiptera and Homoptera such as, plant bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g. Empoasca spp.) from the family Cicadellidae, bed bugs (e.g., Cimex lectularius Linnaeus) from the family Cimicidae, planthoppers from the families Fulgoroidae and 35 Delphacidae, treehoppers from the family Membracidae, psyllids from the family Psyllidae, whiteflies from the family Aleyrodidae, aphids from the family Aphididae, phylloxera from the family Phylloxeridae, mealybugs from the family Pseudococcidae, scales from the families Coccidae, Diaspididae and Margarodidae, lace bugs from the family Tingidae, stink WO 2007/123853 PCT/US2007/009181 73 bugs from the family Pentatomidae, chinch bugs (e.g., hairy chinch bug (Blissus leucopterus hirtus Montandon) and southern chinch bug (Blissus insularis Barber)) and other seed bugs from the family Lygaeidae, spittlebugs from the family Cercopidae squash bugs from the family Coreidae, and red bugs and cotton stainers from the family Pyrrhocoridae. Also 5 included are eggs, larvae, nymphs and adults of the order Acari (mites) such as spider mites and red mites in the family Tetranychidae (e.g., European red mite (Panonychus ulmi Koch), two spotted spider mite (Tetranychus urticae Koch), McDaniel mite (Tetranychus mcdanieli McGregor)); flat mites in the family Tenuipalpidae (e.g., citrus flat mite (Brevipalpus lewisi McGregor)); rust and bud mites in the family Eriophyidae and other foliar feeding mites and 10 mites important in human and animal health, i.e. dust mites in the family Epidermoptidae, follicle mites in the family Demodicidae, grain mites in the family Glycyphagidae, ticks in the family Ixodidae, commonly known as hard ticks (e.g., deer tick (Ixodes scapularis Say), Australian paralysis tick (Ixodes holocyclus Neumann), American dog tick (Dermacentor variabilis Say), lone star tick (Amblyomma americanum Linnaeus)) and ticks in the family 15 Argasidae, commonly known as soft ticks (e.g., relapsing fever tick (Ornithodoros turicata), common fowl tick (Argas radiatus)); scab and itch mites in the families Psoroptidae, Pyemotidae, and Sarcoptidae; eggs, adults and immatures of the order Orthoptera including grasshoppers, locusts and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differentialis Thomas), American grasshoppers (e.g., Schistocerca 20 americana Drury), desert locust (Schistocerca gregaria Forskal), migratory locust (Locusta migratoria Linnaeus), bush locust (Zonocerus spp.), house cricket (Acheta domesticus Linnaeus), mole crickets (e.g., tawny mole cricket (Scapteriscus vicinus Scudder) and southern mole cricket (Scapteriscus borellii Giglio-Tos)); eggs, adults and immatures of the order Diptera including leafminers (e.g., Liriomyza spp. such as serpentine vegetable 25 leafminer (Liriomyza sativae Blanchard)), midges, fruit flies (Tephritidae), frit flies (e.g., Oscinella frit Linnaeus), soil maggots, house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g., Fannia canicularis Linnaeus, F. femoralis Stein), stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g., Chrysomya spp., Phormia spp.), and other muscoid fly pests, horse flies (e.g., Tabanus spp.), bot flies (e.g., 30 Gastrophilus spp., Oestrus spp.), cattle grubs (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.), keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g., Prosimulium spp., Simulium spp.), biting midges, sand flies, sciarids, and other Nematocera; eggs, adults and immatures of the order Thysanoptera including onion thrips (Thrips tabaci Lindeman), flower thrips 35 (Frankliniella spp.), and other foliar feeding thrips; insect pests of the order Hymenoptera including ants of the Family Formicidae including the Florida carpenter ant (Camponotus floridanus Buckley), red carpenter ant (Camponotusferrugineus Fabricius), black carpenter ant (Camponotus pennsylvanicus De Geer), white-footed ant (Technomyrmex albipes fr.
WO 2007/123853 PCT/US2007/009181 74 Smith), big headed ants (Pheidole sp.), ghost ant (Tapinoma melanocephalum Fabricius); Pharaoh ant (Monomorium pharaonis Linnaeus), little fire ant (Wasmannia auropunctata Roger), fire ant (Solenopsis geminata Fabricius), red imported fire ant (Solenopsis invicta Buren), Argentine ant (Iridomyrmex humilis Mayr), crazy ant (Paratrechina longicornis 5 Latreille), pavement ant (Tetramorium caespitum Linnaeus), cornfield ant (Lasius alienus Forster) and odorous house ant (Tapinoma sessile Say). Other Hymenoptera including bees (including carpenter bees), hornets, yellow jackets, wasps, and sawflies (Neodiprion spp.; Cephus spp.); insect pests of the order Isoptera including termites in the Termitidae (e.g., Macrotermes sp., Odontotermes obesus Rambur), Kalotermitidae (e.g., Cryptotermes sp.), 10 and Rhinotermitidae (e.g., Reticulitermes sp., Coptotermes sp., Heterotermes tenuis Hagen) families, the eastern subterranean termite (Reticulitermes flavipes Kollar), western subterranean termite (Reticulitermes hesperus Banks), Formosan subterranean termite (Coptotermes formosanus Shiraki), West Indian drywood termite (Incisitermes immigrans Snyder), powder post termite (Cryptotermes brevis Walker), drywood termite (Incisitermes 15 snyderi Light), southeastern subterranean termite (Reticulitermes virginicus Banks), western drywood termite (Incisitermes minor Hagen), arboreal termites such as Nasutitermes sp. and other termites of economic importance; insect pests of the order Thysanura such as silverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobia domestica Packard); insect pests of the order Mallophaga and including the head louse (Pediculus humanus capitis De Geer), 20 body louse (Pediculus humanus Linnaeus), chicken body louse (Menacanthus stramineus Nitszch), dog biting louse (Trichodectes canis De Geer), fluff louse (Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank), short-nosed cattle louse (Haematopinus eurysternus Nitzsch), long-nosed cattle louse (Linognathus vituli Linnaeus) and other sucking and chewing parasitic lice that attack man and animals; insect pests of the order 25 Siphonoptera including the oriental rat flea (Xenopsylla cheopis Rothschild), cat flea (Ctenocephalides felis Bouche), dog flea (Ctenocephalides canis Curtis), hen flea (Ceratophyllus gallinae Schrank), sticktight flea (Echidnophaga gallinacea Westwood), human flea (Pulex irritans Linnaeus) and other fleas afflicting mammals and birds. Additional arthropod pests covered include: spiders in the order Araneae such as the brown 30 recluse spider (Loxosceles reclusa Gertsch & Mulaik) and the black widow spider (Latrodectus mactans Fabricius), and centipedes in the order Scutigeromorpha such as the house centipede (Scutigera coleoptrata Linnaeus). Compounds of the present invention also have activity on members of the Classes Nematoda, Cestoda, Trematoda, and Acanthocephala including economically important members of the orders Strongylida, 35 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 Prarylenchus, stubby root nematodes in the genus Trichodorus, etc.) and animal and human health pests (i.e. all economically important WO 2007/123853 PCT/US2007/009181 75 flukes, tapeworms, and roundworms, such as Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs, Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.). Compounds of the invention show particularly high activity against pests in the order 5 Lepidoptera (e.g., Alabama argillacea Htibner (cotton leaf worm), Archips argyrospila Walker (fruit tree leaf roller), A. rosana Linnaeus (European leaf roller) and other Archips species, Chilo suppressalis Walker (rice stem borer), Cnaphalocrosis medinalis Guen6e (rice leaf roller), Crambus caliginosellus Clemens (corn root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Earias insulana 10 Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoverpa armigera HUibner (American bollworm), Helicoverpa zea Boddie (corn earworm), Heliothis virescens Fabricius (tobacco budworm), Herpetogramma licarsisalis Walker (sod webworm), Lobesia botrana Denis & SchiffermiUller (grape berry moth), Pectinophora gossypiella Saunders (pink bollworm), Phyllocnistis citrella Stainton (citrus leafminer), 15 Pieris brassicae Linnaeus (large white butterfly), Pieris rapae Linnaeus (small white butterfly), Plutella xylostella Linnaeus (diamondback moth), Spodoptera exigua Hibner (beet armyworm), Spodoptera litura Fabricius (tobacco cutworm, cluster caterpillar), Spodoptera frugiperda J. E. Smith (fall armyworm), Trichoplusia ni Htibner (cabbage looper) and Tuta absoluta Meyrick (tomato leafminer)). 20 Compounds of the invention also have significant activity on members from the order Homoptera including: Acyrthosiphon pisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer (apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solani Kaltenbach (foxglove aphid), Chaetosiphon fragaefolii 25 Cockerell (strawberry aphid), Diuraphis noxia Kurdjumov/Mordvilko (Russian wheat aphid), Dysaphis plantaginea Paaserini (rosy apple aphid), Eriosoma lanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffroy (mealy plum aphid), Lipaphis erysimi Kaltenbach (turnip aphid), Metopolophium dirrhodum Walker (cereal aphid), Macrosiphum euphorbiae Thomas (potato aphid), Myzus persicae Sulzer (peach-potato aphid, green peach 30 aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigus spp. (root aphids and gall aphids), Rhopalosiphum maidis Fitch (corn leaf aphid), Rhopalosiphum padi Linnaeus (bird cherry-oat aphid), Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius (English grain aphid), Therioaphis maculata Buckton (spotted alfalfa aphid), Toxoptera aurantii Boyer de Fonscolombe (black citrus aphid), and Toxoptera citricida Kirkaldy 35 (brown citrus aphid); Adelges spp. (adelgids); Phylloxera devastatrix Pergande (pecan phylloxera); Bemisia tabaci Gennadius (tobacco whitefly, sweetpotato whitefly), Bemisia argentifolii Bellows & Perring (silverleaf whitefly), Dialeurodes citri Ashmead (citrus whitefly) and Trialeurodes vaporariorum Westwood (greenhouse whitefly); Empoasca WO 2007/123853 PCT/US2007/009181 76 fabae Harris (potato leafhopper), Laodelphax striatellus Fallen (smaller brown planthopper), Macrolestes quadrilineatus Forbes (aster leafhopper), Nephotettix cinticeps Uhler (green leafhopper), Nephotettix nigropictus Sthl (rice leafhopper), Nilaparvata lugens Sthl (brown planthopper), Peregrinus maidis Ashmead (corn planthopper), Sogatella furcifera Horvath 5 (white-backed planthopper), Sogatodes orizicola Muir (rice delphacid), Typhlocyba pomaria McAtee white apple leafhopper, Erythroneoura spp. (grape leafhoppers); Magicidada septendecim Linnaeus (periodical cicada); Icerya purchasi Maskell (cottony cushion scale), Quadraspidiotus perniciosus Comstock (San Jose scale); Planococcus citri Risso (citrus mealybug); Pseudococcus spp. (other mealybug complex); Cacopsylla pyricola Foerster 10 (pear psylla), Trioza diospyri Ashmead (persimmon psylla). Compounds of this invention also have activity on members from the order Hemiptera including: Acrosternum hilare Say (green stink bug), Anasa tristis De Geer (squash bug), Blissus leucopterus leucopterus Say (chinch bug), Cimex lectularius Linnaeus (bed bug) Corythuca gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), 15 Dysdercus suturellus Herrich-SchAiffer (cotton stainer), Euchistus servus Say (brown stink bug), Euchistus variolarius Palisot de Beauvois (one-spotted stink bug), Graptosthetus spp. (complex of seed bugs), Leptoglossus corculus Say (leaf-footed pine seed bug), Lygus lineolaris Palisot de Beauvois (tarnished plant bug), Nezara viridula Linnaeus (southern green stink bug), Oebalus pugnax Fabricius (rice stink bug), Oncopeltus fasciatus Dallas 20 (large milkweed bug), Pseudatomoscelis seriatus Reuter (cotton fleahopper). Other insect orders controlled by compounds of the invention include Thysanoptera (e.g., Frankliniella occidentalis Pergande (western flower thrips), Scirthothrips citri Moulton (citrus thrips), Sericothrips variabilis Beach (soybean thrips), and Thrips tabaci Lindeman (onion thrips); and the order Coleoptera (e.g., Leptinotarsa decemlineata Say (Colorado potato beetle), 25 Epilachna varivestis Mulsant (Mexican bean beetle) and wireworms of the genera Agriotes, Athous or Limonius). Note that some contemporary classification systems place Homoptera as a suborder within the order Hemiptera. Of note is use of compounds of this invention for controlling diamondback moth 30 (Plutella xylostella). Of note is use of compounds of this invention for controlling fall armyworm (Spodoptera frugiperda). Of note is use of compounds of this invention for controlling western flower thrip (Frankliniella occidentalis). Of note is use of compounds of this invention for controlling potato leafhopper (Empoasca fabae). Of note is use of compounds of this invention for controlling cotton melon aphid (Aphis gossypii). Of note is 35 use of compounds of this invention for controlling green peach aphid (Myzus persicae). 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, growth regulators such as rooting stimulants, chemosterilants, WO 2007/123853 PCT/US2007/009181 77 semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agronomic and nonagronomic utility. Thus the present invention also pertains to a composition comprising a biologically effective amount 5 of a compound of Formula 1, an N-oxide or salt thereof, and an effective amount of at least one additional biologically active compound or agent and can further comprise at least one of surfactants, solid diluents or liquid diluents. For mixtures of the present invention, the other biologically active compounds or agents can be formulated together with the present compounds, including the compounds of Formula 1, to form a premix, or the other 10 biologically active compounds or agents can be formulated separately from the present compounds, including the compounds of Formula 1, and the two formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession. Other biologically active compounds or agents useful in the compositions of the present invention can be selected from invertebrate pest control agents having a different 15 mode of action or a different chemical class including macrocyclic lactones, neonicotinoids, octopamine receptor ligands, ryanodine receptor ligands, ecdysone agonists, sodium channel modulators, chitin synthesis inhibitors, nereisotoxin analogs, mitochondrial electron transport inhibitors, cholinesterase inhibitors, cyclodiene insecticides, molting inhibitors, GABA (y-aminobutyric acid)-regulated chloride channel blockers, juvenile hormone 20 mimics, lipid biosynthesis inhibitors and biological agents including nucleopolyhedro viruses (NPV), members of Bacillus thuringiensis, encapsulated delta-endotoxins of Bacillus thuringiensis, and other naturally occurring or genetically modified insecticidal viruses. Of note are additional biologically active compounds or agents selected from insecticides of the group consisting of pyrethroids, carbamates, neonicotinoids, neuronal 25 sodium channel blockers, insecticidal macrocyclic lactones, y-aminobutyric acid antagonists, insecticidal ureas and juvenile hormone mimics, a member of Bacillus thuringiensis, a Bacillus thuringiensis delta-endotoxin, and a naturally occurring or a genetically modified viral insecticide. Examples of such biologically active compounds or agents with which compounds of 30 this invention can be formulated are: insecticides such as abamectin, acephate, acetamiprid, acetoprole, amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, bistrifluron, buprofezin, carbofuran, cartap, chlorfenapyr, chlorfluazuron, chlorantraniliprole (DPX-E2Y45), chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, 35 lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid, flubendiamide, .flucythrinate, tau-fluvalinate, flufenerim (UR-50701), WO 2007/123853 PCT/US2007/009181 78 flufenoxuron, fonophos, halofenozide, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, metaflumizone, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide, monocrotophos, nitenpyram, nithiazine, novaluron, 5 noviflumuron (XDE-007), oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, protrifenbute, pymetrozine, pyrafluprole, pyrethrin, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen (BSN 2060), spirotetramat, sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, 10 thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate, trichlorfon and triflumuron; fungicides such as acibenzolar, aldimorph, amisulbrom, azaconazole, azoxystrobin, benalaxyl, benomyl, benthiavalicarb, benthiavalicarb-isopropyl, binomial, biphenyl, bitertanol, blasticidin-S, Bordeaux mixture (Tribasic copper sulfate), boscalid/nicobifen, bromuconazole, bupirimate, buthiobate, 15 carboxin, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, chlozolinate, clotrimazole, copper oxychloride, copper salts such as copper sulfate and copper hydroxide, cyazofamid, cyflunamid, cymoxanil, cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinocap, discostrobin, 20 dithianon, dodemorph, dodine, econazole, etaconazole, edifenphos, epoxiconazole, ethaboxam, ethirimol, ethridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fencaramid, fenfuram, fenhexamide, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferfurazoate, ferimzone, fluazinam, fludioxonil, flumetover, fluopicolide, fluoxastrobin, fluquinconazole, fluquinconazole, flusilazole, 25 flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum, fuberidazole, furalaxyl, furametapyr, hexaconazole, hymexazole, guazatine, imazalil, imibenconazole, iminoctadine, iodicarb, ipconazole, iprobenfos, iprodione, iprovalicarb, isoconazole, isoprothiolane, kasugamycin, kresoxim-methyl, mancozeb, mandipropamid, maneb, mapanipyrin, mefenoxam, mepronil, metalaxyl, metconazole, methasulfocarb, metiram, 30 metominostrobin/fenominostrobin, mepanipyrim, metrafenone, miconazole, myclobutanil, neo-asozin (ferric methanearsonate), nuarimol, octhilinone, ofurace, orysastrobin, oxadixyl, oxolinic acid, oxpoconazole, oxycarboxin, paclobutrazol, penconazole, pencycuron, penthiopyrad, perfurazoate, phosphonic acid, phthalide, picobenzamid, picoxystrobin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propamocarb-hydrochloride, 35 propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pryazophos, pyrifenox, pyrimethanil, pyrifenox, pyrolnitrine, pyroquilon, quinconazole, quinoxyfen, quintozene, silthiofam, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, techrazene, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate, WO 2007/123853 PCT/US2007/009181 79 thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolyfluanid, triadimefon, triadimenol, triarimol, triazoxide, tridemorph, trimoprhamide tricyclazole, trifloxystrobin, triforine, triticonazole, uniconazole, validamycin, vinclozolin, zineb, ziram, and zoxamide; nematocides such as aldicarb, imicyafos, oxamyl and fenamiphos; bactericides such as 5 streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and biological agents including entomopathogenic bacteria, such as Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, and the encapsulated delta-endotoxins of Bacillus thuringiensis 10 (e.g., Cellcap, MPV, MIPVII); entomopathogenic fungi, such as green muscardine fungus; and entomopathogenic virus 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). Compounds of this invention and compositions thereof can be applied to plants 15 genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis delta-endotoxins). The effect of the exogenously applied invertebrate pest control compounds of this invention may be synergistic with the expressed toxin proteins. General references for these agricultural protectants (i.e. insecticides, fungicides, nematocides, acaricides, herbicides and biological agents) include The Pesticide Manual, 20 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2003 and The BioPesticide Manual, 2 nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2001. Of note is a composition of the present invention wherein at least one additional biologically active compound or agent is selected from the group consisting of abamectin, 25 acephate, acetamiprid, acetoprole, aldicarb, amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, bistrifluron, buprofezin, carbofuran, cartap, chinomethionat, chlorfenapyr, chlorfluazuron, chlorantraniliprole, chlorpyrifos, chlorpyrifos methyl, chlorobenzilate, chromafenozide, clothianidin, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cyhexatin, 30 cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dicofol, dieldrin, dienochlor, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etoxazole, fenamiphos, fenazaquin, fenbutatin oxide, fenothiocarb, fenoxycarb, fenpropathrin, fenpyroximate, fenvalerate, fipronil, flonicamid, flubendiamide, flucythrinate, tau-fluvalinate, flufenerim, flufenoxuron, fonophos, 35 halofenozide, hexaflumuron, hexythiazox, hydramethylnon, imicyafos, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, metaflumizone, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, methoxyfenozide, metofluthrin, monocrotophos, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, WO 2007/123853 PCT/US2007/009181 80 parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, propargite, protrifenbute, pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spiridiclofen, spiromesifen, spirotetramat, sulprofos, 5 tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate, trichlorfon, triflumuron, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, nucleopolyhedro viruses, an encapsulated delta-endotoxins of Bacillus thuringiensis, baculoviruses, entomopathogenic bacteria, entomopathogenic viruses 10 and entomopathogenic fungi. Of particular note is a composition of the present invention wherein the at least one additional biologically active compound or agent is selected from the group consisting of abamnectin, acephate, acetamiprid, acetoprole, amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, bistrifluron, buprofezin, carbofuran, 15 cartap, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid, 20 flubendiamide, flucythrinate, tau-fluvalinate, flufenerim (UR-50701), flufenoxuron, halofenozide, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, metaflumizone, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, methoxyfenozide, metofluthrin, monocrotophos, methoxyfenozide, nitenpyram, nithiazine, novaluron, noviflumuron (XDE-007), oxamyl, 25 parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, protrifenbute, pymetrozine, pyrethrin, pyridalyl, pyriproxyfen, rotenone, ryanodine, S1812 (Valent), spinosad, spiridiclofen, spiromesifen (BSN 2060), sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, 30 triazamate, trichlorfon, triflumuron, aldicarb, fenamiphos, amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpyroximate, hexythiazox, propargite, pyridaben, tebufenpyrad, Bacillus thuringiensis aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, entomopathogenic virus and entomopathogenic fungi. 35 Also of note is a composition of the present invention wherein at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acetamiprid, amitraz, avermectin, azadirachtin, bifenthrin, buprofezin, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyfluthrin, beta-cyfluthrin, WO 2007/123853 PCT/US2007/009181 81 cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamrnectin, endosulfan, esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flonicamid, flubendiamide, flufenoxuron, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, metaflumizone, methomyl, 5 methoprene, methoxyfenozide, nitenpyram, nithiazine, novaluron, oxamyl, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, tebufenozide, thiacloprid, thiamethoxam, thiodicarb, thiosultap sodium, tralomethrin, triazamate, triflumuron, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, nucleopolyhedro viruses and an encapsulated delta 10 endotoxins of Bacillus thuringiensis. Of further note is a composition of the present invention wherein the at least one additional biologically active compound or agent is selected from the group consisting of cypermethrin, cyhalothrin, cyfluthrin and beta-cyfluthrin, esfenvalerate, fenvalerate, tralomethrin, fenothiocarb, methomyl, oxamyl, thiodicarb, acetamiprid, clothianidin, 15 imidacloprid, thiamethoxam, thiacloprid, indoxacarb, spinosad, abamectin, avermectin, emamectin, endosulfan, ethiprole, fipronil, flufenoxuron, triflumuron, diofenolan, pyriproxyfen, pymetrozine, amitraz, Bacillus thuringiensis aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis delta endotoxin and entomophagous fungi. For embodiments where one or more of these various mixing partners are used, the 20 weight ratio of these various mixing partners (in total) to the compound of Formula 1 is typically between about 1:3000 and about 3000:1. Of note are weight ratios between about 1:300 and about 300:1 (for example ratios between about 1:30 and about 30:1). One skilled in the art can easily determine through simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity. It 25 will be evident that including these additional components may expand the spectrum of invertebrate pests controlled beyond the spectrum controlled by the compound of Formula 1 alone. In certain instances, combinations of a compound of this invention with other biologically active (particularly invertebrate pest control) compounds or agents (i.e. active 30 ingredients) can result in a greater-than-additive (i.e. synergistic) effect. Reducing the quantity of active ingredients released in the environment while ensuring effective pest control is always desirable. When synergism of invertebrate pest control active ingredients occurs at application rates giving agronomically satisfactory levels of invertebrate pest control, such combinations can be advantageous for reducing crop production cost and 35 decreasing environmental load. Of note is a combination of a compound of Formula 1 with at least one other invertebrate pest control active ingredient. Of particular note is such a combination where the other invertebrate pest control active ingredient has a different site of action from the WO 2007/123853 PCT/US2007/009181 82 compound of Formula 1. In certain instances, a combination with at least one other invertebrate pest control active ingredient having a similar spectrum of control but a different site of action will be particularly advantageous for resistance management. Thus, a composition of the present invention can further comprise a biologically effective amount of 5 at least one additional invertebrate pest control active ingredient having a similar spectrum of control but a different site of action. Contacting a plant genetically modified to express an invertebrate pest compound (e.g., protein) or the locus of the plant with a biologically effective amount of a compound of this invention can also provide a broader spectrum of plant protection and be advantageous for resistance management. 10 Table A lists specific combinations of a compound of Formula 1 with other invertebrate pest control agents illustrative of the mixtures, compositions and methods of the present invention. The first column of Table A lists the specific invertebrate pest control agents (e.g., "Abamectin" in the first line). The second column of Table A lists the mode of action (if known) or chemical class of the invertebrate pest control agents. The third column 15 of Table A lists embodiment(s) of ranges of weight ratios for rates at which the invertebrate pest control agent can be applied relative to a compound of Formula 1, an N-oxide, or a salt thereof, (e.g., "50:1 to 1:50" of abamectin relative to a compound of Formula 1 by weight). Thus, for example, the first line of Table A specifically discloses the combination of a compound of Formula 1 with abamectin can be applied in a weight ratio between 50:1 to 20 1:50. The remaining lines of Table A are to be construed similarly. Of further note Table A lists specific combinations of a compound of Formula 1 with other invertebrate pest control agents illustrative of the mixtures, compositions and methods of the present invention and includes additional embodiments of weight ratio ranges for application rates. Table A Invertebrate Pest Mode of Action or Chemical Class Typical Control Agent Weight Ratio Abamectin macrocyclic lactones 50:1 to 1:50 Acetamiprid neonicotinoids 150:1 to 1:200 Amitraz octopamine receptor ligands 200:1 to 1:100 Avermectin macrocyclic lactones 50:1 to 1:50 Azadirachtin ecdysone agonists 100:1 to 1:120 Beta-cyfluthrin sodium channel modulators 150:1 to 1:200 Bifenthrin sodium channel modulators 100:1 to 1:10 Buprofezin chitin synthesis inhibitors 500:1 to 1:50 Cartap nereistoxin analogs 100:1 to 1:200 Chlorantraniliprole ryanodine receptor ligands 100:1 to 1:120 Chlorfenapyr mitochondrial electron transport 300:1 to 1:200 inhibitors WO 2007/123853 PCT/US2007/009181 83 Invertebrate Pest Mode of Action or Chemical Class Typical Control Agent Weight Ratio Chlorpyrifos cholinesterase inhibitors 500:1 to 1:200 Clothianidin neonicotinoids 100:1 to 1:400 Cyfluthrin sodium channel modulators 150:1 to 1:200 Cyhalothrin sodium channel modulators 150:1 to 1:200 Cypermethrin sodium channel modulators 150:1 to 1:200 Cyromazine chitin synthesis inhibitors 400:1 to 1:50 Deltamethrin sodium channel modulators 50:1 to 1:400 Dieldrin cyclodiene insecticides 200:1 to 1:100 Dinotefuran neonicotinoids 150:1 to 1:200 Diofenolan molting inhibitor 150:1 to 1:200 Emamectin macrocyclic lactones 50:1 to 1:10 Endosulfan cyclodiene insecticides 200:1 to 1:100 Esfenvalerate sodium channel modulators 100:1 to 1:400 Ethiprole GABA-regulated chloride channel 200:1 to 1:100 blockers Fenothiocarb 150:1 to 1:200 Fenoxycarb juvenile hormone mimics 500:1 to 1:100 Fenvalerate sodium channel modulators 150:1 to 1:200 Fipronil GABA-regulated chloride channel 150:1 to 1:100 blockers Flonicamid 200:1 to 1:100 Flubendiamide ryanodine receptor ligands 100:1 to 1:120 Flufenoxuron chitin synthesis inhibitors 200:1 to 1:100 Hexaflumuron chitin synthesis inhibitors 300:1 to 1:50 Hydramethylnon mitochondrial electron transport 150:1 to 1:250 inhibitors Imidacloprid neonicotinoids 1000:1 to 1:1000 Indoxacarb sodium channel modulators 200:1 to 1:50 Lambda-cyhalothrin sodium channel modulators 50:1 to 1:250 Lufenuron chitin synthesis inhibitors 500:1 to 1:250 Metaflumizone 200:1 to 1:200 Methomyl cholinesterase inhibitors 500:1 to 1:100 Methoprene juvenile hormone mimics 500:1 to 1:100 Methoxyfenozide ecdysone agonists 50:1 to 1:50 Nitenpyram neonicotinoids 150:1 to 1:200 WO 2007/123853 PCT/US2007/009181 84 Invertebrate Pest Mode of Action or Chemical Class Typical Control Agent Weight Ratio Nithiazine neonicotinoids 150:1 to 1:200 Novaluron chitin synthesis inhibitors 500:1 to 1:150 Oxamyl cholinesterase inhibitors 200:1 to 1:200 Pymetrozine 200:1 to 1:100 Pyrethrin sodium channel modulators 100:1 to 1:10 Pyridaben mitochondrial electron transport 200:1 to 1:100 inhibitors Pyridalyl 200:1 to 1:100 Pyriproxyfen juvenile hormone mimics 500:1 to 1:100 Ryanodine ryanodine receptor ligands 100:1 to 1:120 Spinetoram macrocyclic lactones 150:1 to 1:100 Spinosad macrocyclic lactones 500:1 to 1:10 Spirodiclofen lipid biosynthesis inhibitors 200:1 to 1:200 Spiromesifen lipid biosynthesis inhibitors 200:1 to 1:200 Tebufenozide ecdysone agonists 500:1 to 1:250 Thiacloprid neonicotinoids 100:1 to 1:200 Thiamethoxam neonicotinoids 1250:1 to 1:1000 Thiodicarb cholinesterase inhibitors 500:1 to 1:400 Thiosultap-sodium 150:1 to 1:100 Tralomethrin sodium channel modulators 150:1 to 1:200 Triazamate cholinesterase inhibitors 250:1 to 1:100 Triflumuron chitin synthesis inhibitors 200:1 to 1:100 Bacillus thuringiensis biological agents 50:1 to 1:10 Bacillus thuringiensis biological agents 50:1 to 1:10 delta-endotoxin NPV (e.g., Gemstar) biological agents 50:1 to 1:10 One embodiment of invertebrate pest control agents (e.g., insecticides and acaricides) for mixing with compounds of this invention include sodium channel modulators such as bifenthrin, cypermethrin, cyhalothrin, lambda-cyhalothrin, cyfluthrin, beta-cyfluthrin, deltamethrin, dimefluthrin, esfenvalerate, fenvalerate, indoxacarb, metofluthrin, profluthrin, 5 pyrethrin and tralomethrin; cholinesterase inhibitors such as chlorpyrifos, methomyl, oxamyl, thiodicarb and triazamate; neonicotinoids such as acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid and thiamethoxam; insecticidal macrocyclic lactones such as spinetoram, spinosad, abamectin, avermectin and emamectin; GABA (y-aminobutyric acid)-regulated chloride channel blockers such as endosulfan, WO 2007/123853 PCT/US2007/009181 85 ethiprole and fipronil; chitin synthesis inhibitors such as buprofezin, cyromazine, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron and triflumuron; juvenile hormone mimics such as diofenolan, fenoxycarb, methoprene and pyriproxyfen; octopamine receptor ligands such as amitraz; ecdysone agonists such as azadirachtin, methoxyfenozide 5 and tebufenozide; ryanodine receptor ligands such as ryanodine, anthranilic diamides such as chlorantraniliprole (see U.S. Patent 6,747,047, PCT Publications WO 2003/015518 and WO 2004/067528) and flubendiamide (see U.S. Patent 6,603,044); nereistoxin analogs such as cartap; mitochondrial electron transport inhibitors such as chlorfenapyr, hydramethylnon and pyridaben; lipid biosynthesis inhibitors such as spirodiclofen and spiromesifen; cyclodiene 0 insecticides such as dieldrin; cyflumetofen; fenothiocarb; flonicamid; metaflumizone; pyrafluprole; pyridalyl; pyriprole; pymetrozine; spirotetramat; and thiosultap-sodium. One embodiment of biological agents for mixing with compounds of this invention include nucleopolyhedro virus such as HzNPV and AfNPV; Bacillus thuringiensis and encapsulated delta-endotoxins of Bacillus thuringiensis such as Cellcap, MPV and MPVII; as well as 5 naturally occurring and genetically modified viral insecticides including members of the family Baculoviridae as well as entomophagous fungi. Of note is the composition of the present invention wherein the at least one additional biologically active compound or agent is selected from the Invertebrate Pest Control Agents listed in Table A above. The weight ratios of a compound, including a compound of Formula 1, an N-oxide or a 0 salt thereof, to the additional invertebrate pest control agent typically are between 1000:1 and 1:1000, with one embodiment being between 500:1 and 1:500, another embodiment being between 250:1 and 1:200 and another embodiment being between 100:1 and 1:50. Listed below in Table B are embodiments of specific compositions comprising a compound of Formula 1 (compound numbers refer to compounds in Index Tables A-C) and !5 an additional invertebrate pest control agent. Table B Mixture Comp. and Invertebrate Pest Control Mixture Comp. and Invertebrate Pest Control No. No. Agent No. No. Agent A-1 2 and Abamectin B-I 12 and Abameetin A-2 2 and Acetamiprid B-2 12 and Acetamiprid A-3 2 and Amitraz B-3 12 and Amitraz A-4 2 and Avermectin B-4 12 and Avermectin A-5 2 and Azadirachtin B-5 12 and Azadirachtin A-6 2 and Beta-cyfluthrin B-6 12 and Beta-cyfluthrin A-7 2 and Bifenthrin B-7 12 and Bifenthrin A-8 2 and Buprofezin B-8 12 and Buprofezin A-9 2 and Cartap B-9 12 and Cartap A-10 2 and Chlorantraniliprole B-10 12 and Chlorantraniliprole WO 2007/123853 PCT/US2007/009181 86 Mixture Comp. and Invertebrate Pest Control Mixture Comp. and Invertebrate Pest Control No. No. Agent No. No. Agent A- 11 2 and Chlorfenapyr B-11 12 and Chlorfenapyr A-12 2 and Chlorpyrifos B-12 12 and Chlorpyrifos A-13 2 and Clothianidin B-13 12 and Clothianidin A-14 2 and Cyfluthrin B-14 12 and Cyfluthrin A-15 2 and Cyhalothrin B-15 12 and Cyhalothrin A-16 2 and Cypermethrin B-16 12 and Cypermethrin A-17 2 and Cyromazine B-17 12 and Cyromazine A-18 2 and Deltamethrin B-18 12 and Deltamethrin A-19 2 and Dieldrin B-19 12 and Dieldrin A-20 2 and Dinotefuran B-20 12 and Dinotefuran A-21 2 and Diofenolan B-21 12 and Diofenolan A-22 2 and Emamectin B-22 12 and Emamectin A-23 2 and Endosulfan B-23 12 and Endosulfan A-24 2 and Esfenvalerate B-24 12 and Esfenvalerate A-25 2 and Ethiprole B-25 12 and Ethiprole A-26 2 and Fenothiocarb B-26 12 and Fenothiocarb A-27 2 and Fenoxycarb B-27 12 and Fenoxycarb A-28 2 and Fenvalerate B-28 12 and Fenvalerate A-29 2 and Fipronil B-29 12 and Fipronil A-30 2 and Flonicamid B-30 12 and Flonicamid A-31 2 and Flubendiamide B-31 12 and Flubendiamide A-32 2 and Flufenoxuron B-32 12 and Flufenoxuron A-33 2 and Hexaflumuron B-33 12 and Hexaflumuron A-34 2 and Hydramethylnon B-34 12 and Hydramethylnon A-35 2 and Imidacloprid B-35 12 and Imidacloprid A-36 2 and Indoxacarb B-36 12 and Indoxacarb A-37 2 and Lambda-cyhalothrin B-37 12 and Lambda-cyhalothrin A-38 2 and Lufenuron B-38 12 and Lufenuron A-39 2 and Metaflumizone B-39 12 and Metaflumizone A-40 2 and Methomyl B-40 12 and Methomyl A-41 2 and Methoprene B-41 12 and Methoprene A-42 2 and Methoxyfenozide B-42 12 and Methoxyfenozide A-43 2 and Nitenpyram B-43 12 and Nitenpyram A-44 2 and Nithiazine B-44 12 and Nithiazine A-45 2 and Novaluron B-45 12 and Novaluron A-46 2 and Oxamyl B-46 12 and Oxamyl WO 2007/123853 PCT/US2007/009181 87 Mixture Comp. and Invertebrate Pest Control Mixture Comp. and Invertebrate Pest Control No. No. Agent No. No. Agent A-47 2 and Pymetrozine B-47 12 and Pymetrozine A-48 2 and Pyrethrin B-48 12 and Pyrethrin A-49 2 and Pyridaben B-49 12 and Pyridaben A-50 2 and Pyridalyl B-50 12 and Pyridalyl A-51 2 and Pyriproxyfen B-51 12 and Pyriproxyfen A-52 2 and Ryanodine B-52 12 and Ryanodine A-53 2 and Spinetoram B-53 12 and Spinetoram A-54 2 and Spinosad B-54 12 and Spinosad A-55 2 and Spirodiclofen B-55 12 and Spirodiclofen A-56 2 and Spiromesifen B-56 12 and Spiromesifen A-57 2 and Tebufenozide B-57 12 and Tebufenozide A-58 2 and Thiacloprid B-58 12 and Thiacloprid A-59 2 and Thiamethoxam B-59 12 and Thiamethoxam A-60 2 and Thiodicarb B-60 12 and Thiodicarb A-61 2 and Thiosultap-sodium B-61 12 and Thiosultap-sodium A-62 2 and Tralomethrin B-62 12 and Tralomethrin A-63 2 and Triazamate B-63 12 and Triazamate A-64 2 and Triflumuron B-64 12 and Triflumuron A-65 2 and Bacillus thuringiensis B-65 12 and Bacillus thuringiensis A-66 2 and Bacillus thuringiensis B-66 12 and Bacillus thuringiensis delta-endotoxin delta-endotoxin A-67 9 and NPV (e.g., Gemstar) B-67 12 and NPV (e.g., Gemstar) C-1 18 and Abamectin D-1 19 and Abamectin C-2 18 and Acetamiprid D-2 19 and Acetamiprid C-3 18 and Amitraz D-3 19 and Amitraz C-4 18 and Avermectin D-4 19 and Avermectin C-5 18 and Azadirachtin D-5 19 and Azadirachtin C-6 18 and Beta-cyfluthrin D-6 19 and Beta-cyfluthrin C-7 18 and Bifenthrin D-7 19 and Bifenthrin C-8 18 and Buprofezin D-8 19 and Buprofezin C-9 18 and Cartap D-9 19 and Cartap C-10 18 and Chlorantraniliprole D-10 19 and Chlorantraniliprole C-I 1 18 and Chlorfenapyr D-11 19 and Chlorfenapyr C-12 18 and Chlorpyrifos D-12 19 and Chlorpyrifos C-13 18 and Clothianidin D-13 19 and Clothianidin C-14 18 and Cyfluthrin D-14 19 and Cyfluthrin WO 2007/123853 PCT/US2007/009181 88 Mixture Comp. and Invertebrate Pest Control Mixture Comp. and Invertebrate Pest Control No. No. Agent No. No. Agent C-15 18 and Cyhalothrin D-15 19 and Cyhalothrin C-16 18 and Cypermethrin D-16 19 and Cypermethrin C-17 18 and Cyromazine D-17 19 and Cyromazine C-18 18 and Deltamethrin D-18 19 and Deltamethrin C-19 18 and Dieldrin D-19 19 and Dieldrin C-20 18 and Dinotefuran D-20 19 and Dinotefuran C-21 18 and Diofenolan D-21 19 and Diofenolan C-22 18 and Emamectin D-22 19 and Emamectin C-23 18 and Endosulfan D-23 19 and Endosulfan C-24 18 and Esfenvalerate D-24 19 and Esfenvalerate C-25 18 and Ethiprole D-25 19 and Ethiprole C-26 18 and Fenothiocarb D-26 19 and Fenothiocarb C-27 18 and Fenoxycarb D-27 19 and Fenoxycarb C-28 18 and Fenvalerate D-28 19 and Fenvalerate C-29 18 and Fipronil D-29 19 and Fipronil C-30 18 and Flonicamid D-30 19 and Flonicamid C-31 18 and Flubendiamide D-31 19 and Flubendiamide C-32 18 and Flufenoxuron D-32 19 and Flufenoxuron C-33 18 and Hexaflumuron D-33 19 and Hexaflumuron C-34 18 and Hydramethylnon D-34 19 and Hydramethylnon C-35 18 and Imidacloprid D-35 19 and Imidacloprid C-36 18 and Indoxacarb D-36 19 and Indoxacarb C-37 18 and Lambda-cyhalothrin D-37 19 and Lambda-cyhalothrin C-38 18 and Lufenuron D-38 19 and Lufenuron C-39 18 and Metaflumizone D-39 19 and Metaflumizone C-40 18 and Methomyl D-40 19 and Methomyl C-41 18 and Methoprene D-41 19 and Methoprene C-42 18 and Methoxyfenozide D-42 19 and Methoxyfenozide C-43 18 and Nitenpyram D-43 19 and Nitenpyram C-44 18 and Nithiazine D-44 19 and Nithiazine C-45 18 and Novaluron D-45 19 and Novaluron C-46 18 and Oxamyl D-46 19 and Oxamyl C-47 18 and Pymetrozine D-47 19 and Pymetrozine C-48 18 and Pyrethrin D-48 19 and Pyrethrin C-49 18 and Pyridaben D-49 19 and Pyridaben C-50 18 and Pyridalyl D-50 19 and Pyridalyl WO 2007/123853 PCT/US2007/009181 89 Mixture Comp. and Invertebrate Pest Control Mixture Comp. and Invertebrate Pest Control No. No. Agent No. No. Agent C-51 18 and Pyriproxyfen D-51 19 and Pyriproxyfen C-52 18 and Ryanodine D-52 19 and Ryanodine C-53 18 and Spinetoram D-53 19 and Spinetoram C-54 18 and Spinosad D-54 19 and Spinosad C-55 18 and Spirodiclofen D-55 19 and Spirodiclofen C-56 18 and Spiromesifen D-56 19 and Spiromesifen C-57 18 and Tebufenozide D-57 19 and Tebufenozide C-58 18 and Thiacloprid D-58 19 and Thiacloprid C-59 18 and Thiamethoxam D-59 19 and Thiamethoxam C-60 18 and Thiodicarb D-60 19 and Thiodicarb C-61 18 and Thiosultap-sodium D-61 19 and Thiosultap-sodium C-62 18 and Tralomethrin D-62 19 and Tralomethrin C-63 18 and Triazamate D-63 19 and Triazamrnate C-64 18 and Triflumuron D-64 19 and Triflumuron C-65 18 and Bacillus thuringiensis D-65 19 and Bacillus thuringiensis C-66 18 and Bacillus thuringiensis D-66 19 and Bacillus thuringiensis delta-endotoxin delta-endotoxin C-67 18 and NPV (e.g., Gemstar) D-67 19 and NPV (e.g., Gemstar) The specific mixtures listed in Table B typically combine a compound of Formula 1 with the other invertebrate pest agent in the ratios specified in Table A. Invertebrate pests are controlled in agronomic and nonagronomic applications by applying one or more compounds of this invention, typically in the form of a composition, in 5 a biologically effective amount, to the environment of the pests, including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. Thus the present invention comprises a method for controlling an invertebrate pest in agronomic and/or nonagronomic applications, comprising contacting the invertebrate pest or 10 its environment with a biologically effective amount of one or more of the compounds of the invention, or with a composition comprising at least one such compound or a composition comprising at least one such compound and a biologically effective amount of at least one additional biologically active compound or agent. Examples of suitable compositions comprising a compound of the invention and a biologically effective amount of at least one 15 additional biologically active compound or agent include granular compositions wherein the additional active compound is present on the same granule as the compound of the invention or on granules separate from those of the compound of the invention.
WO 2007/123853 PCT/US2007/009181 90 To achieve contact with a compound or composition of the invention to protect a field crop from invertebrate pests, the compound or composition is typically applied to the seed of the crop before planting, to the foliage (e.g., leaves, stems, flowers, fruits) of crop plants, or to the soil or other growth medium before or after the crop is planted. 5 One embodiment of a method of contact is by spraying. Alternatively, a granular composition comprising a compound of the invention can be applied to the plant foliage or the soil. Compounds of this invention can also be effectively delivered through plant uptake by contacting the plant with a composition comprising a compound of this invention applied as a soil drench of a liquid formulation, a granular formulation to the soil, a nursery box 10 treatment or a dip of transplants. Of note is a composition of the present invention in the form of a soil drench liquid formulation. Also of note is a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of the present invention or with a composition comprising a biologically effective amount of a compound of the present invention. Of 15 further note is this method wherein the environment is soil and the composition is applied to the soil as a soil drench formulation. Of further note is that compounds of this invention are also effective by localized application to the locus of infestation. Other methods of contact include application of a compound or a composition of the invention by direct and residual sprays, aerial sprays, gels, seed coatings, microencapsulations, systemic uptake, baits, ear 20 tags, boluses, foggers, fumigants, aerosols, dusts and many others. One embodiment of a method of contact is a dimensionally stable fertilizer granule, stick or tablet comprising a compound or composition of the invention. The compounds of this invention can also be impregnated into materials for fabricating invertebrate control devices (e.g., insect netting). Compounds of this invention are also useful in seed treatments for protecting seeds 25 from invertebrate pests. In the context of the present disclosure and claims, treating a seed means contacting the seed with a biologically effective amount of a compound of this invention, which is typically formulated as a composition of the invention. This seed treatment protects the seed from invertebrate soil pests and generally can also protect roots and other plant parts in contact with the soil of the seedling developing from the germinating 30 seed. The seed treatment may also provide protection of foliage by translocation of the compound of this invention or a second active ingredient within the developing plant. Seed treatments can be applied to all types of seeds, including those from which plants genetically transformed to express specialized traits will germinate. Representative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis toxin or 35 those expressing herbicide resistance such as glyphosate acetyltransferase, which provides resistance to glyphosate. One method of seed treatment is by spraying or dusting the seed with a compound of the invention (i.e. as a formulated composition) before sowing the seeds. Compositions WO 2007/123853 PCT/US2007/009181 91 formulated for seed treatment generally comprise a film former or adhesive agent. Therefore typically a seed coating composition of the present invention comprises a biologically effective amount of a compound of Formula 1, an N-oxide or salt thereof, and a film former or adhesive agent. Seed can be coated by spraying a flowable suspension concentrate 5 directly into a tumbling bed of seeds and then drying the seeds. Alternatively, other formulation types such as wetted powders, solutions, suspoemulsions, emulsifiable concentrates and emulsions in water can be sprayed on the seed. This process is particularly useful for applying film coatings on seeds. Various coating machines and processes are available to one skilled in the art. Suitable processes include those listed in P. Kosters et al., 10 Seed Treatment: Progress and Prospects, 1994 BCPC Mongraph No. 57, and references listed therein. The treated seed typically comprises a compound of the present invention in an amount from about 0.1 g to 1 kg per 100 kg of seed (i.e. from about 0.0001 to 1% by weight of the seed before treatment). A flowable suspension formulated for seed treatment typically 15 comprises from about 0.5 to about 70% of the active ingredient, from about 0.5 to about 30% of a film-forming adhesive, from about 0.5 to about 20% of a dispersing agent, from 0 to about 5% of a thickener, from 0 to about 5% of a pigment and/or dye, from 0 to about 2% of an antifoaming agent, from 0 to about 1% of a preservative, and from 0 to about 75% of a volatile liquid diluent. 20 The compounds of this invention can be incorporated into a bait composition that is consumed by an invertebrate pest or used within a device such as a trap, bait station, and the like. Such a bait composition can be in the form of granules which comprise (a) active ingredients, namely a biologically effective amount of a compound of Formula 1, an N-oxide, or salt thereof; (b) one or more food materials; optionally (c) an attractant, and 25 optionally (d) one or more humectants. Of note are granules or bait compositions which comprise between about 0.001-5% active ingredients, about 40-99% food material and/or attractant; and optionally about 0.05-10% humectants, which are effective in controlling soil invertebrate pests at very low application rates, particularly at doses of active ingredient that are lethal by ingestion rather than by direct contact. Some food materials can function both 30 as a food source and an attractant. Food materials include carbohydrates, proteins and lipids. Examples of food materials are vegetable flour, sugar, starches, animal fat, vegetable oil, yeast extracts and milk solids. Examples of attractants are odorants and flavorants, such as fruit or plant extracts, perfume, or other animal or plant component, pheromones or other agents known to attract a target invertebrate pest. Examples of humectants, i.e. moisture 35 retaining agents, are glycols and other polyols, glycerine and sorbitol. Of note is a bait composition (and a method utilizing such a bait composition) used to control at least one invertebrate pest selected from the group consisting of ants, termites and cockroaches. A device for controlling an invertebrate pest can comprise the present bait composition and a WO 2007/123853 PCT/US2007/009181 92 housing adapted to receive the bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to the bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity 5 for the invertebrate pest. The compounds of this invention can be applied without other adjuvants, but most often application will be of a formulation comprising one or more active ingredients with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. One method of application involves spraying a 10 water dispersion or refined oil solution of a compound of the present invention. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance compound efficacy. For nonagronomic uses such sprays can be applied from spray containers such as a can, a bottle or other container, either by means of a pump or by releasing it from a pressurized container, 15 e.g., a pressurized aerosol spray can. Such spray compositions can take various forms, for example, sprays, mists, foams, fumes or fog. Such spray compositions thus can further comprise propellants, foaming agents, etc. as the case may be. Of note is a spray composition comprising a biologically effective amount of a compound or a composition of the present invention and a carrier. One embodiment of such a spray composition comprises 20 a biologically effective amount of a compound or a composition of the present invention and a propellant. Representative propellants include, but are not limited to, methane, ethane, propane, - butane, isobutane, butene, pentane, isopentane, neopentane, pentene, hydrofluorocarbons, chlorofluorocarbons, dimethyl ether, and mixtures of the foregoing. Of note is a spray composition (and a method utilizing such a spray composition dispensed from 25 a spray container) used to control at least one invertebrate pest selected from the group consisting of mosquitoes, black flies, stable flies, deer flies, horse flies, wasps, yellow jackets, hornets, ticks, spiders, ants, gnats, and the like, including individually or in combinations. Nonagronomic applications include protecting an animal, particularly a vertebrate, 30 more particularly a homeothermic vertebrate (e.g., mammal or bird) and most particularly a mammal, from an invertebrate parasitic pest by administering a parasiticidally effective (i.e. biologically effective) amount of a compound of the invention, typically in the form of a composition formulated for veterinary use, to the animal to be protected. Therefore of note is a method for protecting an animal comprising administering to the animal a parasiticidally 35 effective amount of a compound of the invention. As referred to in the present disclosure and claims, the terms "parasiticidal" and "parasiticidally" refers to observable effects on an invertebrate parasite pest to provide protection of an animal from the pest. Parasiticidal effects typically relate to diminishing the occurrence or activity of the target invertebrate WO 2007/123853 PCT/US2007/009181 93 parasitic pest. Such effects on the pest include necrosis, death, retarded growth, diminished mobility or lessened ability to remain on or in the host animal, reduced feeding and inhibition of reproduction. These effects on invertebrate parasite pests provide control (including prevention, reduction or elimination) of parasitic infestation or infection of the 5 animal. Examples of invertebrate parasitic pests controlled by administering a parasiticidally effective amount of a compound of the invention to an animal to be protected include ectoparasites (arthropods, acarines, etc) and endoparasites (helminths, e.g., nematodes, trematodes, cestodes, acanthocephalans, etc.). In particular, the compounds of this invention are effective against ectoparasites including: flies such as Haematobia 10 (Lyperosia) irritans (horn fly), Stomoxys calcitrans (stable fly), Simulium spp. (blackfly), Glossina spp. (tsetse flies), Hydrotaea irritans (head fly), Musca autumnalis (face fly), Musca domestica (house fly), Morellia simplex (sweat fly), Tabanus spp. (horse fly), Hypoderma bovis, Hypoderma lineatum, Lucilia sericata, Lucilia cuprina (green blowfly), Calliphora spp. (blowfly), Protophormia spp., Oestrus ovis (nasal botfly), Culicoides spp. 15 (midges), Hippobosca equine, Gastrophilus instestinalis, Gastrophilus haemorrhoidalis and Gastrophilus naslis; lices such as Bovicola (Damalinia) bovis, Bovicola equi, Haematopinus asini, Felicola subrostratus, Heterodoxus spiniger, Lignonathus setosus and Trichodectes canis; keds such as Melophagus ovinus; mites such as Psoroptes spp., Sarcoptes scabei, Chorioptes bovis, Demodex equi, Cheyletiella spp., Notoedres cati, Trombicula spp. and 20 Otodectes cyanotis (ear mites); ticks such as Ixodes spp., Boophilus spp., Rhipicephalus spp., Amblyomma spp., Dermacentor spp., Hyalomma spp. and Haemaphysalis spp.; and fleas such as Ctenocephalidesfelis (cat flea) and Ctenocephalides canis (dog flea). Nonagronomic applications in the veterinary sector are by conventional means such as by enteral administration in the form of, for example, tablets, capsules, drinks, drenching 25 preparations, granulates, pastes, boli, feed-through procedures, or suppositories; or by parenteral administration, such as by injection (including intramuscular, subcutaneous, intravenous, intraperitoneal), implants; by nasal administration; by topical administration, for example, in the form of immersion or dipping, spraying, washing, coating with powder, or application to a small area of the animal, and through articles such as neck collars, ear 30 tags, tail bands, limb bands or halters which comprise compounds or compositions of the present invention. Typically a parasiticidal composition according to the present invention comprises a mixture of a compound of Formula 1, an N-oxide or a salt thereof, with one or more pharmaceutically or veterinarily acceptable carriers comprising excipients and auxiliaries 35 selected with regard to the intended route of administration (e.g., oral, topical or parenteral administration such as injection) and in accordance with standard practice. In addition, a suitable carrier is selected on the basis of compatibility with the one or more active ingredients in the composition, including such considerations as stability relative to pH and WO 2007/123853 PCT/US2007/009181 94 moisture content. Therefore of note is a composition for protecting an animal from an invertebrate parasitic pest comprising a parasitically effective amount of a compound of the invention and at least one carrier. For parenteral administration including intravenous, intramuscular and subcutaneous 5 injection, a compound of the present invention can be formulated in suspension, solution or emulsion in oily or aqueous vehicles, and may contain adjuncts such as suspending, stabilizing and/or dispersing agents. Pharmaceutical compositions for injection include aqueous solutions of water-soluble forms of active ingredients (e.g., a salt of an active compound), preferably in physiologically compatible buffers containing other excipients or 10 auxiliaries as are known in the art of pharmaceutical formulation. For oral administration including solutions (the most readily available form for absorption), emulsions, suspensions, pastes, gels, capsules, tablets, boluses powders, granules, rumen-retention and feed/water/lick blocks, a compound of the present invention can be formulated with binders/fillers known in the art to be suitable for oral administration 15 compositions, such as sugars (e.g., lactose, sucrose, mannitol, sorbitol), starch (e.g., maize starch, wheat starch, rice starch, potato starch), cellulose and derivatives (e.g., methylcellulose, carboxymethylcellulose, ethylhydroxycellulose), protein derivatives (e.g., zein, gelatin), and synthetic polymers (e.g., polyvinyl alcohol, polyvinylpyrrolidone). If desired, lubricants (e.g., magnesium stearate), disintegrating agents (e.g., cross-linked 20 polyvinylpyrrolidinone, agar, alginic acid) and dyes or pigments can be added. Pastes and gels often also contain adhesives (e.g., acacia, alginic acid, bentonite, cellulose, xanthangum, colloidal magnesium aluminum silicate) to aid in keeping the composition in contact with the oral cavity and not being easily ejected. If the parasiticidal compositions are in the form of feed concentrates, the carrier is 25 typically selected from high-performance feed, feed cereals or protein concentrates. Such feed concentrate-containing compositions can, in addition to the parasiticidal active ingredients, comprise additives promoting animal health or growth, improving quality of meat from animals for slaughter or otherwise useful to animal husbandry. These additives can include, for example, vitamins, antibiotics, chemotherapeutics, bacteriostats, fungistats, 30 coccidiostats and hormones. Compounds of the present invention have been discovered to have favorable pharmacokinetic and pharmacodynamic properties providing systemic availability from oral administration and ingestion. Therefore after ingestion by the animal to be protected, parasiticidally effective concentrations of compounds of the invention in the bloodstream 35 protect the treated animal from blood-sucking pests such as fleas, ticks and lice. Therefore of note is a composition for protecting an animal from an invertebrate parasite pest in a form for oral administration (i.e. comprising, in addition to a parasiticidally effective amount of a WO 2007/123853 PCT/US2007/009181 95 compound of the invention, one or more carriers selected from binders and fillers suitable for oral administration and feed concentrate carriers). Formulations for topical administration are typically in the form of a powder, cream, suspension, spray, emulsion, foam, paste, aerosol, ointment, salve or gel. More typically a 5 topical formulation is a water-soluble solution, which can be in the form of a concentrate that is diluted before use. Parasiticidal compositions suitable for topical administration typically comprise a compound of the present invention and one or more topically suitable carriers. In applications of a parasiticidal composition topically to the exterior of an animal as a line or spot (i.e. "spot-on" treatment), the active ingredient is expected to migrate over 10 the surface of the active to cover most or all of its external surface area. As a result, the treated animal is particularly protected from invertebrate pests that feed off the epidermis of the animal such as ticks, fleas and lice. Therefore formulations for topical localized administration often comprise at least one organic solvent to facilitate transport of the active ingredient over the skin and/or penetration into the epidermis of the animal. Solvents 15 commonly used as carriers in such formulations include propylene glycol, paraffins, aromatics, esters such as isopropyl myristate, glycol ethers, and alcohols such as ethanol and n-propanol. The rate of application required for effective control (i.e. "biologically effective amount") will depend on such factors as the species of invertebrate to be controlled, the 20 pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredients per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.0001 kg/hectare may be sufficient or as much as 8 kgthectare may be required. For nonagronomic applications, 25 effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required. One skilled in the art can easily determine the biologically effective amount necessary for the desired level of invertebrate pest control. In general for veterinary use, a compound of Formula 1, an N-oxide or a salt thereof, is 30 administered in a parasiticidally effective amount to an animal to be protected from invertebrate parasite pests. A parasiticidally effective amount is the amount of active ingredient needed to achieve an observable effect diminishing the occurrence or activity of the target invertebrate parasite pest. One skilled in the art will appreciate that the parasitically effective dose can vary for the various compounds and compositions of the 35 present invention, the desired parasitical effect and duration, the target invertebrate pest species, the animal to be protected, the mode of application and the like, and the amount needed to achieve a particular result can be determined through simple experimentation.
WO 2007/123853 PCT/US2007/009181 96 For oral administration to homeothermic animals, the daily dosage of a compound of the present invention typically ranges from about 0.01 mg/kg to about 100 mg/kg, more typically from about 0.5 mg/kg to about 100 mg/kg, of animal body weight. For topical (e.g., dermal) administration, dips and sprays typically contain from about 0.5 ppm to about 5 5000 ppm, more typically from about 1 ppm to about 3000 ppm, of a compound of the present invention. The following abbreviations are used in the Index Tables A-D which follow: CF 3 means trifluoromethyl, -CN is cyano and -NO 2 is nitro. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is 10 prepared. In Index Tables A, B and C, (R 2 )m refers to the combination of (R 2 )n as shown with instance of Z being CR 2 as specified for Formula 1. INDEX TABLE A
CF
3 O'U 2 j 7 25 3 0 N (R )m R 5 Compound (R 2 )m U R 5
R
7 Q .p.) 1 (Ex. 1) 3-CI, 5-Cl C(=O) CH 3 H C(=O)NHCH 2
CF
3 ** 2 (Ex. 2) 3-CI, 5-Cl C(=O) CH 3 H C(--O)NHCH 2 -2-pyridinyl ** 3 (Ex. 4) H C(=O) H -CN -NO 2 ** 4 (Ex. 3) 3-CI, 5-CI S(=O) CH 3 H C(=O)NHCH 2 -2-pyridinyl ** 5 3-F C(=O) CH 3 H 1IH-1,2,4-triazol-1-yl * 6 3-CI, 5-Cl C(=O) CH 3 H 1IH-1,2,4-triazol-1-yl * 7 3-F C(=O) CH 3 H C(=O)NHCH 2 -2-pyridinyl * 8 3-C1, 5-CI C(=O) Cl H 4-morpholinyl * 9 3-Cl, 5-CI C(=O) H H -CN * 10 3-CI, 4-CI C(=O) CH 3 H 1H-1,2,4-triazol-1-yl * 11 3-Cl C(=O) CH 3 H IH-1,2,4-triazol-1 -yl * 12 3-CI, 4-CI C(=O) CH 3 H C(=O)NHCH 2 -2-pyridinyl * 13 3-C1 C(=O) CH 3 H C(=O)NHCH 2 -2-pyridinyl * 14 3-Cl, 5-Cl S(=O) CH 3 H IH-1,2,4-triazol-1-yl * 15 3-C. 5-CI S(=O) 2
CH
3 H 1H-1,2,4-triazol-1-yl * 16 3-Cl, 5-Cl C(=O) -CN H 1H-1,2,4-triazol-1-yl * 17 3-CI, 5-Cl C(=O) CH 3 H Br * 18 3-C1, 5-Cl S(=O) 2
CH
3 H C(=O)NHCH 2 -2-pyridinyl * 19 3-CI, 5-CI C(=O) CH 3 H C(=O)NHCH(CH 3 )-2-pyridinyl * WO 2007/123853 PCT/US2007/009181 97 *See Index Table C for IH NMR data **See synthesis example for IH NMR data. Index Table B
CF
3 O"I U 2 N N 4Q (R 2)m Compound R" U Q m...C) 101 3-CI, 5-Cl C(--O) Br * 102 3-Cl, 5-Cl C(=O) C(=O)NHCH 2 -2-pyridinyl * 103 3-Cl, 5-Cl C(=O) C(=O)NHCH 2
CF
3 * 5 *See Index Table C for 'H NMR data Index Table C R3
CF
3 N-- u 2 \ N 36 4 /-/
(R
2 )m 5 RS Compound (R 2 )m R 3 U Q m.P.(C) 201 (Ex. 5) 3-Cl, 5-Cl H C(=O) C(=O)NHCH 2 -2-pyridinyl ** 202 (Ex. 6) 3-Cl, 5-Cl Me C(=O) C(=O)NHCH 2 -2-pyridinyl ** **See synthesis example for IH NMR data. INDEX TABLE D Compd. No. IH NMR Data (CDCI 3 solution unless indicated otherwise)a 5 6 8.25 (s, 1H), 8.12 (s, IH), 7.58 (br d, 2H), 7.53-7.47 (m, 4H), 7.39-7.33 (m, 6H), 7.21 (dt, 2H), 7.68 (d, 1H), 4.68 (d, 1H), 4.36 (d, 1H-), 2.27 (s, 3H). 6 5 8.26 (s, 1H), 8.12 (s, 1H), 7.57-7.50 (m, 5H), 7.36 (d, 1H), 4.68 (d, 1H), 4.35 (d, 2H), 2.27 (s, 3H). 7 6 7.80-7.20 (m, 11H), 4.74 (d, 2H), 4.65 (d, 1-1), 4.34 (d, 1I), 2.50 (s, 3H). 8 6 7.56-7.35 (m, 5H), 7.06 (d, 1H), 4.57 (d, 1H), 4.24 (d. IH), 3.87 (m, 4H), 3.03 (m, 4H). 9 6 7.73 - 7.68 (m, 4H), 7.51 (s, IH), 7.48 (s, 211). 4.64 (d, IH), 4.30 (d, 1I). 10 6 8.60 (s, 1H), 8.09 (s, IH), 7.91 (d, IH), 7.81 (d, 1H), 7.75-7.69 (m, 3H), 7.47 (d, 111), 5.05 (d, 1H), 4.84 (d, IH), 2.26 (s, 3H).
WO 2007/123853 PCT/US2007/009181 98 Compd. No. 1H NMR Data (CDCI 3 solution unless indicated otherwise)a 11 8 8.60 (s, IH), 8.09 (s, 1H), 7.76-7.60 (m, 6H), 7.47 (d, 11H), 5.05 (d, IH), 4.82 (d, IH), 2.26 (s, 3H). 12 8 8.50 (d, 1H), 8.02 (t, IH), 7.88 (d, IH), 7.78-7.61 (m, 6H), 7.41 (d, 1H), 7.21 (dd, 1H), 4.98 (d, IH), 4.77 (d, IH), 4.65 (d, 2H11), 2.45 (s, 3H1). 13 8 8.48 (d, 1H), 8.04 (t, 1H), 7.74-7.52 (m, 8H1), 7.41 (d, IH), 7.21 (dd, IH), 4.98 (d, 1H), 4.75 (d, IH), 4.65 (d, 2H), 2.45 (s, 31H). 14 (1:1 mixture of diastereomers) 8 8.25 (s, 0.51H), 8.22 (s, 0.5H), 8.13 (s, 0.5H1), 8.12 (s, 0.51H), 7.50 (m, 3H), 7.34 (t, 1H), 7.12-7.04 (m, 2H), 4.75 (d, 0.51H), 4.58 (d, 0.5H), 4.42 (d, 0.5H), 4.22 (d, 0.5H), 2.25 (s, 1.5H), 2.23 (s, 1.5H) 15 8 8.27 (s, 1H), 8.13 (s, 1H), 7.54 (t, 1H), 7.49 (br s, 2H), 7.40 (d, 1H), 7.33 (br d, 1H), 7.28 (dd, 1H), 4.68 (d, 1H), 4.33 (d, 1H), 2.27 (s, 31H). 16 8 8.76 (s, IH), 8.18 (s, 1H), 8.02 (m, 211), 7.84 (d, 1H), 7.52 (m, 3H), 4.70 (d, 11), 4.38 (d, IH). 17 8 7.54 (d, 1H), 7.50-7.48 (m, 3H), 7.41 (d, 1H), 7.22 (dd, 1H), 4.58 (d, 11), 4.24 (d, 11). 18 858.51 (d, 1H), 8.03 (br t, 11H), 7.79-7.75 (m, 4H), 7.62 (d, 1H1), 7.46 (d, 1H1), 7.34 (m, 2H), 7.25 (dd, IH), 5.14 (d, 1H), 4.92 (d, IH), 4.68 (d, 21H1), 2.47 (s, 31H1). 19 8 8.51 (d, 1H), 7.70 (dt, 1H), 7.49 (br s, 4H), 7.41 (dd, 1H), 7.35-7.29 (m, 3H), 7.21 (dd, 1H), 5.31 (quintet, 1IH), 4.62 (d, 1H), 4.28 (d, 1H), 2.49 (s, 3H11), 1.58 (d, 3H11). 101 8 8.32 (d, 11), 7.81 (d, IH), 7.73 (br d, 1H), 7.65 (m, 2H), 7.53 (t, IH), 7.50 (m, 21H1), 7.31 (d, 1H), 4.63 (d, 1H), 4.29 (d, 1H). 102 5 8.47 (d, IH), 8.39 (m, 11), 7.73 (m, 1H), 7.64 (m, 2H), 7.57 (m, 3H), 7.51 (br s, 3H), 7.31 (dd, 2H), 7.18 (t, 1H), 4.77 (d, 2H1), 4.58 (d, 1H), 4.28 (d, 1I1H). 103 8 8.40 (br t, 1H1), 8.34 (m, 1IH), 7.95 (m, 11), 7.79-7.66 (m, 8H), 4.97 (d, 1IH), 4.86 (d, 1IH), 4.40 (m, 2H). a 1H NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (m)-multiplet, (br s)-broad singlet, (br d)-broad doublet, (br t) broad triplet, (dd)-doublet of doublet and (dt)-doublet of triplet. BIOLOGICAL EXAMPLES OF THE INVENTION 5 The following Tests demonstrate the control efficacy of compounds of this invention on specific pests. "Control efficacy" represents inhibition of invertebrate pest development (including mortality) that causes significantly reduced feeding. The pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-D for compound descriptions. 10 TEST A For evaluating control of diamondback moth (Plutella xylostella) the test unit consisted of a small open container with a 12-14-day-old radish plant inside. This was pre infested with 10-15 neonate larvae on a piece of insect diet by use of a core sampler to WO 2007/123853 PCT/US2007/009181 99 remove a plug from a sheet of hardened insect diet having many larvae growing on it and transfer the plug containing larvae and diet to the test unit. The larvae moved onto the test plant as the diet plug dried out. Test compounds were formulated using a solution containing 10% acetone, 90% water 5 and 300 ppm X-77 T m Spreader Lo-Foam Formula non-ionic surfactant containing alkylarylpolyoxyethylene, free fatty acids, glycols and isopropanol (Loveland Industries, Inc. Greeley, Colorado, USA). The formulated compounds were applied in 1 mL of liquid through a SUJ2 atomizer nozzle with 1/8 JJ custom body (Spraying Systems Co. Wheaton, Illinois, USA) positioned 1.27 cm (0.5 inches) above the top of each test unit. All 10 experimental compounds in these tests were sprayed at 50 ppm and replicated three times. After spraying of the formulated test compound, each test unit was allowed to dry for I hour and then a black, screened cap was placed on top. The test units were held for 6 days in a growth chamber at 25 oC and 70% relative humidity. The level of control efficacy of the test compound was then visually assessed based on the foliage feeding damage and the larval 15 mortality of each test unit. Of the compounds of Formula 1 tested the following provided very good to excellent levels of plant protection (20% or less feeding damage or 80% or more mortality): 1, 2, 6, 10, 12, 13, 15, 16, 18, 19 and 102. TEST B 20 For evaluating control of fall armyworm (Spodoptera frugiperda) the test unit consisted of a small open container with a 4-5-day-old corn (maize) plant inside. This was pre-infested (using a core sampler) with 10-15 1-day-old larvae on a piece of insect diet. Test compounds were formulated and sprayed at 250 ppm as described for Test A and replicated three times. After spraying, the test units were maintained in a growth chamber 25 and then visually rated as described for Test A. Of the compounds of Formula 1 tested, the following provided very good to excellent levels of plant protection (20% or less feeding damage or 80% or more mortality): 1, 2, 16, 18 and 19. TEST C 30 For evaluating control of the western flower thrips (Frankliniella occidentalis) through contact and/or systemic means, the test unit consisted of a small open container with a 5-7 day old Longio Bean plant inside. Test compounds were formulated and sprayed at 250 ppm and replicated three times as described for Test A. After spraying, the test units were allowed to dry for 1 h and then 22 35 27 adult thrips were added to each unit and a black, screened cap was placed on top. The test units were held for 7 days at 25 'C and 45-55% relative humidity. A mortality rating was assessed for each test unit.
WO 2007/123853 PCT/US2007/009181 100 Of the compounds tested, the following provided very good to excellent levels of plant protection (20% or less feeding damage or 80% or more mortality): 2, 12, 18 and 19. TEST D For evaluating control of potato leafhopper (Empoasca fabae Harris) through contact 5 and/or systemic means, the test unit consisted of a small open container with a 5-6 day old Soleil bean plant (primary leaves emerged) inside. White sand was added to the top of the soil and one of the primary leaves was excised prior to application. Test compounds were formulated and sprayed at 250 ppm, and the test was replicated three times as described for Test A. After spraying, the test units were allowed to dry for 1 hour before they were post 10 infested with 5 potato leafhoppers (18- to 21-day old adults). A black, screened cap was placed on the top of the cylinder. The test units were held for 6 days in a growth chamber at 19-21 'C and 50-70% relative humidity. The control efficacy of each test unit was then visually assessed by the insect mortality. Of the compounds of Formula 1 tested the following provided very good to excellent 15 levels of control efficacy (70% or more mortality): 2, 12, 16, 18, 19 and 103. TEST E For evaluating control of green peach aphid (Myzus persicae) through contact and/or systemic means, the test unit consisted of a small open container with a 12-15-day-old radish plant inside. This was pre-infested by placing on a leaf of the test plant 30-40 aphids 20 on a piece of leaf excised from a culture plant (cut-leaf method). The larvae moved onto the test plant as the leaf piece desiccated. After pre-infestation, the soil of the test unit was covered with a layer of sand. All test compounds were formulated and sprayed at 250 ppm as described for Test A and replicated three times. After spraying of the formulated test compound, each test unit 25 was allowed to dry for 1 hour and then a black, screened cap was placed on top. The test units were held for 6 days in a growth chamber at 19-21 'C and 50-70% relative humidity. Each test unit was then visually assessed for insect mortality. Of the compounds of Formula 1 tested, the following resulted in 50% or more mortality: 2, 18 and 19. 30 TEST F For evaluating control of cotton melon aphid (Aphis gossypii) through contact and/or systemic means, the test unit consisted of a small open container with a 6-7-day-old cotton plant inside. This was pre-infested with 30-40 insects on a piece of leaf according to the cut-leaf method described for Test C, and the soil of the test unit was covered with a layer of 35 sand. Test compounds were formulated and sprayed at 250 ppm as described for Test A. The applications were replicated three times. After spraying of the formulated test compound, each test unit was allowed to dry for 1 hour and then a black, screened cap was WO 2007/123853 PCT/US2007/009181 101 placed on top. The test units were held for 6 days in a growth chamber at 19-21 oC and 50 70% relative humidity. Each test unit was then visually assessed for insect mortality. Of the compounds of Formula 1 tested, the following resulted in 50% or more mortality: 16, 18 and 19. 5 TEST G For evaluating control of the cat flea (Ctenocephalides felis Bouche), a CD-1 mouse (about 30 g, male, obtained from Charles River Laboratories, Wilmington, MA) was orally dosed with a test compound at 30 ppm solubilized in propylene glycol/glycerol formal (60:40). Two hours after oral administration of the test compound, approximately 8 to 16 10 adult fleas were applied to each mouse. The fleas were then evaluated for mortality 48 hours after flea application to the mouse. Of the compounds tested, the following compounds caused 50% or more mortality: 1, 2, 12, 13, 16, 18, 19 and 102.

Claims (27)

1. A compound of Formula 1, an N-oxide, or a salt thereof, R 1 N ZK ' c A (R2)n 1 A2- Q 5 wherein GisOorNR 3 ; U is C(=O), S(=O), C(=S), or S(0)2; Z is N or CR 2 ; A 1 is CR 4 or N; 10 A 2 is CR 5 or N; A 3 is CR 6 or N; A 4 is CR 7 or N; Q is a 5 or 6-membered saturated or unsaturated heterocycle optionally substituted with one or more substituents independently selected from halogen, C 1 -C 6 alkyl, 15 C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, Ct-C 6 alkylthio, CI-C 6 haloalkylthio, CI-C 6 alkylsulfinyl, CI-C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, CI-C 6 haloalkylsulfonyl, CI-C 6 alkylamino, C 2 -C 8 dialkylamino, cyano, nitro, C(=O)NR 8 R 9 , C(=O)ORIO, phenyl and pyridinyl, each phenyl or pyridinyl optionally substituted with one or 20 more substituents independently selected from R 1; or Q is C(O)NRI 2 R 1 3 , C(S)NR 1 2 R 1 3 , S(O) 2 NRI 4 R 1 5 or R 1 6 ; R 1 is cyano; or C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 4 -C 7 alkylcycloalkyl or C 4 -C 7 cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from R 1 7 ; 25 each R 2 is independently H, halogen, CI-C 6 alkyl, Cl-C 6 haloalkyl, CI-C 6 alkoxy, C-C 6 haloalkoxy, CI-C 6 alkylthio, Ct-C 6 haloalkylthio, C-C 6 alkylsulfinyl, CI-C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, CI-C 6 haloalkylsulfonyl, CI-C 6 alkylamino, C 2 -C 8 dialkylamino, C 2 -C 4 alkoxycarbonyl, C 2 -C 4 alkylaminocarbonyl, C 3 -C 9 dialkylaminocarbonyl, cyano or nitro; 30 R 3 is H, cyano or -CHO; or C-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 4 -C 7 alkylcycloalkyl, C 4 -C 7 cycloalkylalkyl, phenyl, CI-C 6 alkylcarbonyl, Ci-C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl or C 3 -C 9 dialkylaminocarbonyl, each optionally substituted with one or more substituents independently selected from RIS; WO 2007/123853 PCT/US2007/009181 103 R 4 , R 5 , R 6 and R 7 are independently selected from H, halogen, C 1 -C 6 alkyl, CI-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, CI-C 6 haloalkoxy, CI-C 6 alkylthio, C 1 -C 6 haloalkylthio, CI-C 6 alkylsulfinyl, CI-C 6 haloalkylsulfinyl, CI-C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, CI-C 6 5 alkylamino, C 2 -C 8 dialkylamino, cyano and nitro; or R 6 and R 7 are taken together to form a fused aromatic ring, the fused aromatic ring containing as ring members in addition to the A 3 and A 4 bridgehead atoms, 3 atoms selected from 1 to 2 carbon atoms, 0 to 2 nitrogen atoms, 0 to 1 oxygen atom and 0 to 1 sulfur atom, or 4 atoms selected from 2 to 4 carbon atoms and 0 10 to 2 nitrogen atoms; each R 8 , R 12 and R 14 is independently H, CI-C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 C 6 alkynyl, C 3 -C 6 cycloalkyl, C 4 -C 7 alkylcycloalkyl, C 4 -C 7 cycloalkylalkyl, C 2 C 7 alkylcarbonyl, C 2 -C 6 alkoxyalkyl or C 2 -C 7 alkoxycarbonyl; each R 9 , R 10 , R 1 3 and R 1 5 is independently H; or CI-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 15 alkynyl, C 3 -C 6 cycloalkyl, C 4 -C 7 alkylcycloalkyl or C 4 -C 7 cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from RI 9 ; each RI 1, R 23 and R 24 is independently halogen, CI-C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, Ct-C 6 alkylthio, C-C 6 haloalkylthio, C 1 -C 6 20 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, CI-C 6 alkylaminosulfonyl, CI-C 8 alkylamino, C 2 -C 8 dialkylamino, C 2 -C 4 alkoxycarbonyl, cyano or nitro; R 16 is halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, CI-C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 25 haloalkylthio, CI-C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, Cl-C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkylamino, C 2 -C 8 dialkylamino, cyano or nitro; each R 17 and R 18 is independently halogen, C 1 -C 6 alkyl, CI-C 6 alkoxy, CI-C 6 alkylthio, C 1 -C 6 alkylsulfinyl, CI-C 6 alkylsulfonyl, cyano or nitro; each R 19 is independently halogen, CI-C 6 alkyl, Ct-C 6 alkoxy, C 1 -C 6 alkylthio, C 1 -C 6 30 alkylsulfinyl, CI-C 6 alkylsulfonyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, trimethylsilyl, cyano, nitro or Q1; each QI is independently a phenyl or a 5- or 6-membered saturated or unsaturated heterocycle, each optionally substituted with one or more substituents independently selected from halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 35 cycloalkyl, C 3 -C 6 halocycloalkyl, CI-C 6 alkoxy, Ci-C 6 haloalkoxy, CI-C 6 alkylthio, CI-C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C I -C 6 haloalkylsulfonyl, C I -C 6 alkylamino, C 2 -C 8 dialkylamino, cyano, nitro, C(O)NR 2 0R 2 1 , C(O)OR 22 , phenyl or pyridinyl, each WO 2007/123853 PCT/US2007/009181 104 phenyl or pyridinyl optionally substituted with one or more substituents independently selected from R 2 3 ; each R 20 is independently H, CI-C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 4 -C 7 alkylcycloalkyl, C 4 -C 7 cycloalkylalkyl, C 2 -C 7 5 alkylcarbonyl or C 2 -C 7 alkoxycarbonyl; each R 2 1 and R 22 is independently H; or C 1 -C 6 alkyl, CI-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 4 -C 7 alkylcycloalkyl, C 4 -C 7 cycloalkylalkyl, phenyl or pyridinyl; each phenyl or pyridinyl optionally substituted with one or more substituents independently selected from R 24 ; and 10 n is 1,2, 3 or4; and provided that R 16 is other than methoxy.
2. The compound of Claim 1 wherein Q is a pyridinyl ring, a pyrimidinyl ring, a triazinyl ring, a pyrazolyl ring, a triazolyl ring, an imidazolyl ring, an oxazolyl ring, an isoxazolyl ring, a thiazolyl ring or 15 an isothiazolyl ring, each ring optionally substituted with one or more substituents independently selected from halogen, Cl-C 6 alkyl, Cl-C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, CI-C 6 haloalkoxy, C 1 -C 6 alkylthio, Cl-C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, CI-C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 20 alkylamino, C 2 -C 8 dialkylamino, cyano, nitro, C(O)NR 8 R 9 , C(O)OR 10 , phenyl and pyridinyl, each phenyl and pyridinyl optionally substituted with one or more substituents independently selected from RI 1; or Q is C(O)NRI 2 RI 13 , S(O) 2 NR 1 4 RI 5 or R16; Z is CR 2 ; 25 R 1 is C 1 -C 3 alkyl optionally substituted with one or more substituents independently selected from RI 7 ; each R 2 is independently selected from H, halogen or Cl-C 2 haloalkyl; R 3 is H or cyano; or CI-C 4 alkyl optionally substituted with one or more substituents selected from halogen; 30 R 4 and R 5 are independently selected from halogen, Ct-C 3 alkyl, C 1 -C 3 haloalkyl, cyano and nitro; R 6 and R 7 are independently selected from halogen, CI-C 3 alkyl, CI-C 3 haloalkyl, cyano and nitro; or R 6 and R 7 are taken together to form a fused aromatic ring, the fused aromatic ring containing as ring members in addition to the A 3 and A 4 35 bridgehead atoms, 4 atoms selected from 3 to 4 carbon atoms and 0 to I nitrogen atom; each R 8 is independently H, C I-C 6 alkyl, C 2 -C 7 alkylcarbonyl or C 2 -C 7 alkoxycarbonyl; WO 2007/123853 PCT/US2007/009181 105 each R 9 and RI 0 is independently H; or CI-C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 4 cycloalkyl, C 4 -C 7 alkylcycloalkyl or C 4 -C 7 cycloalkylalkyl, each optionally substituted with one or more substituents selected from R 19 ; R 1 2 and R 14 are independently H, CI-C 6 alkyl, C 2 -C 7 alkylcarbonyl or C2-C 7 5 alkoxycarbonyl; R 13 and R 15 are independently H; or Cl-C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 4 cycloalkyl, C 4 -C 7 alkylcycloalkyl or C 4 -C 7 cycloalkylalkyl, each optionally substituted with one or more substituents selected from R 19 ; R 16 is halogen, CI-C 3 haloalkyl, C 2 -C 4 dialkylamino, cyano or nitro; 10 each R 19 is independently selected from halogen, CI-C 4 alkyl, CI-C 4 alkoxy, Ct-C 4 alkylthio, C 1 -C 4 alkylsulfonyl, cyano, nitro and Q 1 ; each QI is independently selected from phenyl, pyridinyl and thiazolyl, each optionally substituted with one or more substituents independently selected from halogen, CI-C 3 alkyl, CI-C 3 haloalkyl, cyano, phenyl and pyridinyl; and 15 n is 1 or 2; provided that at most 1 of A 1 , A 2 , A 3 and A 4 is N.
3. The compound of Claim 2 wherein RI is CI-C 3 alkyl substituted with halogen; and U is C(=o). 20
4. The compound of Claim 3 wherein Q is a pyrazolyl ring, a triazolyl ring or an imidazolyl ring, each ring attached through nitrogen and optionally substituted with one or more substituents independently selected from halogen, C -C 4 alkyl, C I-C 4 haloalkyl, C -C 4 alkoxy, C I-C 4 haloalkoxy, cyano, nitro, C(O)NR 8 R 9 and C(O)OR10; or Q is C(O)NR 1 2 RI3; 25 RI is CF 3 ; R 6 and R 7 are independently selected from H, halogen, Ci-C 3 alkyl, CI-C 3 haloalkyl, cyano and nitro; or R 6 and R 7 are taken together to form a fused aromatic ring, the fused aromatic ring containing 4 carbon atoms as ring members in addition to the A 3 and A 4 bridgehead atoms; 30 each R 8 is H; each R 9 and R 10 is independently CI-C 4 alkyl optionally substituted with one Q l and optionally substituted with one or more substituents selected from halogen, Ct-C 4 alkyl, CI-C 4 alkoxy, Ct-C 4 alkylthio, Ct-C 4 alkylsulfonyl and cyano; R 12 is H; 35 R 13 is H; or Cl-C 4 alkyl optionally substituted with one or more substituents selected from RI 9 ; and each R 19 is independently selected from halogen and Q1. WO 2007/123853 PCT/US2007/009181 106
5. The compound of Claim 4 wherein each R 2 is independently H, halogen or CF 3 ; and R 3 is CH 3 , CH 2 CH 3 , or CH 2 CF 3 .
6. The compound of Claim 5 wherein 5 G is O; and [El] provided that A 1 , A 2 , A 3 and A 4 are each other than N.
7. The compound of Claim 1 that is selected from the group consisting of: 4-[5-(3,5-dichlorophenyl)-2-oxo-5-(trifluoromethyl)-3-oxazolidinyl]-2-methyl N-(2-pyridinylmethyl)benzamide; 4-[5-(3,5-dichlorophenyl)-2-oxo-5-(trifluoromethyl)-3-oxazolidinyl]-2-methyl N-(2,2,2-trifluoroethyl)benzamide; 4-[5-(3,5-dichlorophenyl)-2-oxido-5-(trifluoromethyl)-1,2,3-oxathiazolidin-3-yl] 2-methyl-N-(2-pyridinylmethyl)benzamide; 2-nitro-5-[2-oxo-5-phenyl-5-(trifluoromethyl)-3-oxazolidinyl]benzonitrile; 4-[4-(3,5-dichlorophenyl)-2-oxo-4-(trifluoromethyl)-l1-imidazolidinyl]-2-methyl N-(2-pyridinylmethyl)benzamide; 4-[4-(3,5-dichlorophenyl)-3-methyl-2-oxo-4-(trifluoromethyl)-1-imidazolidinyl] 2-methyl-N-(2-pyridinylmethyl)benzamide; 4-[5-(3,4-dichlorophenyl)-2-oxo-5-(trifluoromethyl)-3-oxazolidinyl]-2-methyl N-(2-pyridinylmethyl)benzamide; 5-[5-(3,5-dichlorophenyl)-2-oxo-5-(trifluoromethyl)-3-oxazolidinyl] 2-(I1H-1,2,4-triazol-1-yl)benzonitrile; 4-[5-(3,5-dichlorophenyl)-2,2-dioxido-5-(trifluoromethyl)-1,2,3-oxathiazolidin 3-yl]-2-methyl-N-(2-pyridinylmethyl)benzamide; and 4-[5-(3,5-dichlorophenyl)-2-oxo-5-(trifluoromethyl)-3-oxazolidinyl]-2-methyl N-[1-(2-pyridinyl)ethyl]benzamide.
8. A composition comprising a compound of Claim 1 and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid 10 diluent, said composition optionally further comprising at least one additional biologically active compound or agent.
9. A composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Claim 1 and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said 15 composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent. WO 2007/123853 PCT/US2007/009181 107
10. The composition of Claim 9 wherein at least one additional biologically active compound or agent is selected insecticides of the group consisting of macrocyclic lactones, neonicotinoids, octopamine receptor ligands, ryanodine receptor ligands, ecdysone agonists, sodium channel modulators, chitin synthesis inhibitors, nereisotoxin analogs, mitochondrial 5 electron transport inhibitors, cholinesterase inhibitors, cyclodiene insecticides, molting inhibitors, y-aminobutyric acid-regulated chloride channel blockers, juvenile hormone mimics, lipid biosynthesis inhibitors and biological agents including nucleopolyhedro viruses, members of Bacillus thuringiensis, encapsulated delta-endotoxins of Bacillus thuringiensis, and other naturally occurring or genetically modified insecticidal viruses. 10
11. The composition of Claim 9 wherein the at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acephate, acetamiprid, acetoprole, aldicarb, amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, bistrifluron, buprofezin, carbofuran, cartap, chinomethionat, chlorfenapyr, chlorfluazuron, chlorantraniliprole, chlorpyrifos, chlorpyrifos 15 methyl, chlorobenzilate, chromafenozide, clothianidin, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dicofol, dieldrin, dienochlor, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etoxazole, fenamiphos, fenazaquin, fenbutatin oxide, 20 fenothiocarb, fenoxycarb, fenpropathrin, fenpyroximate, fenvalerate, fipronil, flonicamid, flubendiamide, flucythrinate, tau-fluvalinate, flufenerim, flufenoxuron, fonophos, halofenozide, hexaflumuron, hexythiazox, hydramethylnon, imicyafos, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, metaflumizone, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, methoxyfenozide, 25 metofluthrin, monocrotophos, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, propargite, protrifenbute, pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spiridiclofen, spiromesifen, spirotetramat, sulprofos, 30 tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate, trichlorfon, triflumuron, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, nucleopolyhedro viruses, encapsulated delta-endotoxins of Bacillus thuringiensis, baculoviruses, entomopathogenic bacteria, entomopathogenic viruses 35 and entomopathogenic fungi.
12. The composition of Claim 11 wherein the at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acetamiprid, amitraz, WO 2007/123853 PCT/US2007/009181 108 avermectin, azadirachtin, bifenthrin, buprofezin, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin; cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenvalerate, fipronil, 5 flonicamid, flubendiamide, flufenoxuron, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, metaflumizone, methomyl, methoprene, methoxyfenozide, nitenpyram, nithiazine, novaluron, oxamyl, pymrnetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, tebufenozide, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamrnate, 10 triflumuron, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, nucleopolyhedro viruses and encapsulated delta-endotoxins of Bacillus thuringiensis.
13. The composition of Claim 9 in the form of a soil drench liquid formulation.
14. A spray composition for controlling an invertebrate pest, comprising:(a) a biologically effective amount of the compound of Claim 1 or the composition of 15 Claim 9; and (b) a propellant.
15. A bait composition for controlling an invertebrate pest, comprising: (a) a biologically effective amount of the compound of Claim 1 or the composition of Claim 9; 20 (b) one or more food materials; (c) optionally an attractant; and (d) optionally a humectant.
16. A trap device for controlling an invertebrate pest, comprising: (a) the bait composition of Claim 15; and 25 (b) a housing adapted to receive the bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to the bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest. 30
17. A method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Claim 1.
18. A method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a composition of Claim 9. 35
19. The method of Claim 18 wherein the environment is soil and the composition is applied to the soil as a soil drench formulation. WO 2007/123853 PCT/US2007/009181 109
20. A method for controlling a cockroach, an ant or a termite, comprising contacting a cockroach, an ant, or a termite with the bait composition in a trap device of Claim 16.
21. A method for controlling a mosquito, a black fly, a stable, fly, a deer fly, a horse fly, a wasp, a yellow jacket, a hornet, a tick, a spider, an ant, or a gnat, comprising contacting 5 a mosquito, a black fly, a stable, fly, a deer fly, a horse fly, a wasp, a yellow jacket, a hornet, a tick, a spider, an ant, or a gnat with the spray composition of Claim 14 dispensed from a spray container.
22. A method for protecting a seed from an invertebrate pest comprising contacting the seed with a biologically effective amount of a compound of Claim 1. 10
23. The method of Claim 22 wherein the seed is coated with the compound of Claim 1 formulated as a composition comprising a film former or adhesive agent.
24. A treated seed comprising a compound of Claim 1 in an amount of from about 0.0001 to 1 % by weight of the seed before treatment.
25. A composition for protecting an animal from an invertebrate parasitic pest 15 comprising a parasiticidally effective amount of a compound of Claim 1 and at least one carrier.
26. The composition of Claim 25 in a form for oral administration.
27. A method for protecting an animal from an invertebrate parasitic pest comprising administering to the animal a parasiticidally effective amount of a compound of 20 Claim 1.
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