Pyridine compounds for controlling invertebrate pests

Abstract

Disclosed are compounds of Formula (1), including all geometric and stereoisomers, N-oxides, and salts thereof, where R1, A, R2, R4, R5, and Q are as defined in the disclosure. Also disclosed are compositions containing these compounds of Formula (1), and methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound or composition of the disclosure. # imgabs0 #

Description

[0001] This application is a divisional application of Chinese Patent Application No. 202180012109.5, filed on January 29, 2021, with the invention title "Pyridine Compounds for Controlling Invertebrate Pests" (the international application number of this application is PCT / US2021 / 015643), the entire content of which is incorporated herein by reference.

[0002] Cross-reference to related applications

[0003] This application claims the benefit of U.S. Provisional Application No. 62 / 967,838, filed on January 30, 2020. TECHNICAL FIELD

[0004] This disclosure relates to certain pyridine compounds, their N-oxides, salts, and compositions suitable for agricultural and non-agricultural uses, and methods for using them to control invertebrate pests such as arthropods in agricultural and non-agricultural environments. BACKGROUND OF THE DISCLOSURE

[0005] Controlling invertebrate pests is extremely important in achieving high crop efficiency. Damage to growing and stored agricultural crops by invertebrate pests can result in a significant reduction in productivity and, consequently, an increase in costs to consumers. The control of invertebrate pests in forestry, greenhouse crops, ornamental plants, nursery crops, stored food and fiber products, livestock, households, turf, wood products, as well as public health and animal health is also important. For these purposes, many products are commercially available, but there is a continuing need for new compounds that are more effective, lower in cost, less toxic, safer to the environment, or have different modes of action. SUMMARY OF THE DISCLOSURE

[0006] This disclosure relates to compounds of Formula 1 (including all geometric and stereoisomers), their N-oxides and salts, and compositions containing them, and their use for controlling invertebrate pests:

[0007]

[0008] Wherein

[0009] R 1 is F, OR 6 or S(O) n R 6 ;

[0010] A is N or CR 3 ;

[0011] R 2is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

[0012] R 3 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

[0013] R 4 is a 5- to 6-membered heterocycle, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O atoms, up to 2 S atoms and up to 4 N atoms, where up to 2 ring members are independently selected from C(=O), C(=S), S(=O) and S(=O)2, each ring optionally being substituted by up to 5 substituents independently selected from R v and r is the number of these substituents;

[0014] Each R v is independently H, cyano, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 cyanoalkyl, C1-C6 hydroxyalkyl, C4-C 10 alkylcycloalkyl, C4-C 10 cycloalkylalkyl, C3-C6 cycloalkenyl, C3-C6 halocycloalkenyl, C2-C6 alkoxyalkyl, C4-C 10 cycloalkoxyalkyl, C3-C 10 alkoxyalkoxyalkyl, C2-C6 alkylthioalkyl, C2-C6 alkylsulfinylalkyl, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-C 10 cycloalkylalkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C2-C6 alkoxyalkoxy, C2-C6 alkylcarbonyloxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C3-C6 cycloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C6 cycloalkylsulfonyl, C1-C6 alkylamino, C2-C6 dialkylamino, C1-C6 haloalkylamino, C2-C6 halodialkylamino or C3-C6 cycloalkylamino;

[0015] r is 1, 2, 3, 4 or 5;

[0016] R5 is H, a halogen, CN, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C3-C4 cycloalkyl group, a C3-C4 halocycloalkyl group, a C1-C4 alkoxy group or a C1-C4 haloalkoxy group;

[0017] R 6 is a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C3-C4 cycloalkyl group or a C3-C4 halocycloalkyl group;

[0018] Q is a six-membered aromatic ring containing ring members selected from carbon atoms and up to 2 nitrogen atoms, each ring optionally being substituted on the carbon atom ring members by up to 5 substituents independently selected from one or more R w ; and s is the number of these substituents;

[0019] R w are independently H, cyano, halogen, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C2-C6 alkynyl group, a C2-C6 haloalkynyl group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a C2-C6 cyanoalkyl group, a C1-C6 hydroxyalkyl group, a C4-C 10 alkylcycloalkyl group, a C4-C 10 cycloalkylalkyl group, a C3-C6 cycloalkenyl group, a C3-C6 halocycloalkenyl group, a C2-C6 alkoxyalkyl group, a C4-C 10 cycloalkoxyalkyl group, a C3-C 10 alkoxyalkoxyalkyl group, a C2-C6 alkylthioalkyl group, a C2-C6 alkylsulfinylalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkoxy group, a C3-C6 halocycloalkoxy group, a C4-C 10 cycloalkylalkoxy group, a C2-C6 alkenyloxy group, a C2-C6 haloalkenyloxy group, a C2-C6 alkoxyalkoxy group, a C2-C6 alkylcarbonyloxy group, a C1-C6 alkylthio group, a C1-C6 haloalkylthio group, a C3-C6 cycloalkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 haloalkylsulfinyl group, a C3-C6 cycloalkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylsulfonyl group, a C3-C6 cycloalkylsulfonyl group, a C1-C6 alkylamino group, a C2-C6 dialkylamino group, a C1-C6 haloalkylamino group, a C2-C6 halodialkylamino group or a C3-C6 cycloalkylamino group; or two R w on adjacent carbon atoms may together form an -OCF2O-, -OCH2O-, -OCF2S-, -OCH2CH2)-, OCF2CF2O- cyclic ether ring;

[0020] s is 1, 2, 3, 4 or 5;

[0021] n is 0, 1 or 2;

[0022] provided that

[0023] 1) when R 1 is F, R 2 is H, A is CR 3 wherein R 3 is F, R 4 is pyrazol-1-yl and R 5 is H, and Q is not 4-OCF3-phenyl; and

[0024] 2) R 4 is not pyridyl.

[0025] The present disclosure also provides a composition comprising a compound of formula 1, its N-oxide or salt, and at least one additional component selected from the group consisting of a surfactant, a solid diluent, and a liquid diluent. In one embodiment, the present disclosure also provides a composition for controlling invertebrate pests, the composition comprising a compound of formula 1, its N-oxide or salt, and at least one additional component selected from the group consisting of a surfactant, a solid diluent, and a liquid diluent, and the composition optionally further comprises at least one additional biologically active compound or agent.

[0026] The present disclosure also provides a method for controlling invertebrate pests, the method comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of formula 1, its N-oxide or salt (e.g., as a composition described herein). The present disclosure also relates to such a method, wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of formula 1, its N-oxide or salt, and at least one additional component selected from the group consisting of a surfactant, a solid diluent, and a liquid diluent, and the composition optionally further comprises a biologically effective amount of at least one additional biologically active compound or agent.

[0027] The present disclosure also provides a method for controlling invertebrate pests, the method comprising contacting the invertebrate pest or its environment with any one of the above-described compositions in a biologically effective amount, wherein the environment is a plant.

[0028] The present disclosure also provides a method for controlling invertebrate pests, the method comprising contacting the invertebrate pest or its environment with any one of the above-described compositions in a biologically effective amount, wherein the environment is an animal.

[0029] The present disclosure also provides a method for controlling invertebrate pests, the method comprising contacting the invertebrate pest or its environment with any one of the above-described compositions in a biologically effective amount, wherein the environment is a seed.

[0030] The present disclosure also provides a method for protecting seeds from invertebrate pests, the method comprising contacting the seeds with a biologically effective amount of a compound of formula 1, its N-oxide or salt (e.g., as a composition described herein). The present disclosure also relates to treated seeds (i.e., seeds contacted with a compound of formula 1).

[0031] The present disclosure also provides a method for increasing the vigor of a crop plant, the method comprising contacting the crop plant, the seeds from which the crop plant grows, or the locus of the crop plant (e.g., the growth medium) with a biologically effective amount of a compound of formula 1 (e.g., as a composition described herein).

[0032] The present disclosure further provides a method for protecting an animal from invertebrate parasitic pests, the method comprising administering to the animal a parasitically effective amount of a compound of formula 1, its N-oxide or salt (e.g., as a composition described herein). The present disclosure also provides the use of a compound of formula 1, its N-oxide or salt (e.g., as a composition described herein) in protecting an animal from invertebrate pests. Detailed Description

[0033] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," "characterized by," or any other variation thereof, are intended to cover non-exclusive inclusion, subject to any limitations expressly recited. For example, a composition, mixture, process, or method that comprises a series of elements is not necessarily limited to those elements, but may include other elements not expressly listed or other elements inherent to such composition, mixture, process, or method.

[0034] The connecting phrase "consisting of" excludes any unrecited element, step, or ingredient. If in a claim, this phrase renders the claim closed, excluding materials other than those recited, except for impurities ordinarily associated therewith. When the phrase "consisting of" appears in a clause of the claim body rather than immediately following the preamble, the phrase limits only the elements set forth in that clause; as a whole, the claim does not exclude other elements.

[0035] The connecting phrase "consisting essentially of" is used to define a composition or method that includes materials, steps, features, components, or elements in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel features of the claimed disclosure. The term "consisting essentially of" lies between "comprising" and "consisting of".

[0036] When an applicant has defined an embodiment or a part thereof with an open - ended term such as "comprising", it should be readily understood (unless otherwise stated) that the specification should be interpreted as also using the term "consisting essentially of" or "consisting of" to describe that embodiment.

[0037] In addition, unless expressly stated to the contrary, "or" means an inclusive or rather than an exclusive or. For example, condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0038] Similarly, the indefinite article "a / an" before an element or component of the present disclosure is intended to be non - restrictive with respect to the number of examples (i.e., occurrences) of the element or component. Thus, "a or an" should be understood to include one or at least one, and the singular word form of an element or component also includes the plural, unless the number clearly means the singular.

[0039] As mentioned in the present disclosure, the term "invertebrate pest" includes arthropods, gastropods, nematodes, and worms that are 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 "nematode" includes members of the phylum Nematoda, such as phytophagous nematodes and worm nematodes parasitic on animals. The term "worm" includes all parasites, such as roundworms (phylum Nematoda), heartworms (phylum Nematoda, class Secernentea), flukes (phylum Platyhelminthes, class Tematoda), acanthocephalans (phylum Acanthocephala), and tapeworms (phylum Platyhelminthes, class Cestoda).

[0040] In the context of the present disclosure, "invertebrate pest control" means inhibiting the development of invertebrate pests (including death, reduced feeding, and / or mating disruption), and related expressions are defined similarly.

[0041] The term "agronomy" refers to the production of field crops; such as for food and fiber, and includes the growth of maize or corn, soybeans and other legumes, rice, grains (e.g., wheat, oats, barley, rye, and rice), leafy vegetables (e.g., lettuce, cabbage, and other brassica crops), fruit vegetables (e.g., tomatoes, peppers, eggplants, crucifers, and cucurbit crops), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone, and citrus), small fruits (e.g., berries and cherries), and other specialty crops (e.g., canola, sunflowers, and olives).

[0042] The term "non - agronomy" refers to applications different from field crops, such as horticultural crops (e.g., greenhouse, nursery, or ornamental plants not grown in the field), residential, agricultural, commercial, and industrial structures, turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.), wood products, stored products, agroforestry and vegetation management, public health (i.e., human), and animal health (e.g., domestic animals such as pets, livestock, and poultry, non - domestic animals such as wildlife).

[0043] The term "crop vigor" refers to the growth rate or biomass accumulation of crop plants. "An increase in vigor" refers to an increase in growth or biomass accumulation of crop plants relative to untreated control crop plants. The term "crop yield" refers to the quantity and quality return of crop material obtained after harvesting crop plants. "An increase in crop yield" refers to an increase in crop yield relative to untreated control crop plants.

[0044] The term "biologically effective amount" refers to the amount of a biologically active compound (e.g., a compound of formula 1) sufficient to produce a desired biological effect when applied to (i.e., contacted with) an invertebrate pest to be controlled or its environment, or to a plant, the seed from which the plant grows, or the location of the plant (e.g., growth medium) to protect the plant from damage by the invertebrate pest or for other desired effects (e.g., increasing plant vigor).

[0045] Non-agricultural applications include protecting animals from invertebrate parasitic pests by administering to the animals to be protected a parasitically effective (i.e., biologically effective) amount of the compounds of the present disclosure, typically in the form of a composition formulated for veterinary use. As used in the present disclosure and the claims, the terms "parasiticidal" and "parasiticidally" refer to the observable effects on invertebrate parasitic pests to protect animals from the pests. Parasiticidal effects typically relate to a reduction in the occurrence or activity of the target invertebrate parasitic pests. Such effects on the pests include necrosis, death, growth retardation, reduced mobility or the ability to remain on or in the host animal, reduced feeding, and reproductive inhibition. These effects on invertebrate parasitic pests prevent (including preventing, reducing, or eliminating) parasitic infestation or infection of the animals.

[0046] In the foregoing detailed description, the term "alkyl", used alone or in compound words such as "alkylthio" or "haloalkyl", includes straight-chain or branched-chain alkyls such as methyl, ethyl, n-propyl, isopropyl, or the different butyl, pentyl, or hexyl isomers. "Alkenyl" includes straight-chain or branched-chain olefins such as vinyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl, and hexenyl isomers. "Alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight-chain or branched-chain alkynes such as ethynyl, 1-propynyl, 2-propynyl, and the different butynyl, pentynyl, and hexynyl isomers. "Alkynyl" may also include moieties composed of multiple triple bonds such as 2,5-hexadiynyl. "Alkylene" represents a straight-chain or branched-chain alkanediyl. Examples of "alkylene" include CH2, CH2CH2, CH(CH3), CH2CH2CH2, CH2CH(CH3), and the different butylene isomers. "Alkenylene" represents a straight-chain or branched-chain alkenediyl containing one double bond. Examples of "alkenylene" include CH═CH, CH2CH═CH, CH═C(CH3), and the different butenylene isomers. "Alkynylene" represents a straight-chain or branched-chain alkynediyl containing one triple bond. Examples of "alkynylene" include C≡C, CH2C≡C, C≡CCH2, and the different butynylene isomers.

[0047] "Alkoxy" includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy and the different butoxy, pentyloxy and hexyloxy isomers. "Alkoxyalkyl" denotes an alkoxy substitution on an alkyl group. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2. "Alkoxyalkoxy" denotes an alkoxy substitution on an alkoxy group. "Alkenyloxy" includes straight-chain or branched alkenyloxy moieties. Examples of "alkenyloxy" include H2C=CHCH2O, (CH3)2C=CHCH2O, (CH3)CH=CHCH2O, (CH3)CH=C(CH3)CH2O and CH2=CHCH2CH2O. "Alkynyloxy" includes straight-chain or branched alkynyloxy moieties. Examples of "alkynyloxy" include HC≡CCH2O, CH3C≡CCH2O and CH3C≡CCH2CH2O. "Alkylthio" includes branched or straight-chain alkylthio moieties, such as methylthio, ethylthio and the different propylthio, butylthio, pentylthio and hexylthio isomers. "Alkylsulfinyl" includes the two enantiomers of alkylsulfinyl. Examples of "alkylsulfinyl" include CH3S(O)-, CH3CH2S(O)-, CH3CH2CH2S(O)-, (CH3)2CHS(O)- and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH3S(O)2-, CH3CH2S(O)2-, CH3CH2CH2S(O)2-, (CH3)2CHS(O)2- and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. "Alkylthioalkyl" denotes an alkylthio substitution on an alkyl group. Examples of "alkylthioalkyl" include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2. "Alkylthioalkoxy" denotes an alkylthio substitution on an alkoxy group. "Alkyldithio" denotes branched or straight-chain alkyldithio moieties. Examples of "alkyldithio" include CH3SS-, CH3CH2SS-, CH3CH2CH2SS-, (CH3)2CHSS- and the different butyldithio and pentyldithio isomers. "Cyanoalkyl" denotes an alkyl group substituted by a cyano group. Examples of "cyanoalkyl" include NCCH2, NCCH2CH2 and CH3CH(CN)CH2. "Alkylamino", "dialkylamino", "alkenylthio", "alkenylsulfinyl", "alkenylsulfonyl", "alkynylthio", "alkynylsulfinyl", "alkynylsulfonyl", etc. are defined analogously to the above examples.

[0048] "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "alkylcycloalkyl" denotes an alkyl substitution on the cycloalkyl moiety and includes, for example, ethylcyclopropyl, isopropylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. The term "cycloalkylalkyl" denotes a cycloalkyl substitution on the alkyl moiety. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight or branched alkyl groups. The term "cycloalkoxy" denotes a cycloalkyl group linked through an oxygen atom, such as cyclopentyloxy and cyclohexyloxy. "Cycloalkylalkoxy" denotes a cycloalkylalkyl group linked through an oxygen atom attached to an alkyl chain. Examples of "cycloalkylalkoxy" include cyclopropylmethoxy, cyclopentylethoxy, and other cycloalkyl moieties bonded to straight or branched alkoxy groups. "Cyano-cycloalkyl" denotes a cycloalkyl group substituted by one cyano group. Examples of "cyano-cycloalkyl" include 4-cyanocyclohexyl and 3-cyanocyclopentyl. "Cycloalkenyl" includes groups such as cyclopentenyl and cyclohexenyl and groups having more than one double bond, such as 1,3-cyclohexadienyl and 1,4-cyclohexadienyl.

[0049] The term "halogen", alone or in a compound word such as "haloalkyl", or when used in a description such as "alkyl substituted by halogen", includes fluorine, chlorine, bromine or iodine. Further, when used in a compound word such as "haloalkyl", or when used in a description such as "alkyl substituted by halogen", the alkyl may be partially or fully substituted by halogen atoms (which may be the same or different). Examples of "haloalkyl" or "alkyl substituted by halogen" include F3C-, ClCH2-, CF3CH2- and CF3CCl2-. The terms "halocycloalkyl", "haloalkoxy", "haloalkylthio", "haloalkenyl", "haloalkynyl", etc. are defined analogously to the term "haloalkyl". Examples of "haloalkoxy" include CF3O-, CCl3CH2O-, HCF2CH2CH2O- and CF3CH2O-. Examples of "haloalkylthio" include CCl3S-, CF3S-, CCl3CH2S- and ClCH2CH2CH2S-. Examples of "haloalkylsulfinyl" include CF3S(O)-, CCl3S(O)-, CF3CH2S(O)- and CF3CF2S(O)-. Examples of "haloalkylsulfonyl" include CF3S(O)2-, CCl3S(O)2-, CF3CH2S(O)2- and CF3CF2S(O)2-. Examples of "haloalkenyl" include (Cl)2C=CHCH2- and CF3CH2CH=CHCH2-. Examples of "haloalkynyl" include HC≡CCHCl-, CF3C≡C-, CCl3C≡C- and FCH2C≡CCH2-. Examples of "haloalkoxyalkoxy" include CF3OCH2O-, ClCH2CH2OCH2CH2O-, Cl3CCH2OCH2O- and branched alkyl derivatives.

[0050] "Alkylcarbonyl" means a straight-chain or branched alkyl moiety bonded to a C(=O) moiety. Examples of "alkylcarbonyl" include CH3C(=O)-, CH3CH2CH2C(=O)- and (CH3)2CHC(=O)-. Examples of "alkoxycarbonyl" include CH3OC(=O)-, CH3CH2OC(=O)-, CH3CH2CH2OC(=O)-, (CH3)2CHOC(=O)- and different butoxy- or pentyloxycarbonyl isomers.

[0051] As used herein, the chemical abbreviations S(O) and S(=O) represent sulfinyl moieties. As used herein, the chemical abbreviations SO2, S(O)2 and S(=O)2 represent sulfonyl moieties. As used herein, the chemical abbreviations C(O) and C(=O) represent carbonyl moieties. As used herein, the chemical abbreviations CO2, C(O)O and C(=O)O represent oxycarbonyl moieties. "CHO" means formyl.

[0052] When R 4 is a 5- to 6-membered heterocycle substituted with up to 5 substituents independently selected from R v , the substituent R v can be attached to the remainder of the compound of formula 1 through any available ring member of the heterocycle.

[0053] When Q is a six-membered aromatic ring substituted with up to 5 substituents independently selected from R w , the substituent R w can be attached to the remainder of the compound of formula 1 through any available ring member of the six-membered aromatic ring.

[0054] The total number of carbon atoms in a substituent is denoted with the "C i -C j " prefix, where i and j are numbers from 1 to 10. For example, C1-C4 alkylsulfonyl denotes methylsulfonyl to butylsulfonyl; C2 alkoxyalkyl denotes CH3OCH2-; C3 alkoxyalkyl denotes, for example, CH3CH(OCH3)-, CH3OCH2CH2- or CH3CH2OCH2-; and C4 alkoxyalkyl denotes the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2- and CH3CH2OCH2CH2-.

[0055] When a compound is substituted with a substituent bearing a subscript (which indicates that the number of said substituents can exceed 1), the substituents (when they exceed 1) are independently selected from the group of defined substituents, for example, [(R v ) r , r is 1, 2, 3, 4 or 5; and [(R w ) s , s is 1, 2, 3, 4 or 5. When a group contains a substituent that can be hydrogen, such as R v or R w , then when the substituent is hydrogen, it is recognized that this is equivalent to the group being unsubstituted. When one or more positions on a group are said to be "unsubstituted" or "not substituted", hydrogen atoms are attached to occupy any free valences.

[0056] Unless otherwise specified, a "ring" (e.g., the substituent R 4 ) that is a component of formula 1 is carbocyclic or heterocyclic. The term "ring member" refers to an atom or other moiety (e.g., C(=O), C(=S), S(O) or S(O)2) that forms the backbone of the ring.

[0057] The terms "carbocyclic ring" and "carbocycle" denote a ring in which the atoms forming the ring skeleton are selected only from carbon. The terms "heterocyclic ring" and "heterocycle" denote a ring in which at least one atom forming the ring skeleton is not carbon (e.g., nitrogen, oxygen, or sulfur). Typically, a heterocycle contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs. Unless otherwise specified, a carbocyclic or heterocyclic ring can be a saturated or unsaturated ring. "Saturated" means a ring having a skeleton composed of atoms connected to each other by single bonds; unless otherwise specified, the remaining valence is occupied by hydrogen atoms. Unless otherwise stated, an "unsaturated ring" can be partially unsaturated or fully unsaturated. The expression "fully unsaturated ring" means a ring of atoms in which the bonds between the atoms in the ring are single or double bonds according to valence bond theory, and furthermore, the bonds between the atoms in the ring include as many double bonds as possible, but no cumulated double bonds (i.e., no C=C=C or C=C=N). The term "partially unsaturated ring" means a ring containing at least one ring member bonded to an adjacent ring member by a double bond, and conceptually may accommodate a number of non-cumulated double bonds (i.e., in its fully unsaturated corresponding form) greater than the number of double bonds present (i.e., in its partially unsaturated form).

[0058] Unless otherwise specified, a heterocycle can be attached by any available carbon or nitrogen by replacing the hydrogen on said carbon or nitrogen.

[0059] "Aromatic" means that each ring atom is substantially in the same plane and has a p-orbital perpendicular to the plane of the ring, and in which (4n + 2) π electrons (where n is a positive integer) are associated with the ring to conform to Hückel's rule. When a fully unsaturated carbocyclic ring satisfies Hückel's rule, then said ring is also referred to as an "aromatic ring" or an "aromatic carbocycle". When a fully unsaturated heterocyclic ring satisfies Hückel's rule, then said ring is also referred to as a "heteroaromatic ring" or an "aromatic heterocycle".

[0060] The term "optionally substituted" in relation to a heterocycle refers to a group that is unsubstituted or has at least one non-hydrogen substituent that does not eliminate the biological activity possessed by the unsubstituted analogue. As used herein, unless otherwise specified, the following definitions will apply. The term "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted" or with the term "(un)substituted". Unless otherwise specified, an optionally substituted group can have a substituent at each substitutable position of the group, and each substitution is independent of each other.

[0061] When R 4When it is a 5- or 6-membered nitrogen-containing heterocycle, unless otherwise described, it can be attached to the remainder of Formula 1 through any available carbon or nitrogen ring atom.

[0062] As described above, R 4 can be a 5- or 6-membered heterocycle, which can be saturated or unsaturated, optionally substituted with one or more substituents selected from the group of substituents defined in the Summary of the Invention. Examples of 5- or 6-membered unsaturated aromatic heterocycles optionally substituted with one or more substituents include Rings U-2 to U-61 shown in Example 1, where R v is any substituent as defined in the Summary of the Invention, and r is an integer from 1 to 4, subject to the number of available positions on each U group. Since U-29, U-30, U-36, U-37, U-38, U-39, U-40, U-41, U-42 and U-43 have only one available position, for these U groups, r is limited to the integer 1, and when R v is H and r is 1, it means that the U group is unsubstituted and hydrogen is present at the position indicated by (R v ) r .

[0063] Example 1

[0064]

[0065]

[0066] It should be noted that when R 4 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 defined in the Summary of the Invention, one or two carbon ring members of the heterocycle can optionally be the oxidized form of a carbonyl moiety.

[0067] Examples of 5- or 6-membered saturated or non-aromatic unsaturated heterocycles include Rings G-1 to G-35 shown in Example 2. It should be noted that when the attachment point on the G group is shown as floating, the G group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the G group by replacing a hydrogen atom. The optional substituents corresponding to R v can be attached to any available carbon or nitrogen by replacing a hydrogen atom. For these G rings, s is typically an integer from 1 to 5, subject to the number of available positions on each G group.

[0068] It should be noted that when R 4 contains a ring selected from G-28 to G-35, G 2 is selected from O, S or N. Note that when G 2 is N, the nitrogen atom can be replaced with a group corresponding to R as defined in the Summary of the Inventionw is substituted by substituents to complete its valence.

[0069] Example 2

[0070]

[0071] Although the R v groups are shown in structures U-2 to U-61, it should be noted that since they are optional substituents, they do not have to be present. It should be noted that when R v is H attached to an atom, this is the same as the atom being unsubstituted. A nitrogen atom that needs substitution to fill its valence is substituted by H or R v . It should be noted that when the attachment point between (R v ) r and the U ring is shown as floating, (R v ) r can be attached to any available carbon or nitrogen atom of the U ring. It should be noted that when the attachment point on the U ring is shown as floating, the U group can be attached to the rest of Formula 1 by replacing a hydrogen atom through any available carbon or nitrogen of the U group. It should be noted that some U rings can only be substituted by fewer than 4 R v groups (e.g., U-2 to U-5, U-7 to U-49, and U-52 to U-61).

[0072] A variety of synthetic methods are known in the art for preparing aromatic and non-aromatic heterocycles and ring systems; for an extensive review, see the eight-volume Comprehensive Heterocyclic Chemistry, edited by A.R. Katritzky and C.W. Rees, Pergamon Press, Oxford, 1984 and the twelve-volume Comprehensive Heterocyclic Chemistry II, edited by A.R. Katritzky, C.W. Rees, and E.F.V. Scriven, Pergamon Press, Oxford, 1996.

[0073] The compounds disclosed herein may exist as one or more stereoisomers. Stereoisomers are isomers that have the same constitution but differ in the arrangement of their atoms in space and include enantiomers, diastereomers, cis-trans isomers (also known as geometric isomers), and atropisomers. Atropisomers result from restricted rotation about a single bond where the rotational barrier is high enough to permit the separation of the isomeric species. Those skilled in the art will understand that a stereoisomer may be more active and / or may exhibit beneficial effects when enriched relative to one or more other stereoisomers or when separated from one or more other stereoisomers. Additionally, those skilled in the art know how to separate, enrich, and / or selectively prepare the stereoisomers. For a comprehensive discussion of all aspects of stereochemistry, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

[0074] The compounds disclosed herein may exist as a mixture of stereoisomers or as individual stereoisomers. For example, the two possible enantiomers of Formula 1 are depicted as Formula 1aa and Formula 1aa’, with respect to the chiral carbon center identified by an asterisk (*). Similarly, there may be other chiral centers, for example, at the R 4 position.

[0075]

[0076] The molecular depictions drawn herein follow the standard convention used to portray stereochemistry. To indicate the stereoconfiguration, a bond that extends out of the plane of the drawing and towards the viewer is represented by a solid wedge, where the wide end of the wedge is attached to the atom extending out of the plane of the drawing towards the viewer. A bond that extends below the plane of the drawing and away from the observer is represented by a dashed wedge, where the wide end of the wedge is attached to the atom further away from the observer.

[0077] Due to the possible presence of chiral carbon atoms in Formula 1, the compounds disclosed herein may exist as stereoisomers. Accordingly, the present disclosure includes the individual stereoisomers of the compounds of Formula 1, as well as mixtures of stereoisomers of the compounds of Formula 1.

[0078] The compounds of Formula 1 may contain additional chiral centers. For example, substituents and other molecular moieties such as R 4 itself may contain chiral centers. The present disclosure includes racemic mixtures as well as stereoconfigurations that are enriched and substantially pure at these additional chiral centers.

[0079] Due to the restricted rotation around any bond in Formula 1, the compounds of the present disclosure can exist as one or more conformational isomers. The present disclosure includes mixtures of conformational isomers. In addition, the present disclosure includes compounds in which one conformational isomer is enriched relative to other conformational isomers.

[0080] The more biologically active enantiomer is considered to be Formula 1a (the R-enantiomer of Formula 1).

[0081] The present disclosure includes a racemic mixture of equal amounts of the enantiomer of Formula 1a (the R-enantiomer of Formula 1) and the enantiomer of Formula 1a' (the S-enantiomer of Formula 1). In addition, the present disclosure includes mixtures enriched in the enantiomer of Formula 1a compared to the racemic mixture of Formula 1a and 1a'. The present disclosure also includes substantially pure enantiomers of Formula 1a.

[0082] Examples of the present disclosure include mixtures of stereoisomers of the compounds of Formula 1a and Formula 1a', wherein the ratio of 1a to 1a' is at least 75:25 (50% enantiomeric excess).

[0083] Examples of the present disclosure include mixtures of stereoisomers of the compounds of Formula 1a and Formula 1a', wherein the ratio of 1a to 1a' is at least 90:10 (80% enantiomeric excess of 1a).

[0084] Examples of the present disclosure include mixtures of stereoisomers of the compounds of Formula 1a and Formula 1a', wherein the ratio of 1a to 1a' is at least 95:5 (90% enantiomeric excess of 1a).

[0085] Examples of the present disclosure include mixtures of stereoisomers of the compounds of Formula 1a and Formula 1a', wherein the ratio of 1a to 1a' is at least 98:2 (96% enantiomeric excess of 1a).

[0086] Examples of the present disclosure include mixtures of stereoisomers of the compounds of Formula 1a and Formula 1a', wherein the ratio of 1a to 1a' is at least 99:1 (98% enantiomeric excess of 1a).

[0087] Examples of the present disclosure include mixtures of stereoisomers of the compounds of Formula 1a and Formula 1a', wherein the ratio of 1a to 1a' is substantially 100:0.

[0088] Examples of the present disclosure include the compound of Formula 1a.

[0089] Those skilled in the art will understand that not all nitrogen-containing heterocycles can form N-oxides because the nitrogen requires an available lone pair of electrons to be oxidized to the oxide; those skilled in the art will recognize those nitrogen-containing heterocycles that can form N-oxides. Those skilled in the art will also recognize that tertiary amines are capable of forming N-oxides. Synthetic methods for preparing N-oxides of heterocycles and tertiary amines are well known to those skilled in the art and include the use of peroxyacids such as peracetic acid and 3-chloroperoxybenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as tert-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane to oxidize heterocycles and tertiary amines. These methods for preparing N-oxides have been widely described and reviewed in the literature, see, for example: T.L. Gilchrist, Comprehensive Organic Synthesis, Volume 7, pages 748-750, edited by S.V. Ley, Pergamon Press; M. Tisler and B. Stanovnik, Comprehensive Heterocyclic Chemistry, Volume 3, pages 18-20, edited by A.J. Boulton and A. McKillop, Pergamon Press; M.R. Grimmett and B.R.T. Keene, Advances in Heterocyclic Chemistry, Volume 43, pages 149-161, edited by A.R. Katritzky, Academic Press; M. Tisler and B. Stanovnik, Advances in Heterocyclic Chemistry, Volume 9, pages 285-291, edited by A.R. Katritzky and A.J. Boulton, Academic Press; and G.W.H. Cheeseman and E.S.G. Werstiuk, Advances in Heterocyclic Chemistry, Volume 22, pages 390-392, edited by A.R. Katritzky and A.J. Boulton, Academic Press.

[0090] Those skilled in the art recognize that, since salts of compounds are in equilibrium with their corresponding non-salt forms in the environment and under physiological conditions, the salts share the biological utility of the non-salt forms. Accordingly, salts of the compounds of Formula 1 can be used to control invertebrate pests. Salts of the compounds of Formula 1 include acid addition salts formed with inorganic or organic acids such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid or valeric acid. When the compounds of Formula 1 contain acidic moieties such as carboxylic acid or phenol, the salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, this disclosure includes compounds of Formula 1, their N-oxides and suitable salts.

[0091] Compounds of Formula 1, their stereoisomers, tautomers, N-oxides and salts typically exist in more than one form, and thus Formula 1 includes all crystalline and non-crystalline forms of the compounds represented by Formula 1. Non-crystalline forms include embodiments that are solids such as waxes and gums, and embodiments that are liquids such as solutions and melts. Crystalline forms include embodiments that represent substantially single crystal types and embodiments that represent mixtures of polymorphs (i.e., different crystalline types). The term "polymorph" refers to specific crystalline forms of a compound that can crystallize in different crystal forms, which have different molecular arrangements and / or conformations in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound within the crystal lattice. Polymorphs can differ in such chemical, physical, and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspendability, dissolution rate and bioavailability. Those skilled in the art will appreciate that a polymorph of a compound represented by Formula 1 can exhibit beneficial effects (e.g., suitable for preparing useful formulations, improved biological properties) relative to another polymorph or mixture of polymorphs of the same compound represented by Formula 1. The preparation and isolation of specific polymorphs of the compounds represented by Formula 1 can be achieved by methods known to those skilled in the art, including, for example, crystallization using selected solvents and temperatures. The compounds of this disclosure can exist as one or more crystalline polymorphs. This disclosure encompasses both individual polymorphs and mixtures of polymorphs, including mixtures of one polymorph that is enriched relative to others. For a comprehensive discussion of polymorphism, see R. Hilfiker, editor, Polymorphism in the Pharmaceutical Industry, Wiley-VCH, Weinheim, 2006.

[0092] Embodiments of the present disclosure as described in the Summary of the Invention include those described below. In the following embodiments, unless further defined in the embodiments, Formula 1 includes its stereoisomers, N-oxides and salts, and references to "compounds of Formula 1" include the definitions of the substituents specified in the Summary of the Invention.

[0093] Example 1. A compound of Formula 1, wherein R 1 is F, OR 6 or SR 6 .

[0094] Example 1a. A compound of Formula 1 as described in Example 1, wherein R 1 is F.

[0095] Example 1b. A compound of Formula 1 as described in Example 1, wherein R 1 is OR 6 .

[0096] Example 1c. A compound of Formula 1 as described in Example 1, wherein R 1 is SR 6 .

[0097] Example 2. A compound of Formula 1 as described in any one of the foregoing examples, wherein A is N or CR 3 .

[0098] Example 2a. A compound of Formula 1 as described in any one of the foregoing examples, wherein A is N.

[0099] Example 2b. A compound of Formula 1 as described in any one of the foregoing examples, wherein A is CR 3 .

[0100] Example 3. A compound of Formula 1 as described in any one of the foregoing examples, wherein R 2 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy.

[0101] Example 3a. A compound of Formula 1 as described in any one of the foregoing examples, wherein R 2 is H, halogen or C1-C4 alkyl.

[0102] Example 3b. A compound as described in Example 3, wherein R 2 is H.

[0103] Example 3c. A compound as described in Example 3, wherein R 2 is halogen.

[0104] Example 3d. A compound as described in Example 3, wherein R 2 is C1-C4 alkyl.

[0105] Example 4. A compound of formula 1 as described in any one of the preceding examples, wherein R 3 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy.

[0106] Example 4a. A compound as described in Example 4, wherein R 3 is H, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy.

[0107] Example 4b. A compound as described in Example 4a, wherein R 3 is H or halogen.

[0108] Example 4c. A compound as described in Example 4b, wherein R 3 is H.

[0109] Example 4d. A compound as described in Example 4a, wherein R 3 is halogen.

[0110] Example 4f. A compound as described in Example 4d, wherein R 3 is F.

[0111] Example 4g. A compound as described in Example 4d, wherein R 3 is Cl.

[0112] Example 4h. A compound as described in Example 4d, wherein R 3 is Br.

[0113] Example 4i. A compound as described in Example 4a, wherein R 3 is C1-C4 alkyl.

[0114] Example 4j. A compound as described in Example 4i, wherein R 3 is Me.

[0115] Example 4k. A compound as described in Example 4a, wherein R 3 is C1-C4 haloalkyl.

[0116] Example 4l. A compound as described in Example 4k, wherein R 3 is CF3.

[0117] Example 5. A compound of formula 1 as described in any one of the preceding examples, wherein R 4 is a 5- to 6-membered heterocycle, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O atoms, up to 2 S atoms, and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(=O), C(=S), S(=O), and S(=O)2, each ring or ring system is optionally substituted with up to 5 substituents independently selected from R v , and r is the number of these substituents.

[0118] Example 5a. A compound as described in Example 5, wherein R 4 is selected from U-2 to U-49 or U52 to U61 as shown in Example 1.

[0119] Example 1

[0120]

[0121]

[0122] Example 5b. A compound as described in Example 5a, wherein R 4 is selected from U-2 to U-49.

[0123] Example 5c. A compound as described in Example 5b, wherein R 4 is selected from U-2, U-3, U-4, U-5, U-7, U-9, U-11, U-12, U-13, U-16, U-21, U-25, U-26, U-27, U-28, U-29, U-31, U-32, U-35, U-36, U-37, U-44, U-48, and U-49.

[0124] Example 5d. A compound as described in Example 5c, wherein R 4 is selected from U-9, U-11, U-32, U-36, and U-44.

[0125] Example 5e. A compound as described in Example 5d, wherein R 4 is selected from U-9 and U-44.

[0126] Example 5f. A compound as described in Example 5e, wherein R 4 is U-9.

[0127] Example 5g. A compound as described in Example 5d, wherein R 4 is U-11.

[0128] Example 5h. A compound as described in Example 5d, wherein R4 is U-32.

[0129] Example 5i. A compound as described in Example 5d, wherein R 4 is U-36.

[0130] Example 5j. A compound as described in Example 5d, wherein R 4 is U-44.

[0131] Example 5k. A compound as described in Example 5, wherein R 4 is independently selected from G-1 to G-37 as shown in Example 2.

[0132] Example 2

[0133]

[0134]

[0135] Example 5l. A compound as described in Example 5k, wherein G 2 is O, S or N.

[0136] Example 5m. A compound as described in Example 5l, wherein G 2 is O.

[0137] Example 5n. A compound as described in Example 5l, wherein G 2 is S.

[0138] Example 5o. A compound as described in Example 5l, wherein G 2 is N.

[0139] Example 6. A compound of formula 1 as described in any one of the foregoing examples, wherein R v is independently H, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or C1-C6 haloalkoxy.

[0140] Example 6a. A compound as described in Example 6, wherein R v is H.

[0141] Example 6b. A compound as described in Example 6, wherein R v is halogen.

[0142] Example 6c. A compound as described in Example 6, wherein R v is C1-C6 alkyl.

[0143] Example 6d. A compound as described in Example 6c, wherein R v is Me.

[0144] Example 7. A compound according to formula 1 or any one of Examples 5 to 6d, wherein r is 1, 2, 3, 4 or 5.

[0145] Example 7a. A compound according to Example 7, wherein r is 1 or 2.

[0146] Example 7b. A compound according to Example 7, wherein r is 1.

[0147] Example 7c. A compound according to Example 7, wherein r is 2.

[0148] Example 7d. A compound according to Example 7, wherein r is 3.

[0149] Example 7e. A compound according to Example 7, wherein r is 4.

[0150] Example 7f. A compound according to Example 7, wherein r is 5.

[0151] Example 8. A compound of formula 1 according to any one of the foregoing examples, wherein R 5 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy.

[0152] Example 8a. A compound according to Example 8, wherein R 5 is H, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy.

[0153] Example 8b. A compound according to Example 8a, wherein R 5 is H or halogen.

[0154] Example 8c. A compound according to Example 8b, wherein R 5 is H.

[0155] Example 8d. A compound according to Example 8b, wherein R 5 is halogen.

[0156] Example 8e. A compound according to Example 8d, wherein R 5 is F.

[0157] Example 8e. A compound according to Example 8d, wherein R 5 is Cl.

[0158] Example 8e. A compound according to Example 8d, wherein R 5 is Br.

[0159] Example 8e. A compound as described in Example 8a, wherein R 5 is C1-C4 alkyl.

[0160] Example 9. A compound of formula 1 as described in any one of the foregoing examples, wherein R 6 is C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl or C3-C4 halocycloalkyl.

[0161] Example 9a. A compound as described in Example 9, wherein R 6 is C1-C4 alkyl or C1-C4 haloalkyl.

[0162] Example 9b. A compound as described in Example 9, wherein R 6 is C1-C4 alkyl.

[0163] Example 9c. A compound as described in Example 9b, wherein R 6 is Me;

[0164] Example 9d. A compound as described in Example 9, wherein R 6 is C1-C4 haloalkyl.

[0165] Example 9e. A compound as described in Example 9b, wherein R 6 is CF3.

[0166] Example 10. A compound of formula 1 as described in any one of the foregoing examples, wherein Q is a six-membered aromatic ring having 0 to 2 N atoms in the ring, each ring optionally being substituted on the carbon ring members with up to 5 substituents independently selected from R w .

[0167] Example 10a. A compound as described in Example 10, wherein Q is a phenyl, pyridyl, pyrimidinyl or pyrazinyl ring, each ring optionally being substituted on the carbon ring members with up to 5 substituents independently selected from R w .

[0168] Example 10b. A compound as described in Example 10a, wherein Q is a phenyl ring optionally substituted on the carbon ring members with up to 5 substituents independently selected from R w .

[0169] Example 10c. A compound as described in Example 10a, wherein Q is a pyridyl ring optionally substituted on the carbon ring members with up to 5 substituents independently selected from R w .

[0170] Example 10d. A compound as described in Example 10a, wherein Q is a pyrimidine ring optionally substituted on the carbon ring members with up to 5 substituents independently selected from R w A pyrimidine ring substituted with up to 5 substituents independently selected from R

[0171] Example 10e. A compound as described in Example 10a, wherein Q is a pyrazine ring optionally substituted on the carbon ring members with up to 5 substituents independently selected from R w A pyrazine ring substituted with up to 5 substituents independently selected from R

[0172] Example 11. A compound as described in Formula 1 or any one of Examples 9 to 9e, wherein R w is independently H, cyano, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 alkoxyalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C3-C6 cycloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl or C3-C6 cycloalkylsulfonyl;

[0173] Example 11a. A compound as described in Example 11, wherein R w is cyano, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl.

[0174] Example 11b. A compound as described in Example 11a, wherein R w is C1-C6 haloalkoxy, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl.

[0175] Example 11c. A compound as described in Example 11b, wherein R w is C1-C6 haloalkoxy, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C1-C6 haloalkylthio, C1-C6 haloalkylsulfinyl, C1-C6 haloalkylsulfonyl.

[0176] Example 11d. A compound as described in Example 11c, wherein R w is OCF3, SCF3, CF3, SOCF3 or SO2CF3.

[0177] Example 11e. A compound as described in Example 11d, wherein R w is OCF3.

[0178] Example 11f. A compound as described in Example 11d, wherein R w is SCF3.

[0179] Example 11g. A compound as described in Example 11d, wherein R w is CF3.

[0180] Example 11h. A compound as described in Example 11d, wherein R w is SOCF3 or SO2CF3.

[0181] Example 12. A compound of formula 1 as described in any one of the preceding examples, wherein s is 1, 2, 3, 4 or 5.

[0182] Example 12a. A compound as described in Example 12, wherein r is 1 or 2.

[0183] Example 12b. A compound as described in Example 12, wherein r is 1.

[0184] Example 12c. A compound as described in Example 12, wherein r is 2.

[0185] Example 12d. A compound as described in Example 12, wherein r is 3.

[0186] Example 12e. A compound as described in Example 12, wherein r is 4.

[0187] Example 12f. A compound as described in Example 12, wherein r is 5.

[0188] Example 13. A compound of formula 1 as described in any one of the preceding examples, wherein n is 0, 1 or 2.

[0189] Example 13a. A compound as described in Example 13, wherein n is 0.

[0190] Example 13b. A compound as described in Example 13, wherein n is 1.

[0191] Example 13c. A compound as described in Example 13, wherein n is 2.

[0192] Example A1. A compound according to any one of Examples 1 - 13c, wherein the compound of Formula 1 is a compound of Formula 1a.

[0193] Example A2. A compound according to any one of Examples 1 - 13c, wherein the compound of Formula 1 is a compound of Formula 1a'.

[0194] Example A3. A composition comprising a compound of Formula 1a and a compound of Formula 1a'.

[0195] Example A3a. A composition according to Example A3, wherein the ratio of the compound of Formula 1a to the compound of Formula 1a' is greater than 60:40.

[0196] Example A3b. A composition according to Example A3a, wherein the ratio of the compound of Formula 1a to the compound of Formula 1a' is greater than 80:20.

[0197] Example A3c. A composition according to Example A3a, wherein the ratio of the compound of Formula 1a to the compound of Formula 1a' is greater than 90:10.

[0198] Example A3d. A composition according to Example A3a, wherein the ratio of the compound of Formula 1a to the compound of Formula 1a' is greater than 99:1.

[0199] Example A4. A composition comprising a compound of Formula 1a' and a compound of Formula 1a.

[0200] Example A4a. A composition according to Example A4, wherein the ratio of the compound of Formula 1a' to the compound of Formula 1a is greater than 60:40.

[0201] Example A4b. A composition according to Example A4, wherein the ratio of the compound of Formula 1a' to the compound of Formula 1a is greater than 80:20.

[0202] Example A4c. A composition according to Example A4, wherein the ratio of the compound of Formula 1a' to the compound of Formula 1a is greater than 90:10.

[0203] Example A4d. A composition according to Example A4, wherein the ratio of the compound of Formula 1a' to the compound of Formula 1a is greater than 99:1.

[0204] Example X. A method for controlling invertebrate pests, the method comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula 1.

[0205] Example X1. A method according to Example X, wherein the invertebrate pest is a member of the Hemiptera.

[0206] Example X2. The method according to Example X1, wherein the member of the Hemiptera is a member of the Homoptera.

[0207] Example X2a. The method according to Example X2, wherein the Homoptera includes planthoppers from the families Cicadellidae and Delphacidae.

[0208] Example X2b. The method according to Example X2, wherein the Homoptera includes aphids from the family Aphididae.

[0209] Example X2c. The method according to Example X2, wherein the Homoptera includes whiteflies from the family Aleyrodidae.

[0210] Example X3. The method according to Example X2, wherein the Homoptera includes CPH, CMA, GPA, and WF.

[0211] Example X4. The method according to Example X2, wherein the Homoptera includes the black bean aphid (Aphis fabae Scopoli) (also known as the black bean aphid), the cotton aphid (Aphis gossypii Glover, cotton aphid or melon aphid), the tobacco whitefly (Bemisia tabaci Gennadius), the sweetpotato whitefly, the silverleaf whitefly (Bemisia argentifolii Bellows & Perring), the citrus whitefly (Dialeurodes citri Ashmead), and the greenhouse whitefly (Trialeurodes vaporariorum Westwood); the potato leafhopper (Empoasca fabae Harris), the small brown planthopper (Laodelphax striatellus Fallen), the four-lined leafhopper (Macrosteles quadrilineatus Forbes), the rice green leafhopper (Nephotettix cincticeps Uhler), the black-tailed leafhopper (Nephotettix nigropictus ) and the brown planthopper (Nilaparvata lugens ) Peregrinus maidis Ashmead, Sogatella furcifera Horvath, Tagosodes orizicolus Muir, Typhlocyba pomaria McAtee, species of the genus Erythroneura (grape leafhoppers).

[0212] Example X5. The method according to Example X1, wherein the Hemiptera is a member of the Heteroptera suborder.

[0213] Example X5a. The method according to Example X5, wherein the Heteroptera suborder includes Acrosternum hilare Say (green stink bug), Anasa tristis De Geer (squash bug), Blissus leucopterus leucopterus Say (chinch bug), Cimex lectularius Llinnaeus (bed bug), Corythucha gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dichelops melacanthus Dallas (green belly Stink bug), Dysdercus suturellus )(cotton stainer), Euschistus heros Fabricius (Neotropical Brown Stink Bug), Euschistus servus Say (brown stink bug), Euschistus variolarius Palisot de Beauvois (one-spotted stink bug), species of the genus Graptostethus (complex of seed bugs), Halyomorpha halys )(Brown marmorated stink bug), 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 (large milkweed bug), Pseudatomoscelis seriatus Reuter (cotton fleahopper).

[0214] Example X6. The method according to Example X5, wherein the Heteroptera includes stink bugs from the family Pentatomidae.

[0215] Example X7. The method according to Example X6, wherein the Heteroptera includes Acrosternum hilare Say (green stink bug), Dichelops melacanthus Dallas (green belly Stink bug), Euschistus heros Fabricius (Neotropical Brown Stink Bug), Euschistus servus Say (brown stink bug), Euschistus variolarius Palisot de Beauvois (one-spotted stink bug), Halyomorpha halys )(Brown marmorated stink bug), Nezara viridula Linnaeus (southern green stink bug), Oebalus pugnax Fabricius (rice stink bug).

[0216] Example X8. The method as described in Example X5, wherein the Heteroptera includes Anasa tristis De Geer (squash bug), Blissus leucopterus Say (chinchbug), Cimex lectularius Linnaeus (bed bug), Corythuca gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomatobug), Dysdercus suturellus Herrich-Schaffer (cotton stainer), Graptosthetus spp. (complex of seedbugs), Leptoglossus corculus Say (leaf-footed pine seed bug), Lygus lineolaris Palisot de Beauvois (tarnished plant bug), Oncopeltus fasciatus Dallas (large milkweed bug), or Pseudatomoscelis seriatus Reuter (cotton fleahopper).

[0217] The embodiments of the present disclosure (including the above-described Embodiments 1-X8 and any other embodiments described herein) can be combined in any manner, and the description of variables in the embodiments relates not only to the compounds of Formula 1, but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1. Additionally, the embodiments of the present disclosure (including the above-described Embodiments 1-X8 and any other embodiments described herein) and any combinations thereof relate to the compositions and methods of the present disclosure.

[0218] The combinations of Embodiments 1-X8 are shown below:

[0219] Embodiment A. A compound of Formula 1, wherein

[0220] R 1 is F;

[0221] A is CR 3 ;

[0222] R2 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

[0223] R 3 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

[0224] R 4 is a 5- to 6-membered heterocycle, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O atoms, up to 2 S atoms and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(=O), C(=S), S(=O) and S(=O)2, each ring or ring system being optionally substituted by up to 5 substituents independently selected from R v and r is the number of these substituents;

[0225] Each R v is independently H, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or C1-C6 haloalkoxy;

[0226] r is 1, 2, 3, 4 or 5;

[0227] R 5 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

[0228] Q is a six-membered aromatic ring having 0 to 2 N atoms on the ring, each ring being optionally substituted by up to 5 substituents independently selected from R w ;

[0229] R w is independently cyano, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl;

[0230] s is 1, 2, 3, 4 or 5;

[0231] n is 0, 1 or 2.

[0232] Example B. A compound as described in Example A, wherein

[0233] R 2 is H, halogen or C1-C4 alkyl;

[0234] R 3 is H, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

[0235] R 4 is selected from U-2 to U-49 or U52 to U61 as shown in Example 1;

[0236] r is 1 or 2;

[0237] R 5 is H, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

[0238] R w is C1-C6 haloalkoxy, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C1-C6 haloalkylthio, C1-C6 haloalkylsulfinyl, C1-C6 haloalkylsulfonyl.

[0239] s is 1 or 2.

[0240] Example C. A compound as described in Example B, wherein

[0241] R 2 is H;

[0242] R 3 is H or halogen;

[0243] R 4 is selected from U-2 to U-49;

[0244] R v is H;

[0245] R 5 is H or halogen;

[0246] Q is a phenyl, pyridyl, pyrimidinyl or pyrazinyl ring, each ring optionally being substituted on the carbon atom ring members with up to 5 substituents independently selected from R w ;

[0247] R w is OCF3, SCF3, CF3, SOCF3 or SO2CF3.

[0248] Example D. A compound as described in Example B, wherein

[0249] R2 is H;

[0250] R 3 is H or halogen;

[0251] R 4 is selected from U-2 to U-49;

[0252] R v is a C1-C6 alkyl group;

[0253] R 5 is H;

[0254] Q is a phenyl, pyridyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on the carbon ring members with up to 5 substituents independently selected from R w as substituents;

[0255] Example E. A compound as described in Example C, wherein

[0256] R 3 is halogen;

[0257] R 4 is selected from U-2, U-3, U-4, U-5, U-7, U-9, U-11, U-12, U-13, U-16, U-21, U-25, U-26, U-27, U-28, U-29, U-31, U-32, U-35, U-36, U-37, U-44, U-48 and U-49;

[0258] R 5 is H;

[0259] Q is a phenyl, pyridyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on the carbon ring members with up to 5 substituents independently selected from R w as substituents.

[0260] Example F. A compound as described in Example E, wherein

[0261] R 3 is F;

[0262] R 4 is selected from U-9, U-11, U-32, U-36 and U-44;

[0263] Q is a phenyl ring optionally substituted on the carbon ring members with up to 5 substituents independently selected from R w as substituents.

[0264] Example G. A compound as described in Example F, wherein

[0265] R 4 is selected from U-9 and U-44.

[0266] Example H. A compound as described in Example G, wherein

[0267] R 4 is selected from the group U-9.

[0268] Example I. A compound as described in Example G, wherein

[0269] R 4 is selected from the group U-44.

[0270] Example J. A compound as described in Example B, wherein

[0271] R 2 is C1-C4 alkyl;

[0272] R 3 is H or halogen;

[0273] R 4 is selected from U-2 to U-49;

[0274] R v is H;

[0275] r is 2;

[0276] R 5 is H;

[0277] Q is a phenyl, pyridyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on the carbon atom ring members with up to 5 substituents independently selected from R w ;

[0278] R w is OCF3, SCF3, CF3, SOCF3 or SO2CF3.

[0279] Example AA. A compound of formula 1, wherein

[0280] R 1 is OR 6 ;

[0281] A is CR 3 ;

[0282] R 2 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

[0283] R 3is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

[0284] R 4 is a 5- to 6-membered heterocycle, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O atoms, up to 2 S atoms and up to 4 N atoms, where up to 2 ring members are independently selected from C(=O), C(=S), S(=O) and S(=O)2, each ring or ring system optionally being substituted by up to 5 substituents independently selected from R v and r is the number of these substituents;

[0285] Each R v is independently H, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or C1-C6 haloalkoxy;

[0286] r is 1, 2, 3, 4 or 5;

[0287] R 5 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

[0288] R 6 is C1-C4 alkyl;

[0289] Q is a six-membered aromatic ring having 0 to 2 N atoms on the ring, each ring optionally being substituted by up to 5 substituents independently selected from R w ;

[0290] R w is independently cyano, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl;

[0291] s is 1, 2, 3, 4 or 5;

[0292] n is 0, 1 or 2.

[0293] Example BB. A compound as described in Example AA, wherein

[0294] R 2is H, a halogen or a C1-C4 alkyl group;

[0295] R 3 is H, a halogen, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C1-C4 alkoxy group or a C1-C4 haloalkoxy group;

[0296] R 4 is selected from U-2 to U-49 or U52 to U61 as shown in Example 1;

[0297] r is 1 or 2;

[0298] R 5 is H, a halogen, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C1-C4 alkoxy group or a C1-C4 haloalkoxy group;

[0299] R 6 is Me;

[0300] R w is a C1-C6 haloalkoxy group, a C1-C6 haloalkyl group, a C2-C6 haloalkenyl group, a C2-C6 haloalkynyl group, a C1-C6 haloalkylthio group, a C1-C6 haloalkylsulfinyl group or a C1-C6 haloalkylsulfonyl group.

[0301] s is 1 or 2.

[0302] Example CC. A compound as described in Example BB, wherein

[0303] R 2 is H;

[0304] R 3 is H or a halogen;

[0305] R 4 is selected from U-2 to U-49;

[0306] R v is H;

[0307] r is 2;

[0308] R 5 is H or a halogen;

[0309] Q is a phenyl, pyridyl, pyrimidinyl or pyrazinyl ring, each ring optionally being substituted on a carbon atom ring member with up to 5 substituents independently selected from R w ;

[0310] R w is OCF3, SCF3, CF3, SOCF3 or SO2CF3.

[0311] Example DD. A compound as described in Example BB, wherein

[0312] R 2 is H;

[0313] R 3 is H or halogen;

[0314] R 4 is selected from U-2 to U-49;

[0315] R v is a C1-C6 alkyl;

[0316] R 5 is H;

[0317] Q is a phenyl, pyridyl, pyrimidinyl or pyrazinyl ring, each ring optionally being substituted on the carbon ring members by up to 5 substituents independently selected from R w as defined below.

[0318] Example EE. A compound as described in Example CC, wherein

[0319] R 3 is halogen;

[0320] R 4 is selected from U-2, U-3, U-4, U-5, U-7, U-9, U-11, U-12, U-13, U-16, U-21, U-25, U-26, U-27, U-28, U-29, U-31, U-32, U-35, U-36, U-37, U-44, U-48 and U-49;

[0321] R 5 is H;

[0322] Q is a phenyl, pyridyl, pyrimidinyl or pyrazinyl ring, each ring optionally being substituted on the carbon ring members by up to 5 substituents independently selected from R w as defined below.

[0323] Example FF. A compound as described in Example EE, wherein

[0324] R 3 is F;

[0325] R 4 is selected from U-9 and U-44;

[0326] Q is a phenyl ring optionally substituted on the carbon ring members by up to 5 substituents independently selected from R w as defined below.

[0327] Example GG. A compound as described in Example FF, wherein

[0328] R 4 is from the group of U-9.

[0329] Example HH. A compound as described in Example FF, wherein

[0330] R 4 is selected from the group consisting of U-44.

[0331] Example AAA. A compound of formula 1, wherein

[0332] R 1 is SR 6 ;

[0333] A is CR 3 ;

[0334] R 2 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

[0335] R 3 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

[0336] R 4 is a 5- to 6-membered heterocycle, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O atoms, up to 2 S atoms and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(=O), C(=S), S(=O) and S(=O)2, each ring or ring system being optionally substituted by up to 5 substituents independently selected from R v and r is the number of these substituents;

[0337] Each R v is independently H, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or C1-C6 haloalkoxy;

[0338] r is 1, 2, 3, 4 or 5;

[0339] R 5 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

[0340] R 6 is C1-C4 alkyl;

[0341] Q is a six-membered aromatic ring having from 0 to 2 N atoms on the ring, each ring optionally being substituted on the carbon atom ring members with up to 5 substituents independently selected from R w ;

[0342] R w is independently cyano, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl;

[0343] s is 1, 2, 3, 4 or 5;

[0344] n is 0, 1 or 2.

[0345] Example BBB. A compound as described in Example AAA, wherein

[0346] R 2 is H, halogen or C1-C4 alkyl;

[0347] R 3 is H, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

[0348] R 4 is selected from U-2 to U-49 or U52 to U61 as shown in Example 1;

[0349] r is 1 or 2;

[0350] R 5 is H, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

[0351] R 6 is Me;

[0352] R w is C1-C6 haloalkoxy, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C1-C6 haloalkylthio, C1-C6 haloalkylsulfinyl, C1-C6 haloalkylsulfonyl.

[0353] s is 1 or 2.

[0354] Example CCC. A compound as described in Example BBB, wherein

[0355] R 2 is H;

[0356] R 3 is H or halogen;

[0357] R 4 is selected from U-2 to U-49;

[0358] R v is H;

[0359] r is 2;

[0360] R 5 is H;

[0361] Q is a phenyl, pyridyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on the carbon atom ring members with up to 5 substituents independently selected from R w substituents;

[0362] R w is OCF3, SCF3, CF3, SOCF3 or SO2CF3.

[0363] Example DDD. A compound as described in Example BBB, wherein

[0364] R 2 is H;

[0365] R 3 is H or halogen;

[0366] R 4 is selected from U-2 to U-49;

[0367] R v is C1-C6 alkyl;

[0368] R 5 is H;

[0369] Q is a phenyl, pyridyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on the carbon atom ring members with up to 5 substituents independently selected from R w substituents;

[0370] Example EEE. A compound as described in Example CCC, wherein

[0371] R 3 is halogen;

[0372] R 4 is selected from U-2, U-3, U-4, U-5, U-7, U-9, U-11, U-12, U-13, U-16, U-21, U-25, U-26, U-27, U-28, U-29, U-31, U-32, U-35, U-36, U-37, U-44, U-48 and U-49;

[0373] R 5 is H;

[0374] Q is a phenyl, pyridyl, pyrimidinyl or pyrazinyl ring, each ring optionally substituted on the carbon atom ring members with up to 5 substituents independently selected from R w substituents.

[0375] Example FFF. A compound as described in Example EEE, wherein

[0376] R 3 is F;

[0377] R 4 is selected from U-9 and U-44;

[0378] Q is a phenyl ring optionally substituted on the carbon atom ring members with up to 5 substituents independently selected from R w substituents.

[0379] Example GGG. A compound as described in Example FFF, wherein

[0380] R 4 is selected from the group consisting of U-9.

[0381] Example HHH. A compound as described in Example FFF, wherein

[0382] R 4 is selected from the group consisting of U-44.

[0383] Specific examples include compounds of formula 1 selected from the group consisting of:

[0384] 3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine;

[0385] 3-Chloro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine;

[0386] 3-Fluoro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine;

[0387] 3-Fluoro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2-oxazolyl)pyridine;

[0388] 3-Fluoro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine;

[0389] 3-Chloro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine;

[0390] 3-Fluoro-4-[fluoro[4-(trifluoromethyl)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine;

[0391] 3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2-oxazolyl)pyridine;

[0392] 3-Fluoro-4-[fluoro[4-[(trifluoromethyl)sulfinyl]phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine;

[0393] 3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(5-oxazolyl)pyridine;

[0394] 3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(3-methyl-1,2,4-oxadiazol-5-yl)pyridine;

[0395] 3-Fluoro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine;

[0396] 3-Chloro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine;

[0397] 3-Bromo-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine; and

[0398] 3-Fluoro-4-[methoxy[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(1,2,4-oxadiazol-3-yl)pyridine.

[0399] More specific embodiments include compounds of Formula 1 selected from the group consisting of:

[0400] 3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine

[0401] 3-Chloro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine

[0402] 3-Fluoro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine

[0403] 3-Fluoro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2-oxazolyl)pyridine

[0404] 3-Fluoro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine

[0405] 3-Bromo-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine

[0406] More specific embodiments include compounds of formula 1 selected from the group consisting of:

[0407] 3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine;

[0408] 3-Chloro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine;

[0409] 3-Chloro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine;

[0410] 3-Fluoro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine;

[0411] 3-Fluoro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2-oxazolyl)pyridine;

[0412] 3-Fluoro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine;

[0413] 3-Bromo-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine.

[0414] More specific embodiments include compounds of formula 1 selected from the group consisting of:

[0415] 3-Fluoro-4-[fluoro[4-(trifluoromethyl)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine;

[0416] 3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2-oxazolyl)pyridine;

[0417] 3-Fluoro-4-[fluoro[4-[(trifluoromethyl)sulfinyl]phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine;

[0418] 3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(5-oxazolyl)pyridine;

[0419] 3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(3-methyl-1,2,4-oxadiazol-5-yl)pyridine;

[0420] 3-Chloro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine; and

[0421] 3-Fluoro-4-[methoxy[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(1,2,4-oxadiazol-3-yl)pyridine.

[0422] 3-Fluoro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine;

[0423] Example Y1. A composition comprising a compound of formula 1 or as described in any of the foregoing examples and at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents, said composition optionally further comprising at least one additional biologically active compound or agent.

[0424] Example Y2. The composition according to Example Y1, wherein the at least one additional biologically active compound or agent is selected from the group consisting of: abamectin, acephate, acequinocyl, acetamiprid, acrinathrin, afidopyropen, amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, benfuracarb, bensultap, bifenthrin, bifenazate, bistrifluron, borate, bromantraniliprole, buprofezin, carbaryl, carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cycloxaprid, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalodiamide, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon,dichlorantraniliprole, dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide, flucythrinate, flufenerim, flufenoxuron, flufenoxystrobin, fluensulfone, fluopyram, flupyradifurone, fluvalinate, tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide, heptafluthrin, hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidal soap, isofenphos, lufenuron, malathion, meperfluthrin, metaflumizone, metaldehyde, methamidophos, methidathion, methiocarb, methomyl, methoprene,methoxychlor, methoxyfenozide, metofluthrin, monocrotophos, monofluorothrin, nicotine, N-[1,1-dimethyl-2-(methylthio)ethyl]-7-fluoro-2-(3-pyridyl)-2H-indazole-4-carboxamide, N-[1,1-dimethyl-2-(methylsulfinyl)ethyl]-7-fluoro-2-(3-pyridyl)-2H-indazole-4-carboxamide, N-[1,1-dimethyl-2-(methylsulfonyl)ethyl]-7-fluoro-2-(3-pyridyl)-2H-indazole-4-carboxamide, N-(1-methylcyclopropyl)-2-(3-pyridyl)-2H-indazole-4-carboxamide, N-[1-(difluoromethyl)cyclopropyl]-2-(3-pyridyl)-2H-indazole-4-carboxamide, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, propargite, protrifenbute, pyflubumide, pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl, pyrifluquinazon, pyriminostrobin, pyriprole, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulprofos, sulfoxaflor, tebufenozideTebufenpyrad, teflubenzuron, tefluthrin, tetrachlorantraniliprole, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tioxazafen, toufenpyrad, tralomethrin, triazamate, trichlorfon, triflumezopyrim, triflumuron, Bacillus thuringiensis δ-endotoxin, entomopathogenic bacteria, entomopathogenic viruses and entomopathogenic fungi.

[0425] Example Y3. The composition according to Example Y2, wherein the at least one additional biologically active compound or agent is selected from the group consisting of: abamectin, acetamiprid, fluvalinate, biprofezin, amitraz, avermectin, azadirachtin, benfuracarb, bensultap, bifenthrin, buprofezin, carbaryl, cartap hydrochloride, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyclaniliprole, ethofenprox, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, esfenvalerate, deltamethrin, dieldrin, dinotefuran, phenthoate, emamectin benzoate, endosulfan, esfenvalerate, ethiprole, ethofenprox, etoxazole, fenitrothion, phenothiocarb, phenoxycarb, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide, flufenoxuron, flutriafol, flufenerim, flupiprole, flupyradifurone, fluvalinate, formetanate hydrochloride, fosthiazate, heptafluthrin, flucycloxuron, indoxacarb, lufenuron, metofluthrin, metaflumizone, methiocarb, methomyl, methoprene, methoxyfenozide, metofluthrin, monofluoroethofenprox, nitenpyram, nithiazine, novaluron, oxamyl, picoxystrobin, pymetrozine, pyrethrins, pyridaben, pyridalyl, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spirotetramat, spirotetramat, sulfoxaflor, tebufenozide, tetramethrin, tetrafluoromethrin, thiacloprid, thiamethoxam, thiodicarb, bisultap, tralomethrin, triazamate, triflumezopyrim, triflumuron, Bacillus thuringiensis delta-endotoxin, all strains of Bacillus thuringiensis and all strains of nuclear polyhedrosis viruses.

[0426] Example Y4. The composition according to any one of Examples Y1 - Y3, further comprising a liquid fertilizer.

[0427] Example Y5. The composition according to Example Y4, wherein the liquid fertilizer is water-based.

[0428] Example Y6. A soil infusion preparation comprising the composition according to any one of Examples Y1 - Y3.

[0429] Example Y7. A spray composition comprising the composition according to any one of Examples Y1 - Y3 and a propellant.

[0430] Example Y8. A bait composition comprising the composition according to any one of Examples Y1 - Y3, one or more food materials, an optional attractant, and an optional wetting agent.

[0431] Example Y9. A trapping device for controlling invertebrate pests, said trapping device comprising: a bait composition as described in Example Y8 and a housing adapted to receive said bait composition, wherein the housing has at least one opening sized to allow invertebrate pests to pass through the opening such that the invertebrate pests can access the bait composition from a location external to the housing, and wherein the housing is further adapted to be placed in or near a location where invertebrate pests are likely or known to be active.

[0432] Example Y10. A composition comprising a composition as described in any one of Examples Y1 - Y3, wherein the composition is a solid composition selected from powders, dusts, granules, pellets, briquettes, tablets, and filled films.

[0433] Example Y11. The composition as described in Example Y10, wherein the composition is water - dispersible or water - soluble.

[0434] Example Y12. A liquid or dry formulation comprising a composition as described in any one of Examples Y1 - Y3, said liquid or dry formulation for use in drip irrigation systems, furrows during planting, hand - held sprayers, backpack sprayers, boom sprayers, ground sprayers, aerial application, unmanned aerial vehicles, or seed treatment.

[0435] Example Y13. The liquid or dry formulation as described in Example Y12, wherein the formulation is sprayed at ultra - low volume.

[0436] It is noted that the compounds of the present disclosure are characterized by favorable metabolic profiles and / or soil residue profiles and exhibit activity against a broad spectrum of agronomic and non - agronomic invertebrate pests.

[0437] Particularly notable is that, due to the invertebrate pest control spectrum and economic importance, protecting agricultural crops from damage or injury caused by invertebrate pests by controlling invertebrate pests is an embodiment of the present disclosure. The compounds of the present disclosure also protect leaves or other plant parts not in direct contact with the compound of formula 1 or a composition comprising the compound due to their favorable translocation properties or systemicity in the plant.

[0438] Also notable as an embodiment of the present disclosure is a composition comprising a compound as described in any one of the foregoing examples and any other example described herein and any combination thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents, said composition optionally further comprising at least one additional biologically active compound or agent.

[0439] Also notable as an embodiment of the present disclosure is a composition for controlling invertebrate pests, which comprises a compound as described in any of the foregoing embodiments and any other embodiment described herein and any combination thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents, and the composition optionally further comprises at least one additional biologically active compound or agent. Embodiments of the present disclosure further include methods for controlling invertebrate pests, which include contacting the invertebrate pests or their environment with a biologically effective amount of a compound as described in any of the foregoing embodiments (e.g., as a composition described herein).

[0440] Embodiments of the present disclosure also include a composition in the form of a soil infusion liquid preparation comprising a compound of any of the foregoing embodiments. Embodiments of the present disclosure further include methods for controlling invertebrate pests, which include contacting the soil with a liquid composition in the form of a soil infusion comprising a biologically effective amount of a compound of any of the foregoing embodiments.

[0441] Embodiments of the present disclosure also include a spray composition for controlling invertebrate pests, which comprises a biologically effective amount of a compound as described in any of the foregoing embodiments and a propellant. Embodiments of the present disclosure further include a bait composition for controlling invertebrate pests, which comprises a biologically effective amount of a compound as described in any of the foregoing embodiments, one or more food materials, an optional attractant, and an optional wetting agent. Embodiments of the present disclosure also include a device for controlling invertebrate pests, which comprises the bait composition and a housing adapted to receive the bait composition, wherein the housing has at least one opening sized to allow invertebrate pests to pass through the opening, enabling the invertebrate pests to access the bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a location where invertebrate pests are likely or known to be active.

[0442] Embodiments of the present disclosure also include methods for protecting seeds from invertebrate pests, which include contacting the seeds with a biologically effective amount of a compound as described in any of the foregoing embodiments.

[0443] Embodiments of the present disclosure also include methods for protecting animals from invertebrate parasitic pests, which include administering to the animals a parasiticide-effective amount of a compound as described in any of the foregoing embodiments.

[0444] Embodiments of the present disclosure also include methods for controlling invertebrate pests, which include contacting the invertebrate pest or its environment with a biologically effective amount of a compound of formula 1, its N-oxide or salt (e.g., as a composition described herein), provided that these methods are not methods of medical treatment of the human or animal body by therapy.

[0445] The present disclosure also relates to such methods, wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of formula 1, its N-oxide or salt and at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents, and the composition optionally further comprises a biologically effective amount of at least one additional biologically active compound or agent, provided that these methods are not methods of medical treatment of the human or animal body by therapy.

[0446] One or more of the following methods and variations described in Schemes 1-11 can be used to prepare the compounds of formula 1. Unless otherwise indicated, R in the following compounds of formula 1-18 1 、R 2 、R 3 、R 4 、R 5 、A and Q are defined as defined in the above disclosure. Unless otherwise specified, the compounds of formula 1a-1d are different subsets of the compounds of formula 1, and all substituents of formula 1a-1d are defined as for formula 1 above. The ambient temperature or room temperature is defined as about 20°C - 25°C.

[0447] As shown in Scheme 1, the compound of formula 1a (a compound of formula 1 wherein R 4 is attached to the remainder of the molecule through a carbon atom) can be prepared by contacting a compound of formula 2a (wherein X is Cl, Br, or I) with boric acid or an organotin compound of formula 3 in the presence of a palladium catalyst. A variety of palladium-containing compounds and complexes can be used as the catalyst for this method. Examples of palladium-containing compounds and complexes that can be used as catalysts in the method of Scheme 1 include Pd(OAc)2 (palladium(II) acetate), PdCl2 (palladium(II) chloride), PdCl2(PPh3)2 bis(triphenylphosphine) palladium(II) dichloride, Pd(PPh3)4 (tetrakis(triphenylphosphine) palladium(0)), Pd(C5H7O2)2 (palladium(II) acetylacetonate), and Pd2(dba)3 tris(dibenzylideneacetone) dipalladium(0). Also as shown in Scheme 1, the compound of formula 1b (a compound of formula 1 wherein R 4Attached to the rest of the molecule through a nitrogen atom) can be prepared by contacting a compound of formula 2a, where X is Cl, Br, or I, with a compound of formula 4 (a heterocyclic compound having NH as a ring member, where H can be replaced by another functional group during a chemical reaction) in the presence of a copper or palladium catalyst. Recent review articles and books on this type of functional group transformation; see, for example, F. Bellina et al., Synthesis 2004, 15, 2419 - 2440; P. Espinet and A. M. Echavarren, Angewandte Chemie, International Edition 2004, 43, 4704 - 4734; and J. J. Li, G. W. Gribble, eds., Palladium in Heterocyclic Chemistry: A Guide for the Synthetic Chemist. 2000. K. W. Anderson et al., Angewandte Chemie, International Edition 2006, 45, 6523 - 6527.

[0448] Scheme 1

[0449]

[0450] As shown in Scheme 2, the compound of formula 1b can also be prepared by contacting a compound of formula 2b, where X is F or Cl, with a compound of formula 4 in the presence of a base such as K2CO3 or Cs2CO3. It is reasonable to believe that those skilled in the art can easily apply a variety of known general procedures to the method of Scheme 2. For example, see, J. D. Culshaw et al., Synlett 2012, 23, 1816 - 1820. The method of Scheme 2 is illustrated by Synthesis Example 1, Step C.

[0451] Scheme 2

[0452]

[0453] Alternatively, as shown in Scheme 3, the compound of formula 1a can be prepared via a compound of formula 5, where R 10It is prepared by constructing a heterocycle with CN, COCH3, or CHO. Methods for forming heterocycles through these functional groups are known in the literature. It is reasonable to believe that those skilled in the art can easily apply a variety of known general procedures to the method of Scheme 3. For example, see World Patent Publication WO 2012 / 002577; World Patent Publication WO 2012 / 087938; M.H. Gezginci et al.; J. Med. Chem. [Journal of Medicinal Chemistry] 2001, 44, 1560 - 1563; K. Gobbis, J. Heterocyclic Chem. [Journal of Heterocyclic Chemistry] 2009, 46, 1271 - 1279. The method of Scheme 3 is illustrated by Synthesis Example 2, Step D.

[0454] Scheme 3

[0455]

[0456] As shown in Scheme 4, the compound of formula 5 can be prepared by converting the X group in the compound of formula 6 into the R group in the compound of formula 5 via a functional group transformation reaction. A variety of general procedures are well-known in the literature. For example, see M. Hatsuda, M. Seki, Tetrahedron [Tetrahedron], 2005, 61, 9908 - 9917; D. Xu et al., Tetrahedron Letters [Tetrahedron Letters], 2008, 6104 - 6107; A. Brennfuehrer et al., Tetrahedron [Tetrahedron], 2007, 63, 6252 - 6258. The method of Scheme 4 is illustrated by Synthesis Example 2, Step C. 10 It is prepared by contacting the corresponding alcohol of formula 7 with a fluorination reagent (such as sulfur trifluoride bis(diethylamino) (DAST) or sulfur trifluoride bis(2 - methoxyethyl)amino (Deoxo - Fluor)) in a haloalkane solvent (such as dichloromethane or chloroform) from -78 °C to room temperature as shown in Scheme 5. General procedures are known in the art. For example, see Lal, G.S. et al. J. Org. Chem. [Journal of Organic Chemistry] 1999, 64, 7048. The method of Scheme 5 is illustrated by Synthesis Example 1, Step B.

[0457] Scheme 4

[0458]

[0459] As shown in Scheme 5, the compound of formula 6 can be prepared by contacting the corresponding alcohol of formula 7 with a fluorination reagent (such as sulfur trifluoride bis(diethylamino) (DAST) or sulfur trifluoride bis(2 - methoxyethyl)amino (Deoxo - Fluor)) in a haloalkane solvent (such as dichloromethane or chloroform) from -78 °C to room temperature. General procedures are known in the art. For example, see Lal, G.S. et al. J. Org. Chem. [Journal of Organic Chemistry] 1999, 64, 7048. The method of Scheme 5 is illustrated by Synthesis Example 1, Step B.

[0460] Scheme 5

[0461]

[0462] As shown in Scheme 6, the compound of formula 1c, wherein R 1 is OR 6 ), can be prepared by reacting the corresponding alcohol of formula 7 with a compound of formula 8, which is R 6 Br or R 6 I, in the presence of a base. The compound of formula 1d, wherein R 1 is SR 6 ), can be prepared by converting the corresponding alcohol of formula 7 to its corresponding chloride compound using SOCl2, and then reacting the chloride compound with a thiol compound of formula 9, which is R 6 SH. This method is well known in the literature. For example, see Qingzhong Hu et al., J. Med. Chem. [Journal of Medicinal Chemistry] 2010, 53, 5749; World Patent Publication WO 2009 / 034976. The method of Scheme 6 is illustrated by Synthesis Example 2, Step B.

[0463] Scheme 6

[0464]

[0465] As shown in Scheme 7, the compound of formula 7 can be readily obtained from the nucleophilic addition of the compound of formula 11 with the aldehyde of formula 10. The nucleophile of formula 11 can be generated by various chemical methods. For example, typically at a temperature between about -100 °C and about -20 °C, a metal-halogen exchange reaction of a haloaromatic compound QX’ (wherein X’ is preferably Br or I) with n-butyllithium or isopropylmagnesium bromide can in situ generate the nucleophile of formula 11. A variety of general procedures for performing the metal-halogen exchange and then reacting with an electrophile are known in the art and can be readily adapted to this method. For related general procedures, see, for example, M. Schlosser, Angew. Chem. Int. Ed. [Angewandte Chemie International Edition] 2004, 43, 2 and P. Knochel et al., Synthesis [Synthesis], 2002, 565. In addition, the nucleophile of formula 11 can be prepared by a Grignard reaction of the corresponding bromide or iodide QBr or QI with magnesium. Some of the nucleophiles of formula 11 are commercially available, for example, 4-tert-butylphenylmagnesium bromide or 4-(trifluoromethoxy)phenylmagnesium bromide. Most of the aldehydes of formula 10 are commercially available or known compounds in the chemical literature.

[0466] Scheme 7

[0467]

[0468] As shown in Scheme 8, in an ether solvent such as THF, diethyl ether or dioxane, at a temperature between -100 °C and -10 °C, treating a compound of formula 12 (wherein X is F or Cl) with a base such as lithium diisopropylamide, 2,2,6,6-tetramethylpiperidinyl magnesium chloride lithium chloride complex, etc. will in-situ generate the desired anion. By quenching the above anion with an aldehyde of formula 13, a compound of formula 7 can be prepared. This method is well-known in the literature, see for example, R.J. Mattson, et al. J. Org. Chem. [Journal of Organic Chemistry], 1990, 55, 3410. The method of Scheme 8 is illustrated by Synthesis Examples 1 and 2, Step A.

[0469] Scheme 8

[0470]

[0471] As shown in Scheme 9, a compound of formula 7 can also be prepared by reducing the corresponding carbonyl compound of formula 14. By treating a compound of formula 14 with a variety of reducing agents such as sodium borohydride, borane-dimethyl sulfide in a solvent such as methanol, ethanol or an ether (such as tetrahydrofuran), a compound of formula 7 can be prepared. Alternatively, the reduction of the carbonyl compound of formula 14 can be accomplished by catalytic hydrogenation. Several general procedures for these transformations are known in the art; see, for example, D. Douglas, et al., J. Med. Chem. [Journal of Medicinal Chemistry] 2009, 52, 4694; M. Moriyasu, et al., Synlett [Synthesis Letters] 1997, 3, 273.

[0472] Scheme 9

[0473]

[0474] As shown in Scheme 10, a compound of formula 14 can be prepared from a CN-substituted aromatic compound of formula 15a (wherein Y is CN) or a Weinreb amide of formula 15b (wherein Y is CONMeOMe). The reaction of a compound of formula 16 with a compound of formula 15a or 15b can provide the carbonyl compound of formula 14. The compound of formula 16 can be prepared using a similar chemical method for in-situ generating the corresponding anion as described in Scheme 8. For related references, see, for example: US Patent Application Publication US2008 / 280891 and Bela., et al. European J. Org. Chem. [European Journal of Organic Chemistry] 2004 17, 3623 - 3632. Many of the compounds of formula 17 and 15 are commercially available or readily obtainable from literature synthetic methods.

[0475] Scheme 10

[0476]

[0477] Alternatively, as shown in Scheme 11, the compound of formula 14 can also be prepared from a 4-halopyridine or pyrimidine compound of formula 17 (wherein Z is Br or I and X is not Br or I). The palladium-catalyzed cross-coupling reaction of the compound of formula 17, carbon monoxide, and the boronic acid of formula 18 can provide an alternative method for preparing the compound of formula 14. Treatment of a mixture of the 4-halopyridine or pyrimidine compound of formula 17 and the boronic acid of formula 18 with a base (such as potassium carbonate, sodium carbonate, or cesium carbonate) in an ether solvent (such as tetrahydrofuran or dioxane) in a pressurized carbon monoxide atmosphere from 1 to 50 bar at a temperature of about 80 to 150 °C in the presence of a palladium catalyst (such as bis(triphenylphosphine)palladium(II) dichloride or tetrakis(triphenylphosphine)palladium(0)) will provide the desired carbonyl compound of formula 14. Detailed experimental procedures are given in Couve-Bonnair et al., Tetrahedron Lett. [Tetrahedron Communications] 2001, 42, 3689-3691. Most of the compounds of formula 17 and the boronic acids of formula 18 are commercially available or readily obtainable from the chemical literature.

[0478] Scheme 11

[0479]

[0480] It should be recognized that some of the reagents and reaction conditions described above for preparing the compound of formula 1 may not be compatible with certain functional groups present in the intermediates. In these cases, incorporating a protecting / deprotecting sequence or functional group interconversion into the synthesis will assist in obtaining the desired product. The use and selection of protecting groups will be apparent to those skilled in the art of chemical synthesis (see, e.g., Greene, T.W.; Wuts, P.G.M. Protective Groups in Organic Synthesis [Protective Groups in Organic Synthesis], 2nd ed.; Wiley: New York, 1991). Those skilled in the art will recognize that in some cases, after the introduction of a given reagent as depicted in any individual scheme, additional conventional synthetic steps that are not described in detail may be necessary to complete the synthesis of the compound of formula 1. Those skilled in the art will also recognize that it may be necessary to carry out the combination of steps shown in the above schemes in an order different from the specific sequence presented for preparing the compound of formula 1.

[0481] Those skilled in the art will also recognize that the compounds of formula 1 and the intermediates described herein are susceptible to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.

[0482] Without further elaboration, it is believed that those skilled in the art can utilize the present disclosure to its fullest extent using the foregoing description. Accordingly, the following synthetic examples are to be construed as merely illustrative and not limiting of the present disclosure in any way. The steps in the following synthetic examples illustrate the procedures for each step in the overall synthetic transformation, and the starting materials used for each step do not necessarily have to be prepared by the specific preparative experiments whose procedures are described in other examples or steps. The ambient temperature or room temperature is defined as about 20 °C - 25 °C. Percentages are by weight, unless otherwise indicated for chromatographic solvent mixtures or as otherwise specified. Unless otherwise indicated, the parts and percentages of chromatographic solvent mixtures are by volume. MPLC refers to medium pressure liquid chromatography on silica gel. 1 1H NMR spectra are reported in ppm at the low field of tetramethylsilane; "s" means singlet, "d" means doublet, "dd" means doublet of doublets, "ddd" means doublet of doublets of doublets, "t" means triplet, "m" means multiplet, and "br s" means broad singlet. For mass spectrometry data, the reported values are the molecular weights of the parent molecular ions (M) formed by adding H (molecular weight = 1) to the molecule to obtain the M+1 peak observed by mass spectrometry using atmospheric pressure chemical ionization (AP + ) + The molecular weight of the parent molecular ion (M) formed by adding H (molecular weight = 1) to the molecule to obtain the M+1 peak observed by mass spectrometry using atmospheric pressure chemical ionization (AP

[0483] Schemes 1 to 11 illustrate methods for preparing compounds of formula 1 having various substituents. Compounds of formula 1 having substituents other than those specifically indicated in Schemes 1 to 11 can be prepared by general methods known in the field of synthetic organic chemistry, including methods similar to those described in Schemes 1 to 11.

[0484] Synthesis Example 1

[0485] Preparation of 3-fluoro-4-[fluoro-[4-(trifluoromethylsulfinyl)phenyl]methyl]-5-(1H-1,2,4-triazol-2-yl)pyridine (Compound 67)

[0486] Step A: Preparation of (3,5-difluoro-4-pyridyl)-[4-(trifluoromethylsulfonyl)phenyl]methanol

[0487] At -20 °C, a freshly prepared solution of lithium diisopropylamide (11.4 mmol, in 10 mL of THF and n-hexane) was slowly added to a stirred solution of 3,5-difluoro-pyridine (1.20 g, 10.4 mmol) in THF (20 mL). After stirring for 1 h at -20 °C to -10 °C, a solution of 4-(trifluoromethylsulfonyl)benzaldehyde (2.15 g, 10.4 mmol) in THF (10 mL) was added to the reaction mixture at -20 °C. After stirring for an additional 1 h at -20 °C to -10 °C, the reaction mixture was quenched with saturated aqueous NH4Cl, then diluted with water and extracted with ethyl acetate. The combined organic phases were washed with water and saturated aqueous NaCl, dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (using hexane / ethyl acetate as the eluent) to afford the title product as a light white solid (1.36 g, 4.2 mmol).

[0488] 1 1H NMR (CDCl3) δ 8.34 (s, 2H), 7.66 (d, 2H), 7.48 (d, 2H), 6.29 (s, 1H).

[0489] Step B: Preparation of 3,5-difluoro-4-[fluoro-[4-(trifluoromethylsulfonyl)phenyl]methyl]pyridine

[0490] At -78 °C, bis(2-methoxyethyl)aminosulfur trifluoride (0.55 mL, 2.96 mmol) was added to a stirred solution of (3,5-difluoro-4-pyridyl)-[4-(trifluoromethylsulfonyl)phenyl]methanol (i.e., the product of step A) (650 mg, 2.02 mmol) in dichloromethane (25 mL). After stirring for 2 h, the reaction mixture was slowly diluted with saturated aqueous NaHCO3 and extracted with dichloromethane. The combined organic phases were washed with water and saturated aqueous NaCl, dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (using hexane / ethyl acetate (80:20 to 40:60) as the eluent) to afford the title product, the compound of the present disclosure, as a pale yellow oil (490 mg, 1.52 mmol).

[0491] 1 1H NMR (CDCl3) δ 8.41 (d, 2H), 7.70 (d, 2H), 7.49 (d, 2H), 6.88 (d, 1H).

[0492] Step C: Preparation of 3-fluoro-4-[fluoro-[4-(trifluoromethylsulfonyl)phenyl]methyl]-5-(1,2,4-triazol-2-yl)pyridine Preparation

[0493] A mixture of 3,5-difluoro-4-[fluoro-[4-(trifluoromethylsulfonyl)phenyl]methyl]pyridine (i.e., the product of Step B) (300 mg, 0.93 mmol), 1,2,3-triazole (64 mg, 0.93 mmol), and K2CO3 (205 mg, 1.49 mmol) in DMF (4 mL) was stirred at 100 °C for 2 h. The reaction mixture was then cooled to room temperature and partitioned between water and ethyl acetate. The organic phase was washed with water and saturated aqueous NaCl, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography (using hexane / ethyl acetate as the eluent) to afford the title product as a white solid (80 mg, 0.22 mmol).

[0494] 1 H NMR (CDCl3) δ 8.96 (s, 1H), 8.57 (s, 1H), 7.96 (s, 2H), 7.68 (d, 2H), 7.60 (d, 2H), 7.24 (d, 1H).

[0495] Step D: Preparation of 3-fluoro-4-[fluoro-[4-(trifluoromethylsulfinyl)phenyl]methyl]-5-(1,2,4-triazol-2-yl)pyridine Preparation

[0496] At 0 °C, 3-chloroperoxybenzoic acid (91 mg, purity < 77%) was added to a stirred solution of 3-fluoro-4-[fluoro-[4-(trifluoromethylsulfonyl)phenyl]methyl]-5-(1H-1,2,3-triazol-2-yl)pyridine (i.e., the product of Step C) (100 mg, 0.27 mmol) in dichloromethane (3 mL). The reaction mixture was slowly warmed to room temperature and stirred for 3 h. The reaction mixture was then quenched with an aqueous solution of NaHSO3 and partitioned between water and dichloromethane. The organic phase was washed with water and saturated aqueous NaCl, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography (using hexane / ethyl acetate as the eluent) to afford the title product as a colorless viscous oil (30 mg, 0.08 mmol).

[0497] 1 H NMR (CDCl3) δ 9.00 (s, 1H), 8.59 (s, 1H), 7.98 (s, 2H), 7.83 (s, 4H), 7.30 (d, 1H).

[0498] Synthesis Example 2

[0499] Preparation of 3-[5-fluoro-4-[methoxy-[4-(trifluoromethylsulfonyl)phenyl]methyl]-3-pyridinyl]-1,2,4-oxadiazole (Compound 83)

[0500] Step A: Preparation of (3-bromo-5-fluoro-4-pyridyl)-[4-(trifluoromethylsulfonyl)phenyl]methanol

[0501] At -20 °C, a freshly prepared solution of lithium diisopropylamide (26 mmol in 20 mL of THF and n-hexane) was slowly added to a stirred solution of 3-bromo-5-fluoropyridine (4.40 g, 25 mmol) in THF (20 mL). After stirring for 1 h at -20 °C to -10 °C, a solution of 4-(trifluoromethylsulfonyl)benzaldehyde (4.85 g, 23.5 mmol) in THF (10 mL) was added to the reaction mixture at -20 °C. After stirring for an additional 1 h at -20 °C to -10 °C, the reaction mixture was quenched with saturated aqueous NH4Cl, then diluted with water and extracted with ethyl acetate. The combined organic phases were washed with water and saturated aqueous NaCl, dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (using hexane / ethyl acetate as the eluent) to afford the title product as a pale yellow oil (6.95 g, 18.2 mmol).

[0502] 1 1H NMR (CDCl3) δ 8.56 (s, 1H), 8.36 (s, 1H), 7.65 (d, 2H), 7.47 (d, 2H), 6.39 (d, 1H), 3.66 (d, 1H).

[0503] Step B: Preparation of 3-bromo-5-fluoro-4-[methoxy-[4-(trifluoromethylsulfonyl)phenyl]methyl]pyridine

[0504] At 0 °C, sodium hydride (165 mg, 4.12 mmol, 60% in mineral oil) was added to a stirred solution of (3-bromo-5-fluoro-4-pyridyl)-[4-(trifluoromethylsulfonyl)phenyl]methanol (i.e., the product of step A) (1.26 g, 3.30 mmol) in dry THF (10 mL). The resulting mixture was stirred at room temperature for 1 h and then treated with iodomethane (0.24 mL, 3.96 mmol). After stirring for an additional 1.5 h at room temperature, the reaction mixture was treated with water and extracted with ethyl acetate / hexane (1:1). The combined organic phases were washed with water and saturated aqueous sodium chloride, dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (using hexane / ethyl acetate (90:10 to 60:40) as the eluent) to afford the title compound as a pale yellow oil (1.10 g, 2.80 mmol).

[0505] 1 1H NMR (CDCl3) δ 8.60 (s, 1H), 8.37 (s, 1H), 7.63 (d, 2H), 7.52 (d, 2H), 5.95 (s, 1H), 3.47 (s, 3H).

[0506] Step C: Preparation of 5-fluoro-4-[methoxy-[4-(trifluoromethylsulfonyl)phenyl]methyl]pyridine-3-carbonitrile

[0507] A mixture of 3-bromo-5-fluoro-4-[methoxy[4-(trifluoromethylsulfonyl)phenyl]methyl]pyridine (i.e., the product of Step B) (1.0 g, 2.52 mmol), Zn(CN)2 (325 mg, 2.76 mmol), and Pd(PPh3)4 (291 mg, 0.25 mmol) in N,N-dimethylformamide (5 mL) was reacted in a vial under a nitrogen atmosphere in a microwave at 150 °C for 10 min. The reaction mixture was then partitioned between water and ethyl acetate. The organic layer was washed with water and saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography (using hexane / ethyl acetate (90:10 to 60:40) as the eluent) to afford the title compound as a yellow oil (0.80 g, 2.42 mmol).

[0508] 1 1H NMR (CDCl3) δ 8.72 (s, 1H), 8.63 (s, 1H), 7.67 (d, 2H), 7.59 (d, 2H), 5.79 (s, 1H), 3.50 (s, 3H).

[0509] Step D: Preparation of 3-[5-fluoro-4-[methoxy-[4-(trifluoromethylsulfonyl)phenyl]methyl]-3-pyridyl]-1,2, 4-oxadiazole

[0510] A mixture of 5-fluoro-4-[methoxy-[4-(trifluoromethylsulfonyl)phenyl]methyl]pyridine-3-carbonitrile (i.e., the product of Step C) (0.27 g, 0.82 mmol) and hydroxylamine (0.25 mL, 3.78 mmol, 50% in H2O) in EtOH (5 mL) was stirred at room temperature for 48 h. The reaction mixture was then concentrated under reduced pressure. Triethyl orthoformate (0.5 mL) and a drop of concentrated hydrochloric acid were added to the residue. The mixture was then stirred at 80 °C for 1 h. The reaction mixture was cooled to room temperature and then partitioned between water and ethyl acetate. The organic layer was washed with water and saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography (using hexane / ethyl acetate (90:10 to 60:40) as the eluent) to afford the title compound as a pale yellow oil (0.17 g, 0.46 mmol).

[0511] 1H NMR (CDCl3) δ 8.96 (s, 1H), 8.91 (s, 1H), 8.57 (s, 1H), 7.62 (d, 2H), 7.57 (d, 2H), 6.29 (s, 1H), 3.39 (s, 3H).

[0512] Synthesis Example 3

[0513] Preparation of 3-Fluoro-4-[(R)-methoxy-[4-(trifluoromethoxy)phenyl]methyl]-5-(triazol-2-yl)pyridine (Compound 125)

[0514] Step A: Preparation of (3,5-difluoro-4-pyridyl)-[4-(trifluoromethoxy)phenyl]methanol

[0515] Under a N2 atmosphere at -78 °C, 2M LDA (191.3 mL, 0.381 mol, 1.1 eq) in THF was slowly added to a solution of 3,5-difluoropyridine (40 g, 0.347 mol, 1.0 eq) in THF (400 mL). The reaction mixture was then stirred for 30 min, and then 4-(trifluoromethoxy)benzaldehyde (72.4 g, 0.381 mol, 1.1 eq) was added at -78 °C and stirred at -78 °C for 2 h. The reaction was monitored by TLC, and the reaction mixture was quenched with saturated aqueous NH4Cl, extracted with EtOAc (3 × 500 mL), then dried over anhydrous Na2SO4 and concentrated under reduced pressure. The obtained crude product was purified by column chromatography on silica gel 100 - 200 using 40% ethyl acetate / petroleum ether as eluent to give the title product as an off-white semi-solid (70 g, 66% yield).

[0516] 1 1H NMR (d6-DMSO) δ 8.49 (s, 2H), 7.51 (d, 2H), 7.35 (d, 2H), 6.59 (d, 1H), 6.16 (d, 1H).

[0517] Step B: Preparation of (3,5-difluoro-4-pyridyl)-[4-(trifluoromethoxy)phenyl]methanone

[0518] Under a N2 atmosphere at room temperature, activated MnO2 (199 g, 2.29 mol, 10 eq) was added to a solution of (3,5-difluoro-4-pyridyl)-[4-(trifluoromethoxy)phenyl]methanol (i.e., the product of step A) (70.0 g, 0.229 mol, 1.0 eq) in dichloromethane (700 mL), and then stirred for 16 h. The reaction was monitored by TLC, and the reaction mixture was filtered through a bed of diatomaceous earth and washed with dichloromethane (200 mL). The solvent was concentrated under reduced pressure to give a crude solid. The obtained crude product was purified by column chromatography on silica gel 100 - 200 using 30% ethyl acetate / petroleum ether as eluent to give the title compound as an off-white solid (65 g, 93% yield).

[0519] 1 1H NMR (d6-DMSO) δ 8.80 (s, 2H), 8.07 (d, 2H), 7.60 (d, 2H).

[0520] Step C: Preparation of [3-fluoro-5-(1,2,4-triazol-2-yl)-4-pyridyl]-[4-(trifluoromethoxy)phenyl]methanone

[0521] At room temperature under a N2 atmosphere, to a solution of the compound (3,5-difluoro-4-pyridyl)-[4-(trifluoromethoxy)phenyl]methanone (i.e., the product of step B) (65 g, 0.214 mol, 1.0 equivalent) in DMF (650 ml) was added K2CO3 (29.6 g, 0.214 mol, 1.0 equivalent) and 1,2,3-triazole (14.8 g, 0.214 mol, 1.0 equivalent). The reaction mixture was then stirred for 48 h. The reaction was monitored by TLC. The reaction mixture was poured into ice-cold water (1000 ml) and extracted with EtOAc (3 × 300 ml). The organic layer was then washed with brine (2 × 200 ml) and ice-cold water (200 ml), then dried over anhydrous Na2SO4 and concentrated under reduced pressure. The obtained crude product was purified by column chromatography using 100-200 silica gel to afford the title product as an off-white solid (19 g, 25% yield).

[0522] 1 1H NMR (d6-DMSO) δ 9.29 (s, 1H), 8.91 (s, 1H), 8.11 (s, 2H), 8.00 (d, 2H), 7.51 (d, 2H).

[0523] Step D: Preparation of (R)-[3-fluoro-5-(1,2,4-triazol-2-yl)-4-pyridyl]-[4-(trifluoromethoxy)phenyl]methanol Preparation

[0524] At room temperature, B(OMe)3 (12.4 g, 0.012 mmol, 0.22 eq) was added to a solution of (S)-(-)-α,α-diphenyl-2-pyrrolidinemethanol (2.73 g, 0.011 mol, 0.2 eq) in THF (190 ml), and then the mixture was stirred for 1 h under a N2 atmosphere at room temperature. Then borane dimethyl sulfide (6.16 g, 0.081 mol, 1.5 eq) was slowly added at 0 °C while observing floating and exotherm. Then the compound [3-fluoro-5-(1H-1,2,3-triazol-2-yl)-4-pyridinyl]-[4-(trifluoromethoxy)phenyl]methanone (i.e., the product of step C) (19 g, 0.054 mol, 1.0 eq) (dissolved in 30 ml of THF) was added at 0 °C - 5 °C, and then the mixture was allowed to reach room temperature and stirred for 3 h. The reaction was monitored by TLC. After the reaction was completed, it was cooled to 0 °C, and then the reaction mixture was quenched by slowly dropwise adding 2N HCl (80 ml) while observing vigorous gas evolution and exotherm, and then extracted with ethyl acetate (3 × 200 ml). The organic layer was dried over anhydrous Na2SO4 and concentrated to obtain the crude product. The obtained crude product was purified by column chromatography using 100 - 200 silica gel eluted with 30% ethyl acetate / petroleum ether to give the title product as a colorless liquid (8.2 g, 43% yield). Chiral HPLC analysis using a Chiralpak IF (4.6*250 mm) 5u column indicated that the product had 95% ee as the R configuration. The R absolute configuration was assigned according to the literature, see: Moriyasu Masui & Takayuki Shioiri, Synlett [Synthesis Letters], 1997, 273 - 274.

[0525] Step E: Preparation of 3-fluoro-4-[(R)-methoxy-[4-(trifluoromethoxy)phenyl]methyl]-5-(1,2,4-triazol-2-yl)pyridine Preparation

[0526] At 0 °C, NaH (1.0 g, 0.046 mol, 2.0 eq) was added portionwise on average to a solution of (R)-[3-fluoro-5-(triazol-2-yl)-4-pyridyl]-[4-(trifluoromethoxy)phenyl]methanol compound (8.2 g, 0.023 mol, 1.0 eq) in THF while observing floating, then stirred at 0 °C for 5 min, and then MeI (4.93 g, 0.034 mol, 1.5 eq) was added at 0 °C. Then it was stirred at room temperature for 2 h. The reaction was monitored by TLC. The reaction mixture was poured into ice water (50 ml) and extracted with ethyl acetate (2 × 100 ml). Then the organic layer was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The obtained crude solid was purified by column chromatography using 100 - 200 silica gel eluted with 20% ethyl acetate / petroleum ether to give the title product as a colorless liquid (6.0 g, 70.5% yield). Chiral HPLC analysis indicated that the product had 93% ee, 25 [α]

[0527] 1 H NMR (d6-DMSO) δ 8.81 (s, 1H), 8.78 (s, 1H), 8.32 (s, 2H), 7.51 (d, 2H), 7.37 (d, 2H), 5.66 (s, 1H), 3.21 (s, 3H).

[0528] By the procedures described herein together with methods known in the art, the following compounds in Tables 1 to 42N can be prepared. The following abbreviations are used in the subsequent tables: t means tertiary, s means secondary, n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, i-Pr means isopropyl, Bu means butyl, Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, SEt means ethylthio, -CN means cyano, Ph means phenyl, Py means pyridyl, -NO2 means nitro, TMS means trimethylsilyl, S(O)Me means methylsulfinyl, and S(O)2Me means methylsulfonyl.

[0529] Fragments Q-1 to Q-19 shown below are mentioned in Tables 1A to 98I. The structures of fragments Q-1 to Q-19 are illustrated in Example 3. The wavy line indicates the attachment point of the fragment to the rest of the molecule.

[0530] Example 3

[0531]

[0532]

[0533] Table 1A-42A relates to the structures shown below.

[0534]

[0535] Table 1AR 1 is F, A is CH, R 2 is H and R 5 is H.

[0536]

[0537]

[0538] This disclosure also includes Tables 2A to 42A, each having the same construction as Table 1A above, except that the row headings under the Markush structure in Table 1A (i.e., "A is CH, R 4 is H and R 5 is H.") are replaced by the corresponding row headings shown below. For example, in Table 2A the row heading is "R 1 is F, A is CF, R 4 is H and R 5 is H, and Q is as defined in Table 1A above. Thus, the first entry in Table 2A specifically discloses 4-[(4-chlorophenyl)-fluoro-methyl]-3-fluoro-5-(triazol-2-yl)pyridine.

[0539]

[0540]

[0541] Table 1B

[0542] Table 1B is the same as Table 1A, except that the chemical structure in the title of Table 1B is replaced by the following structure:

[0543]

[0544] For example, the first compound in Table 1B is the structure shown directly above, where R 1 is F, A is CH, R 2 is H, R 5 is H, and Q is 4-chlorophenyl.

[0545] Table 2B - 42B

[0546] Tables 2B to 42B are constructed in the same manner as Tables 2A to 42A.

[0547] Table 1C

[0548] Table 1C is the same as Table 1A, except that the chemical structure in the title of Table 1B is replaced by the following structure:

[0549]

[0550] For example, the first compound in Table 1C is the structure directly shown above, where R 1 is F, A is CH, R 2 is H, R 5 is H, and Q is 4-chlorophenyl.

[0551] Table 2C - 42C

[0552] Tables 2C to 42C are constructed in a similar manner to Tables 2A to 42A.

[0553] Table 1D

[0554] Table 1D is the same as Table 1A, except that the chemical structure in the title of Table 1D is replaced by the following structure:

[0555]

[0556] For example, the first compound in Table 1D is the structure directly shown above, where R 1 is F, A is CH, R 2 is H, R 5 is H, and Q is 4-chlorophenyl.

[0557] Table 2D - 42D

[0558] Tables 2D to 42D are constructed in a similar manner to Tables 2A to 42A.

[0559] Table 1E

[0560] Table 1E is the same as Table 1A, except that the chemical structure in the title of Table 1E is replaced by the following structure:

[0561]

[0562] For example, the first compound in Table 1D is the structure directly shown above, where R 1 is F, A is CH, R 2 is H, R 5 is H, and Q is 4-chlorophenyl.

[0563] Table 2E - 42E

[0564] Tables 2E to 42E are constructed in a similar manner to Tables 2A to 42A.

[0565] Table 1F

[0566] Table 1F is the same as Table 1A, except that the chemical structure in the title of Table 1F is replaced by the following structure:

[0567]

[0568] For example, the first compound in Table 1F is the structure directly shown above, where R 1 is F, A is CH, R 2 is H, R 5 is H, and Q is 4-chlorophenyl.

[0569] Table 2F - 42F

[0570] Tables 2F to 42F are constructed in a similar manner to Tables 2A to 42A.

[0571] Table 1G

[0572] Table 1G is the same as Table 1A, except that the chemical structure in the title of Table 1G is replaced by the following structure:

[0573]

[0574] For example, the first compound in Table 1G is the structure directly shown above, where R 1 is F, A is CH, R 2 is H, R 5 is H, and Q is 4-chlorophenyl.

[0575] Table 2G - 42G

[0576] Tables 2G to 42G are constructed in a similar manner to Tables 2A to 42A.

[0577] Table 1H

[0578] Table 1H is the same as Table 1A, except that the chemical structure in the title of Table 1H is replaced by the following structure:

[0579]

[0580] For example, the first compound in Table 1H is the structure directly shown above, where R 1 is F, A is CH, R 2 is H, R 5 is H, and Q is 4-chlorophenyl.

[0581] Table 2H - 42H

[0582] Tables 2H to 42H are constructed in a similar manner to Tables 2A to 42A.

[0583] Table 1I

[0584] Table 1I is the same as Table 1A, except that the chemical structure in the title of Table 1H is replaced by the following structure:

[0585]

[0586] For example, the first compound in Table 1I is the structure directly shown above, where R 1 is F, A is CH, R 2 is H, R 5 is H, and Q is 4-chlorophenyl.

[0587] Table 2I - 42I

[0588] Tables 2I to 42I are constructed in a similar manner to Tables 2A to 42A.

[0589] Table 1J

[0590] Table 1J is the same as Table 1A, except that the chemical structure in the title of Table 1J is replaced by the following structure:

[0591]

[0592] For example, the first compound in Table 1J is the structure directly shown above, where R 1 is F, A is CH, R 2 is H, R 5 is H, and Q is 4-chlorophenyl.

[0593] Table 2J - 42J

[0594] Tables 2J to 42J are constructed in a similar manner to Tables 2A to 42A.

[0595] Table 1K

[0596] Table 1K is the same as Table 1A, except that the chemical structure in the title of Table 1K is replaced by the following structure:

[0597]

[0598] For example, the first compound in Table 1K is the structure directly shown above, where R 1 is F, A is CH, R 2 is H, R 5 is H, and Q is 4-chlorophenyl.

[0599] Table 2K - 42K

[0600] Table 2K to 42K are constructed in a similar manner to Table 2A to 42A.

[0601] Table 1L

[0602] Table 1L is the same as Table 1A, except that the chemical structure in the title of Table 1L is replaced by the following structure:

[0603]

[0604] For example, the first compound in Table 1L is the structure directly shown above, where R 1 is F, A is CH, R 2 is H, R 5 is H, and Q is 4-chlorophenyl.

[0605] Table 2L - 42L

[0606] Table 2L to 42L are constructed in a similar manner to Table 2A to 42A.

[0607] Table 1M

[0608] Table 1M is the same as Table 1A, except that the chemical structure in the title of Table 1M is replaced by the following structure:

[0609]

[0610] For example, the first compound in Table 1M is the structure directly shown above, where R 1 is F, A is CH, R 2 is H, R 5 is H, and Q is 4-chlorophenyl.

[0611] Table 2M - 42M

[0612] Table 2M to 42M are constructed in a similar manner to Table 2A to 42A.

[0613] Table 1N

[0614] Table 1N is the same as Table 1A, except that the chemical structure in the title of Table 1N is replaced by the following structure:

[0615]

[0616] For example, the first compound in Table 1N is the structure directly shown above, where R1 is F, A is CH, R 2 is H, R5 is H, and Q is 4-chlorophenyl.

[0617] Table 2N - 42N

[0618] Table 2N to 42N are constructed in a manner similar to Table 2A to 42A.

[0619] The compounds of the present disclosure will generally be used as active ingredients for invertebrate pest control in a composition (i.e., formulation), where at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents is used as a carrier. The components of the formulation or composition are selected to be consistent with the physical properties of the active ingredient, the mode of application, and environmental factors such as soil type, moisture, and temperature.

[0620] Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates) that can optionally be thickened into gels, suspensions, emulsions (including microemulsions, oil-in-water emulsions, flowable concentrates, and / or suspoemulsions), etc. The general types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions, oil-in-water emulsions, flowable concentrates, and suspoemulsions. The general types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates, and oil dispersions.

[0621] The general types of solid compositions are powders, dusts, granules, balls, pellets, lozenges, tablets, filled films (including seed coatings), etc., 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. The active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively, the entire formulation of the active ingredient can be encapsulated (or "coated"). Encapsulation can control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsifiable concentrate formulations and dry granule formulations. High-strength compositions are mainly used as intermediates for further formulations.

[0622] Sprayable formulations are typically dispersed in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily dilutable in a spray medium, usually water, but occasionally another suitable medium such as aromatic hydrocarbons or paraffinic hydrocarbons or vegetable oils. The spray volume can range from about one liter to several thousand liters per hectare, but more typically ranges from about ten to several hundred liters per hectare. Sprayable formulations can be tank-mixed with water or another suitable medium for foliar treatment by air or ground application, or for application to the growth medium of plants. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into furrows during planting. Liquid and solid formulations can be applied as a seed treatment to the seeds of crops and other desired vegetation before planting to protect the developing roots and other below-ground plant parts and / or leaves by systemic absorption.

[0623] The formulation will typically contain up to 100 weight percent of an active ingredient, diluent, and surfactant in the approximate ranges set forth below.

[0624]

[0625] Solid diluents include, for example, clays (such as bentonite, montmorillonite, attapulgite, and kaolin), gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (such as lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and sodium bicarbonate, and sodium sulfate. Representative solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Edition, Dorland Books, Caldwell, New Jersey.

[0626] Liquid diluents include, for example, water, N,N-dimethylalkanamides (such as N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (such as N-methylpyrrolidone), alkyl phosphates (such as triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (such as white mineral oil, n-alkanes, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerol, triacetin, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone, and 4-hydroxy-4-methyl-2-pentanone, acetates such as isopentyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate, and isobornyl acetate, other esters such as alkylated lactates, diesters, alkyl and aryl benzoates, γ-butyrolactone, and alcohols which may be straight-chain, branched-chain, saturated or unsaturated such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecanol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresols, and benzyl alcohol. Liquid diluents also include saturated and unsaturated fatty acids (typically C6-C 22The glycerides of (), such as vegetable seed and fruit oils (e.g., olive oil, castor oil, linseed oil, sesame oil, corn oil (maize oil), peanut oil, sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil, and palm kernel oil), animal fats (e.g., tallow, lard, hog fat, fish liver oil, fish oil), and mixtures thereof. The liquid diluent also includes alkylated (e.g., methylated, ethylated, butylated) fatty acids, where the fatty acids can be obtained by hydrolysis of glycerides from plant and animal sources and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Edition, Interscience, New York, 1950.

[0627] The solid and liquid compositions of the present disclosure often include one or more surfactants. When added to a liquid, a surfactant (also referred to as a "surface-active agent") typically alters, most often reduces, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, the surfactant can be used as a wetting agent, dispersant, emulsifier, or defoamer.

[0628] Surfactants can be classified as nonionic, anionic, or cationic. Nonionic surfactants useful in the compositions of the present invention include, but are not limited to: alcohol alkoxylates, such as those based on natural and synthetic alcohols (which may be branched or straight-chain) and prepared from alcohols and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof; amine ethoxylates, alkanolamides, and ethoxylated alkanolamides; alkoxylated triglycerides, such as ethoxylated soybean oil, castor oil, and rapeseed oil; alkylphenol alkoxylates, such as octylphenol ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate, and dodecylphenol ethoxylate (prepared from phenol and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and inverse block polymers in which the terminal block is prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated triphenylvinylphenols (including those prepared from ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylated esters (such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters, and polyethoxylated glycerol fatty acid esters); other sorbitan derivatives such as sorbitan esters; polymeric surfactants, such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, graft or comb polymers, and star polymers; polyethylene glycol (peg); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar derivatives, such as sucrose esters, alkyl polyglycosides, and alkyl polysaccharides.

[0629] 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 acid or their anhydrides; olefin sulfonates; phosphate esters, such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates, and phosphate esters of styrenylphenol ethoxylates; protein-based surfactants; sarcosine derivatives; styrenylphenol ether sulfates; 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-alkyl taurates; sulfonates of benzene, cumene, toluene, xylene, and dodecylbenzene and tridecylbenzene; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkylnaphthalenes; sulfonates of petroleum fractions; sulfosuccinamates; and sulfosuccinates and their derivatives, such as dialkyl sulfosuccinates.

[0630] Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propanediamines, tripropylene triamine, and dipropylene tetramine, and ethoxylated amines, ethoxylated diamines, and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); amine salts such as ammonium acetate and diamine salts; quaternary ammonium salts such as quats, ethoxylated quats, and diquats; and amine oxides, such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

[0631] Mixtures of nonionic surfactants and anionic surfactants, or mixtures of nonionic surfactants and cationic surfactants, may also be used in the compositions of the present invention. Nonionic surfactants, anionic surfactants, and cationic surfactants and their recommended uses are disclosed in a number of published references, including McCutcheon’s Emulsifiers and Detergents, annual American and International Editions, published by The Manufacturing Confectioner Publishing Co., McCutcheon Division; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A.S. Davidson and B. Milwidsky, Synthetic Detergents, 7th Edition, John Wiley and Sons, New York, 1987.

[0632] The compositions of the present disclosure may also contain formulation aids and additives known to those skilled in the art as adjuvants (some of which may also be considered to act as solid diluents, liquid diluents, or surfactants). Such formulation aids and additives can control: pH (buffering agents), foaming during processing (antifoaming agents such as polyorganosiloxanes), sedimentation of the active ingredient (suspending agents), viscosity (thixotropic thickeners), microbial growth within the container (antimicrobial agents), product freezing (antifreezing agents), color (dye / pigment dispersions), elution (film-forming agents or adhesives), evaporation (evaporation retardants), and other formulation properties. Film-forming agents include, for example, polyvinyl acetate, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol, polyvinyl alcohol copolymers, and waxes. Examples of formulation aids and additives include those listed in the following: McCutcheon’s Volume 2: Functional Materials, published by the McCutcheon Division of Manufacturing Confectioner Publishing Company, annual International and North American editions; and PCT Publication WO 03 / 024222.

[0633] Typically, the compounds of formula 1 and any other active ingredients are incorporated into the compositions of the invention by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent. Solutions including emulsifiable concentrates can be prepared by simply mixing these ingredients. If the solvent of the liquid composition intended to be used as an emulsifiable concentrate is immiscible with water, an emulsifier is typically added to emulsify the solvent containing the active ingredient upon dilution with water. An active ingredient slurry with a particle size up to 2,000 μm can be wet milled using a media mill to obtain particles with an average particle size below 3 μm. An aqueous slurry can be made into a finished suspending agent (see, e.g., U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations generally require a dry milling process, resulting in an average particle size in the range of 2 to 10 μm. Dusts and powders can be prepared by blending and typically by grinding (e.g., with a hammer mill or a fluid energy mill). Granules and pellets can be prepared by spraying the active substance onto a preformed granule carrier or by an agglomeration technique. See, Browning, “Agglomeration”, Chemical Engineering, December 4, 1967, pp. 147-48; Perry’s Chemical Engineer’s Handbook, 4th ed., McGraw-Hill, New York, 1963, pp. 8-57 et seq., and WO 91 / 13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442, and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701, and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.

[0634] For further information in the area of formulations, see “The Formulator’s Toolbox–Product Forms for Modern Agriculture” in T.S. Woods, Pesticide Chemistry and Bioscience, The Food–Environment Challenge, edited by T. Brooks and T.R. Roberts, 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, column 6, lines 16 to column 7, line 19 and Examples 10-41; U.S 3,309,192, column 5, line 43 to column 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, column 3, line 66 to column 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp. 81–96; Hance et al., Weed Control Handbook, 8th Edition, Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

[0635] In the following examples, all formulations were prepared in a conventional manner. Compound numbers refer to the compounds in Index Tables A to B. Without further elaboration, it is believed that those skilled in the art can utilize the present disclosure to its fullest extent using the foregoing description. Accordingly, the following examples should be construed as merely illustrative and not limiting the present disclosure in any way. Percentages are by weight unless otherwise indicated.

[0636] Example A

[0637] High-strength concentrate

[0638] Compound 8 98.5%

[0639] Silica aerogel 0.5%

[0640] Synthetic amorphous fine silica 1.0%

[0641] Example B

[0642] Wettable powder

[0643]

[0644] Example C

[0645] Granule

[0646] Compound 19 10.0%

[0647] Attapulgite granules (low volatile matter, 0.71 / 0.30mm; 90.0%

[0648] U.S.S. No. 25 - 50 sieve)

[0649] Example D

[0650] Extruded pellet

[0651]

[0652] Example E

[0653] Emulsifiable concentrate

[0654] Compound 3 10.0% Polyoxyethylene sorbitan hexaoleate 20.0%

[0655] C6 - C 10 Fatty acid methyl ester 70.0%

[0656] Example F

[0657] Microemulsion

[0658]

[0659] Example G

[0660] Seed treatment

[0661]

[0662] Example H

[0663] Fertilizer stick

[0664]

[0665]

[0666] Example I Suspension concentrate

[0667]

[0668] Example J Emulsion in water

[0669]

[0670] Example K Oil dispersion

[0671]

[0672] Example L

[0673] Suspension emulsion

[0674]

[0675] The compounds of the present disclosure exhibit activity against a broad spectrum of invertebrate pests. These pests include invertebrates inhabiting a variety of environments such as the leaves, roots, soil, harvested crops or other foods, building structures or the integument of animals. These pests include, for example, invertebrates that feed on leaves (including leaves, stems, flowers and fruits), seeds, wood, textile fibers or animal blood or tissues and thus cause damage or harm to, for example, growing or stored agronomic crops, forests, greenhouse crops, ornamental plants, nursery crops, stored food and fiber products, or houses or other structures or their contents, or are harmful to animal health or public health. Those skilled in the art will understand that not all compounds are equally effective against all growth stages of all pests.

[0676] Accordingly, the compounds and compositions of the invention are agriculturally useful for protecting field crops against phytophagous invertebrate pests and are also useful non-agriculturally for protecting other horticultural crops and plants against phytophagous invertebrate pests. Such utility includes protecting crops and other plants (i.e., agricultural and non-agricultural) containing 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 tolerance to adverse growth conditions (such as high or low temperature, low or high soil moisture, and high salinity), increased flowering or fruiting, greater harvest yields, faster maturity, higher quality and / or nutritional value of harvested products, or improved storage or processing characteristics of harvested products. Transgenic plants can be modified to express multiple traits. Examples of plants containing traits provided by genetic engineering or mutagenesis include corn, cotton, soybean, and potato varieties expressing Bacillus thuringiensis insecticidal toxins, such as YIELD and INVICTARR2PRO TM , and herbicide-tolerant corn, cotton, soybean, and canola varieties, such as ROUNDUP LIBERTY and and crops expressing N-acetyltransferase (GAT) to provide resistance to glyphosate herbicides, or crops containing the HRA gene providing resistance to herbicides that inhibit acetolactate synthase (ALS). The compounds and compositions of the invention can exhibit an enhancing effect on traits introduced by genetic engineering or modified by mutagenesis, thereby enhancing the phenotypic expression or effectiveness of the traits, or increasing the invertebrate pest control effectiveness of the compounds and compositions of the invention. In particular, the compounds and compositions of the invention can exhibit an enhancing effect on the phenotypic expression of proteins or other natural products toxic to invertebrate pests to provide greater than additive control of these pests.

[0677] The compositions of the present disclosure may also optionally comprise phyto-nutrients, e.g., a fertilizer composition comprising at least one phyto-nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium, magnesium, iron, copper, boron, manganese, zinc, and molybdenum. Notably, the compositions comprising at least one fertilizer composition, said at least one fertilizer composition comprising at least one phyto-nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium, and magnesium. The compositions of the present disclosure further comprising at least one phyto-nutrient may be in liquid or solid form. Notably, solid formulations in the form of granules, rods, or tablets. Solid formulations comprising a fertilizer composition may be prepared by mixing the compounds or compositions of the present disclosure with a fertilizer composition and formulation ingredients and then preparing the formulation by methods such as granulation or extrusion. Alternatively, solid formulations may be prepared by spraying a solution or suspension of the compounds or compositions of the present disclosure in a volatile solvent onto a fertilizer composition in the form of a previously prepared dimensionally stable mixture (e.g., granules, rods, or tablets) and then evaporating the solvent.

[0678] Non-agronomic use refers to the control of invertebrate pests in areas other than in crop fields. Non-agronomic uses of the compounds and compositions of the present invention include the control of invertebrate pests in stored grains, legumes, and other foods, and in textiles such as clothing and carpets. Non-agronomic uses of the compounds and compositions of the present invention also include the control of invertebrate pests in ornamental plants, forests, gardens, roadside and railway land, and turf such as lawns, golf courses, and pastures. Non-agronomic uses of the compounds and compositions of the present invention also include the control of invertebrate pests in houses and other buildings that may be occupied by humans and / or companion animals, farm animals, ranch animals, zoo animals, or other animals. Non-agronomic uses of the compounds and compositions of the present invention also include the control of pests such as termites that may damage wood or other structural materials used in buildings.

[0679] The non-agronomic uses of the compounds and compositions of the present invention also include protecting human and animal health by controlling parasitic or disease-transmitting invertebrate pests. The control of animal parasites includes controlling external parasites that parasitize on the body surface of the host animal (e.g., shoulders, armpits, abdomen, inner thighs) and internal parasites that parasitize within the host animal (e.g., stomach, intestine, lungs, veins, subcutaneous, lymphatic tissues). External parasitic or disease-transmitting pests include, for example, chiggers, ticks, lice, mosquitoes, flies, mites, and fleas. Internal parasites include heartworms, hookworms, and worms. The compounds and compositions disclosed herein are suitable for systemic and / or non-systemic control of parasite infestations or infections on animals. The compounds and compositions disclosed herein are particularly suitable for combating external parasitic or disease-transmitting pests. The compounds and compositions disclosed herein are suitable for combating parasites that infest the following animals: agricultural working animals such as cattle, sheep, goats, horses, pigs, donkeys, camels, water buffalo, rabbits, hens, turkeys, ducks, geese, and bees; pet animals and domestic animals such as dogs, cats, pet birds, and aquarium fish; and so-called laboratory animals such as hamsters, guinea pigs, rats, and mice. By combating these parasites, mortality and performance degradation (in terms of meat, milk, wool, fur, eggs, honey, etc.) are reduced, and thus applying a composition containing the compounds disclosed herein allows for more economical and simple animal rearing.

[0680] Examples of agricultural or non-agricultural invertebrate pests include eggs, larvae, and adults of Lepidoptera, such as armyworms, cutworms, loopers, and heliothines (e.g., Sesamia inferens Walker, Sesamia nonagrioides Lefebvre, Spodoptera eridania Cramer, Spodoptera frugiperda J.E. Smith, Spodoptera exigua Hübner, Spodoptera littoralis Boisduval, Spodoptera ornithogalli Guenée, Agrotis ipsilon Hufnagel, Anticarsia gemmatalis Hübner, Lithophane antennata Walker, Barathra brassicae Linnaeus, Pseudoplusia includens Walker, Trichoplusia ni Hübner, Heliothis virescens Fabricius) of Noctuidae;Borers, casebearers, webworms, coneworms, cabbageworms, and skeletonizers from the family Pyralidae (e.g., European corn borer (Ostrinia nubilalis Hübner), navel orangeworm (Amyelois transitella Walker), corn root webworm (Crambus caliginosellus Clemens), sod webworms (Pyralidae: Crambinae), such as Herpetogramma licarsisalis Walker, Chilo infuscatellus Snellen, Neoleucinodes elegantalis Guenée, Cnaphalocrocis medinalis Guenée, Desmia funeralis Hübner, Diaphania nitidalis Stoll, Hellula hydralis Guenée, Scirpophaga incertulas Walker, Scirpophaga innotata Walker, (Scirpophaga nivella Fabricius), Chilo polychrysus Meyrick, Chilo suppressalis Walker, Crocidolomia binotalis Zeller;Leafrollers, budworms, seed worms, and fruit worms (e.g., codling moth (Cydia pomonella Linnaeus), grape berry moth (Paralobesia viteana Clemens), oriental fruit moth (Grapholita molesta Busck), false codling moth (Cryptophlebia leucotreta Meyrick), citrus longhorned beetle (Gymnandrosoma aurantianum Lima), red-banded leafroller (Argyrotaenia velutinana Walker), oblique-banded leafroller (Choristoneura rosaceana Harris), light brown apple moth (Epiphyas postvittana Walker), vine moth (Eupoecilia ambiguella Hübner), apple top borer (Pandemis pyrusana Kearfott), omnivorous leafroller (Platynota stultana Walsingham), brown apple leafroller (Pandemis cerasana Hübner), apple leafroller (Pandemis heparana Denis & Schiffermüller)) of the family Tortricidae; and many other economically important Lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth (Lymantria dispar Linnaeus), peach fruit moth (Carposina niponensis Walsingham), peach twig borer (Anarsia lineatella Zeller), potato tuber moth (Phthorimaea operculella Zeller), (ermine moth (Phyllonorycter blancardella Fabricius), apple ermine moth (Lithocolletis ringoniella Matsumura), rice leafroller (Lerodea eufala Edwards), apple leafminer (Leucoptera scitella Zeller));Eggs, nymphs, and adults of Blattodea, including cockroaches from the families Blattellidae and Blattidae (e.g., Blatta orientalis Linnaeus, Blatella asahinai Mizukubo, Blattella germanica Linnaeus, Supella longipalpa Fabricius, Periplaneta americana Linnaeus, Periplaneta brunnea Burmeister, Madeira cockroach (Leucophaea maderae Fabricius), Periplaneta fuliginosa Serville, Periplaneta australasiae Fabr., Nauphoeta cinerea Olivier, and Symploce pallens Stephens); eggs, leaf-feeding, fruit-feeding, root-feeding, seed-feeding, and gall-feeding larvae and adults of Coleoptera, including weevils from the families Anthribidae, Bruchidae, and Curculionidae (e.g., Anthonomus grandis Boheman, Lissorhoptrus oryzophilus Kuschel, Sitophilus granarius Linnaeus, Sitophilus oryzae Linnaeus, Listronotus maculicollis Dietz, Sphenophorus parvulus Gyllenhal, Sphenophorus venatus vestitus Chittenden, Sphenophorus cicatristriatus Fahraeus);Flea beetles, cucumber beetles, rootworms, leaf beetles, potato beetles, and leafminers (e.g., Colorado potato beetle (Leptinotarsa decemlineata Say), western corn rootworm (Diabrotica virgifera LeConte)) from the family Chrysomelidae; chafers and other beetles (e.g., Japanese beetle (Popillia japonica Newman), Oriental beetle (Anomala orientalis Waterhouse), northern masked chafer (Cyclocephala borealis Arrow), southern masked chafer (Cyclocephala immaculata Olivier or C. lurida Bland), dung beetle, and white grub (Aphodius species), black turfgrass ataenius (Ataenius spretulus Haldeman), green June beetle (Cotinis nitida Linnaeus), Asian garden beetle (Maladera castanea Arrow), May / June beetle (Phyllophaga species), and European chafer (Rhizotrogus majalis Razoumowsky)) from the family Scarabaeidae; carpet beetles from the family Dermestidae; wireworms from the family Elateridae; bark beetles from the family Scolytidae; and flour beetles from the family Tenebrionidae.;

[0681] In addition, agricultural and non-agricultural pests include: eggs, adults, and larvae of Dermaptera, including earwigs from the family Forficulidae (e.g., European earwig (Forficula auricularia Linnaeus), black earwig (Chelisoches morio Fabricius));Eggs, larvae, adults, and nymphs of Hemiptera, such as plant bugs from Miridae, cicadas from Cicadidae, leafhoppers from Cicadellidae (e.g., species of Empoasca), bed bugs from Cimicidae (e.g., Cimex lectularius Linnaeus), planthoppers from Fulgoridae and Delphacidae, treehoppers from Membracidae, psyllids from Liviidae, Psyllidae, and Triozidae, whiteflies from Aleyrodidae, aphids from Aphididae, phylloxera from Phylloxeridae, mealybugs from Pseudococcidae, scales from Coccidae, Diaspididae, and Margarodidae, lace bugs from Tingidae, stink bugs from Pentatomidae, chinch bugs from Lygaeidae (e.g., Blissus leucopterus hirtus Montandon and Blissus insularis Barber) and other seed bugs from Lygaeidae, spittlebugs from Cercopidae, squash bugs from Coreidae, and red bugs and cotton stainers from Pyrrhocoridae.;

[0682] Agronomic and non-agronomic pests also include: eggs, larvae, nymphs, and adults of Acari (mites), such as spider mites and red mites of the family Tetranychidae (e.g., Panonychus ulmi Koch, Tetranychus urticae Koch, Tetranychus mcdanieli McGregor); flat mites of the family Tenuipalpidae (e.g., citrus flat mite (Brevipalpus lewisi McGregor)); rust mites and bud mites of the family Eriophyidae, and other leaf-feeding mites and mites important in human and animal health, namely house dust mites of the family Epidermoptidae, follicle mites of the family Demodecidae, and grain mites of the family Glycyphagidae; ticks of the family Ixodidae, commonly known as hard ticks (e.g., Ixodes scapularis Say, Ixodes holocyclus Neumann, Dermacentor variabilis Say, Amblyomma americanum Linnaeus) and ticks of the family Argasidae, commonly known as soft ticks (e.g., Ornithodoros turicata Duges, Argas radiatus Raillet); scab mites and itch mites of the families Psoroptidae, Pyemotidae, and Sarcoptidae; eggs, adults, and larvae of Orthoptera, including grasshoppers, locusts, and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differentialis Thomas), American grasshoppers (e.g., Schistocerca americana Drury), desert locust (Schistocerca gregaria )), Locusta migratoria Linnaeus, bushlocust (species of Zonocerus), Acheta domesticus Linnaeus, molecrickets (e.g., Scapteriscus vicinus Scudder and Scapteriscus borellii Giglio-Tos); eggs, adults and larvae of Diptera, including leaf miners (e.g., species of Liriomyza such as Liriomyza sativae Blanchard), midges, fruit flies (Tephritidae), wheat stem flies (e.g., Oscinella frit Linnaeus), soil maggots, house flies (e.g., Musca domestica Linnaeus), little house flies (e.g., Fannia canicularis Linnaeus, Fannia scalaris (Loew)),Stein's stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g., Chrysomya species, Phormia species), and other muscoid fly pests, horse flies (e.g., Tabanus species), bot flies (e.g., Gasterophilus species, Oestrus species), cattle grubs (e.g., Hypoderma species), deer flies (e.g., Chrysops species), keds (e.g., Melophagus ovinus Linnaeus), and other Brachycera, mosquitoes (e.g., Aedes species, Anopheles species, Culex species), black flies (e.g., Prosimulium species, Simulium species), biting midges, sand flies, sciarids, and other Nematocera; eggs, adults, and larvae of Thysanoptera, including onion thrips (Thrips tabaci Lindeman), flower thrips (Frankliniella species), and other leaf-feeding thrips; insect pests of Hymenoptera, including ants of Formicidae, including Camponotus floridanus Buckley, Camponotus ferrugineus Fabricius, Camponotus pennsylvanicus DeGeer, Technomyrmex albipes F.Smith), big-headed ants (species of the genus Pheidole), ghost ants (Tapinoma melanocephalum Fabricius); Pharaoh ants (Monomorium pharaonis Linnaeus), little fire ants (Wasmannia auropunctata Roger), fire ants (Solenopsis geminata Fabricius), red imported fire ants (Solenopsis invicta Buren), Argentine ants (Iridomyrmex humilis Mayr), crazy ants (Paratrechina longicornis Latreille), pavement ants (Tetramorium caespitum Linnaeus), cornfield ants (Lasius alienus. and the odorous house ant (Tapinoma sessile Say). Other Hymenoptera, including bees (including carpenter bees), hornets, yellow jackets, wasps, and sawflies (Neodiprion species; Cephus species); insect pests of the order Isoptera, including the Termitidae (e.g., Macrotermes species, Odontotermes obesus Rambur), Kalotermitidae (e.g., Cryptotermes species), and Rhinotermitidae (e.g., Reticulitermes species, Coptotermes species, Heterotermes tenuis Hagen) of termites, Reticulitermes flavipes Kollar, Reticulitermes hesperus Bank, Coptotermes formosanus Shiraki, Incisitermes immigrans Snyder, Cryptotermes brevis Walker, Incisitermes snyderi Light, Reticulitermes virginicus Banks, Incisitermes minor Hagen, arboreal termites such as Nasutitermes species, 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 orders Mallophaga and Phthiraptera, including head lice (Pediculus humanus capitis De Geer), body lice (Pediculus humanus Linnaeus), chicken body lice (Menacanthus stramineus Nitzsch), dog biting lice (Trichodectes canis De Geer), fluff lice (Goniocotes gallinae De Geer), sheep body lice (Bovicola ovis Schrank), short-nosed cattle lice (Haematopinus eurysternus Nitzsch), long-nosed cattle lice (Linognathus vituli Linnaeus), and other sucking and chewing parasitic lice that attack humans and animals; insect pests of the order Siphonoptera, including oriental rat fleas (Xenopsylla cheopis Rothschild), cat fleas (Ctenocephalides felis Bouché), dog fleas (Ctenocephalides canis Curtis), chicken fleas (Ceratophyllus gallinae Schrank), sticktight fleas (Echidnophaga gallinacea Westwood), human fleas (Pulex irritans Linnaeus), and other fleas that afflict mammals and birds. Other arthropod pests covered include: spiders of the order Araneae, such as the brown recluse spider (Loxosceles reclusa Gertsch & Mulaik) and the black widow spider (Latrodectus mactans Fabricius), and centipedes of the order Scutigeromorpha, such as the house centipede (Scutigera coleoptrata Linnaeus).;

[0683] Examples of invertebrate pests in stored grain include Prostephanus truncatus Horn, Rhyzopertha dominica Fabricius, Sitophilus oryzae Linnaeus, Sitophilus zeamais Motschulsky, Callosobruchus maculatus Fabricius, Tribolium castaneum Herbst, Sitophilus granarius Linnaeus, Plodia interpunctella Hübner, Ephestia kuehniella Zeller, and Cryptolestes ferrugineus Stephens.

[0684] The compounds of the present disclosure can be active against members of the classes Nematoda, Cestoda, Trematoda, and Acanthocephala, including members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida that are economically important, such as but not limited to economically important agricultural pests (i.e., root-knot nematodes in the genus Meloidogyne, lesion nematodes in the genus Pratylenchus, stubby root nematodes in the genus Trichodorus, etc.) and pests harmful to animal and human health (i.e., all economically important flukes, tapeworms, and roundworms, such as Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs, Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.).

[0685] The compounds of the present disclosure can have activity against pests in Lepidoptera (e.g., Alabama argillacea Hübner (cotton leafworm), Archips argyrospila Walker (fruit tree leafroller), A.Rosana Linnaeus (European leafroller) and other species of the genus Archips, Chilo suppressalis Walker (rice stem borer), Cnaphalocrocis medinalis Guenée (rice leaf roller), Crambus caliginosellus Clemens (corn root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Earias insulana Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoverpa armigera Hübner (Old World bollworm), Helicoverpa zea Boddie (corn earworm), Heliothis virescens Fabricius (tobacco budworm), Herpetogramma licarsisalis Walker (sod webworm), Lobesia botrana Denis & Schiffermüller (grapevine moth), Pectinophora gossypiella Saunders (pink bollworm), Phyllocnistis citrella Stainton (citrus leafminer), Pieris brassicae Linnaeus (large white), Pieris rapae Linnaeus (small white), Plutella xylostella Linnaeus (diamondback moth), Spodoptera exigua Hübner (beet armyworm), Spodoptera litura Fabricius (tobacco cutworm, cluster caterpillar), Spodoptera frugiperda J.E.Smith) (Autographa gamma), Trichoplusia ni Hübner (cabbage looper), and Tuta absoluta Meyrick (tomato leafminer).

[0686] The compounds of the present disclosure have significant activity against members of the Hemiptera, including: Acyrthosiphon pisum Harris, Aphis craccivora Koch, Aphis fabae Scopoli, Aphis gossypii Glover, Aphis pomi De Geer, Aphis spiraecola Patch, Aulacorthum solani Kaltenbach, Chaetosiphon fragaefolii Cockerell, Diuraphis noxia Kurdjumov / Mordvilko, Dysaphis plantaginea Passerini, Eriosoma lanigerum Hausmann, Hyalopterus pruni Geoffroy, Lipaphis pseudobrassicae Davis, Metopolophium dirrhodum Walker, Macrosiphum euphorbiae Thomas, Myzus persicae Sulzer, Nasonovia ribisnigri Mosley, Pemphigus species (root aphids and gall aphids), Rhopalosiphum maidis Fitch, Rhopalosiphum padi Linnaeus, Schizaphis graminum Rondani, Sitobion avenae Fabricius, Therioaphis maculata Buckton, Toxoptera aurantii Boyer de Fonscolombe, and Toxoptera citricidus Kirkaldy; Adelges species (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 fabae Harris, Laodelphax striatellus Fallén, Macrosteles quadrilineatus Forbes, Nephotettix cincticeps Uhler, Nephotettix nigropictus; ), Nilaparvata lugens ), Peregrinus maidis Ashmead, Sogatella furcifera Horváth, Tagosodes orizicolus Muir, Typhlocyba pomaria McAtee, Erythroneura species (grape leafhoppers); Magicicada septendecim Linnaeus (periodical cicada); Icerya purchasi Maskell (cottony cushion scale), Quadraspidiotus perniciosus Comstock (San Jose scale); Planococcus citri Risso (citrus mealybug); Pseudococcus species (other mealybug groups); Cacopsylla pyricola Foerster (pear psylla), Trioza diospyri Ashmead (persimmon psylla).

[0687] The compounds of the present disclosure are also active against members of the Hemiptera order, including: Acrosternum hilare Say, Anasa tristis De Geer, Blissus leucopterus leucopterus Say, Cimex lectularius Linnaeus, Corythucha gossypii Fabricius, Cyrtopeltis modesta Distant, Dysdercus suturellus ), Euschistus servus Say, Euschistus variolarius Palisot de Beauvois, species of the genus Graptostethus (lygaeid group), Halyomorpha halys ), Leptoglossus corculus Say, Lygus lineolaris Palisot de Beauvois, Nezara viridula Linnaeus, Oebalus pugnax Fabricius, Oncopeltus fasciatus Dallas, Pseudatomoscelis seriatus Reuter. Other insect orders controlled by the compounds of the present disclosure include Thysanoptera (e.g., Frankliniella occidentalis Pergande, Scirtothrips citri Moulton, Scirtothrips variabilis Beach, and onion thrips); and Coleoptera (e.g., Leptinotarsa decemlineata (Colorado potato beetle), Epilachna varivestis Mulsant (Mexican bean beetle), and wireworms of the genus Agriotes, Athous, or Limonius).

[0688] It is noted that the compounds of the present disclosure are useful for controlling Frankliniella occidentalis. It is noted that the compounds of the present disclosure are useful for controlling Empoasca fabae (Harris) (potato leafhopper). It is noted that the compounds of the present disclosure are useful for controlling Aphis gossypii Glover (cotton aphid). It is noted that the compounds of the present disclosure are useful for controlling Myzus persicae. It is noted that the compounds of the present disclosure are useful for controlling Bemisia tabaci biotype B (sweetpotato whitefly).

[0689] The compounds of the present disclosure can also be used to increase the vigor of crop plants. The method comprises contacting a crop plant (e.g., a leaf, flower, fruit or root) or a seed from which the crop plant grows with an amount (i.e., a biologically effective amount) of a compound of Formula 1 sufficient to effect the desired plant vigor effect. Typically, the compounds of Formula 1 are applied in a formulated composition. Although the compounds of Formula 1 are generally applied directly to the crop plant or its seed, these compounds can also be applied to the locus of the crop plant, i.e., the environment of the crop plant, particularly sufficiently close to allow the compounds of Formula 1 to migrate to the environmental portion of the crop plant. The locus associated with the method most commonly includes the growth medium (i.e., the medium that provides nutrients to the plant), typically the soil in which the plant is growing. Thus, treatment of a crop plant to increase the vigor of the crop plant comprises contacting the crop plant, a seed from which the crop plant grows or the locus of the crop plant with a biologically effective amount of a compound of Formula 1.

[0690] Increasing crop vigor can result in one or more of the following observed effects: (a) optimal crop establishment as demonstrated by excellent seed germination, crop emergence and crop stand; (b) enhanced crop growth as demonstrated by rapid and robust leaf growth (e.g., measured by leaf area index), plant height, number of tillers (e.g., for rice), root mass and total dry weight of the vegetative parts of the crop; (c) improved crop yield as demonstrated by time to flowering, duration of flowering, number of flowers, total biomass accumulation (i.e., yield) and / or marketability of the product grade of the fruit or grain (i.e., quality of yield); (d) enhanced ability of the crop to tolerate or prevent infection by plant diseases and infestation by arthropod, nematode or mollusc pests; and (e) increased ability of the crop to tolerate environmental stresses (such as exposure to extreme heat, sub-optimal moisture or phytotoxic chemicals).

[0691] Compared to untreated plants, the compounds of the present disclosure can increase the vigor of treated plants by killing phytophagous invertebrate pests or otherwise preventing their feeding in the plant environment. In the absence of such control of phytophagous invertebrate pests, the pests reduce plant vigor by consuming plant tissue or sap, or by transmitting plant pathogens such as viruses. Even in the absence of phytophagous invertebrate pests, the compounds of the present disclosure can increase plant vigor by altering the metabolism of the plant. Generally, if a plant is grown in a non-ideal environment, i.e., an environment that includes one or more aspects that are not conducive to the plant achieving its full genetic potential as it would exhibit in an ideal environment, then the vigor of the crop plant will be most significantly increased by treating the plant with the compounds of the present disclosure.

[0692] Notably, methods for increasing the vigor of crop plants are provided, wherein the crop plant is grown in an environment that includes phytophagous invertebrate pests. Also notable are methods for increasing the vigor of crop plants, wherein the crop plant is grown in an environment that does not include phytophagous invertebrate pests. Also notable are methods for increasing the vigor of crop plants, wherein the crop plant is grown in an environment that includes a quantity of moisture that is less than the ideal quantity of moisture to support the growth of the crop plant. Notable are methods for increasing the vigor of crop plants, wherein the crop is rice. Also notable are methods for increasing the vigor of crop plants, wherein the crop is maize (corn). Also notable are methods for increasing the vigor of crop plants, wherein the crop is soybean.

[0693] The compounds of the present disclosure can also be mixed with one or more other biologically active compounds or agents to form multi-component pesticidal agents, thereby conferring even broader agronomic and non-agronomic utilities. These biologically active compounds or agents include insecticides, fungicides, nematicides, bactericides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and root stimulants, chemical sterilants, chemical pheromones, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopathogenic bacteria, viruses or fungi. Accordingly, the present disclosure also relates to compositions comprising a biologically effective amount of a compound of formula 1, at least one additional component, and at least one additional biologically active compound or agent, wherein the at least one additional component is selected from the group consisting of surfactants, solid diluents, and liquid diluents. For the mixtures of the present disclosure, the other biologically active compounds or agents can be formulated together with the compounds of the invention (including compounds of formula 1) to form a premix, or the other biologically active compounds or agents can be formulated separately from the compounds of the invention (including compounds of formula 1), and the two formulations can be combined together (e.g., in a spray tank) prior to application, or alternatively, the two formulations can be applied sequentially.

[0694] Examples of such biologically active compounds or agents that can be formulated with the compounds of the present disclosure are insecticides such as abamectin, acephate, acequinocyl, acetamiprid, allethrin, (3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl cyclopropanecarboxylate, amidoflumet, amitraz, avermectin, azadirachtin,azinphos-methyl, benfuracarb, bensultap, bifenthrin, bifenazate, bistrifluron, borate, buprofezin, cadusafos, carbaryl, carbofuran, cartap, chlordimeform, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezine, clothianidin, (3-bromo-1-(3-chloro-2-pyridyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide), (3-bromo-N-[2-bromo-4-chloro-6-[[(1-cyclopropylethyl)amino]carbonyl]phenyl]-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide), cycloprothrin, (5S,8R)-1-[(6-chloro-3-pyridyl)methyl]-2,3,5,6,7,8-hexahydro-9-nitro-5,8-epoxy-1H-imidazo[1,2-a]azepine, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, ethofenprox, emamectin benzoate, endosulfan, esfenvalerate, ethiprole, ethofenprox, fenazaquin, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, (2-ethyl-3,7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]-4-quinolylmethyl carbonate), flonicamid, flubendiamide, flucythrinate, flonicamid, flufenoxuron, (αE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)phenyl acetate, flufenerim, fluopyram, 1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[(2-methyl-2-propen-1-yl)amino]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile), flupyradifurone (4-[[(6-chloro-3-pyridinyl)methyl](2,2-difluoroethyl)amino]-2(5H)-furanone), flumethrin, tau-fluvalinate, fosthiazate, formetanate, fosthiazate, chlorantraniliprole, heptaflumethrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl 2,2-dimethyl-3-[(1Z)-3,3,3-trifluoro-1-propen-1-yl]cyclopropanecarboxylate), hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidal soap, isopropylamine phosphate, lufenuron, malathion, metofluthrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl (1R,3S)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate), metaflumizone, metaldehyde, methamidophos, methidathion, methiocarb, methomyl, methoprene, methoxychlor, metofluthrin, methoxyfenozide, metofluthrin, monocrotophos, monofluthrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl 3-(2-cyano-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate), nicotine, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion, methyl parathion, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, pyridaben, pyridalyl, pyrifluquinazon, pyrimidifen ((αE)-2-[[[2-[(2,4-dichlorophenyl)amino]-6-(trifluoromethyl)-4-pyrimidinyl]oxy]methyl]-α-(methoxymethylene)phenylacetic acid methyl ester), pyrafluprole, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram, spinosad, spirodiclofen, spirotetramat, spirotetramat, sulfotep, sulfoxaflor (N-[methyloxide[1-[6-(trifluoromethyl)-3-pyridinyl]ethyl]-λ, 4-sulfinyl]cyanamide), tebufenozide, pyridaben, chlorfluazuron, tefluthrin, terbufos, insecticide, tetramethrin, tetramethrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl 2,2,3,3-tetramethylcyclopropanecarboxylate), tetraniliprole, thiacloprid, thiamethoxam, thiodicarb, bisultap, thiazosulfen (3-phenyl-5-(2-thienyl)-1,2,4-oxadiazole), tolfenpyrad, tralomethrin, triazamate, trichlorfon, triflumezopyrim (2,4-dioxo-1-(5-pyrimidinylmethyl)-3-[3-(trifluoromethyl)phenyl]-2H-pyrido[1,2-a]pyrimidinium inner salt), triflumuron, Bacillus thuringiensis δ-endotoxin, entomopathogenic bacteria, entomopathogenic viruses and entomopathogenic fungi.

[0695] Of note are insecticides such as abamectin, acetamiprid, alphacypermethrin, bicycloproprole, amitraz, avermectin, azadirachtin, benfuracarb, bensultap, bifenthrin, buprofezin, cadusafos, carbaryl, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyclaniliprole, cyphenothrin, deltamethrin, diflubenzuron, dimehypo, dinotefuran, ethofenprox, etoxazole, fenitrothion, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide, flufenoxuron, fluacrypyrim, flufiprole, flupyradifurone, fluvalinate, formetanate, fosthiazate, heptafluthrin, flucycloxuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, metofluthrin, metaflumizone, methomyl, methoprene, methoxyfenozide, metofluthrin, monofluoroacetate, nitenpyram, nithiazine, novaluron, oxamyl, pymetrozine, pyrethrins, pyridaben, pyridalyl, pyridaben, pyridalyl, pyridalyl, spinetoram, spinosad, spirodiclofen, spirotetramat, spirotetramat, sulfoxaflor, tebufenozide, tetramethrin, tetramethrin, thiacloprid, thiamethoxam, thiodicarb, bisultap, tralomethrin, triazamate, triflumuron, Bacillus thuringiensis δ-endotoxin, all strains of Bacillus thuringiensis and all strains of nuclear polyhedrosis virus.

[0696] An example of a biologic agent for mixing with the compounds of the present disclosure includes entomopathogenic bacteria such as Bacillus thuringiensis, and encapsulated δ-endotoxins of Bacillus thuringiensis prepared by processes such as and biological insecticides ( and (trademark of Mycogen Corporation, Indianapolis, Indiana, USA); entomopathogenic fungi such as green muscardine fungus; and entomopathogenic (naturally occurring and genetically modified) viruses, including baculoviruses, nucleopolyhedroviruses (NPV) such as Helicoverpa zea nucleopolyhedrovirus (HzNPV), Anagrapha falcifera nucleopolyhedrovirus (AfNPV); and granulosis viruses (GV) such as Cydia pomonella granulosisvirus (CpGV).

[0697] One embodiment of the biological agent for mixing with the compounds of the present disclosure includes one or a combination of the following: (i) bacteria of the genus Actinomycetes, Agrobacterium, Arthrobacter, Alcaligenes, Aureobacterium, Azobacter, Bacillus, Beijerinckia, Bradyrhizobium, Brevibacillus, Burkholderia, Chromobacterium, Clostridium, Clavibacter, Comamonas, Corynebacterium, Curtobacterium, Enterobacter, Flavobacterium, Gluconobacter, Hydrogenophaga, Klebsiella, Methylobacterium, Paenibacillus, Pasteuria, Photorhabdus, Phyllobacterium, Pseudomonas, Rhizobium, Serratia, Sphingobacterium, Stenotrophomonas, Streptomyces, Variovorax, or Xenorhabdus,For example, bacteria such as Bacillus amyloliquefaciens, Bacillus cereus, Bacillus firmus, Bacillus licheniformis, Bacillus pumilus, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Bradyrhizobium japonicum, Chromobacterium subtsugae, Pasteuria nishizawae, Pasteuria penetrans, Pasteuria usage, Pseudomonas fluorescens, and Streptomyces lydicus; (ii) fungi such as Metarhizium; (iii) viruses including baculoviruses, nuclear polyhedrosis viruses such as Helicoverpa zea nuclear polyhedrosis virus, Anagrapha falcifera nuclear polyhedrosis virus; granulosis viruses such as Cydia pomonella granulosis virus.,

[0698] Particularly noteworthy is such a combination wherein another invertebrate pest control active ingredient belongs to a different chemical class than the compounds of formula 1 or has a different site of action than that of the compound. In certain cases, a combination with at least one other invertebrate pest control active ingredient having a similar control spectrum but a different site of action will be particularly advantageous for resistance management. Accordingly, the compositions of the present disclosure may further comprise a biologically effective amount of at least one additional invertebrate pest control active ingredient having a similar control spectrum but belonging to a different chemical class or having a different site of action. These additional biologically active compounds or agents include, but are not limited to, acetylcholinesterase (AChE) inhibitors such as the carbamates methomyl, oxamyl, thiodicarb, triazamate, and the organophosphates chlorpyrifos; GABA-gated chloride channel antagonists such as the cyclodienes dieldrin and endosulfan, and the phenylpyrazoles ethiprole and fipronil; sodium channel modulators such as the pyrethroids bifenthrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, permethrin, deltamethrin, tetramethrin, esfenvalerate, metofluthrin, and profluthrin; nicotinic acetylcholine receptor (nAChR) agonists such as the neonicotinoids acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid, and thiamethoxam, the sulfoximines sulfoxaflor, the butenolides flupyradifurone, and the mesoionics triflumezopyrim; nicotinic acetylcholine receptor (nAChR) allosteric activators such as the spinosyns spinetoram and spinosad; chloride channel activators such as the avermectins abamectin and emamectin; juvenile hormone mimics such as phenoxycarb, methoprene, pyriproxyfen, and fenoxycarb; chordotonal organ modulators such as pymetrozine, pyflubumide, and flonicamid; mite growth inhibitors such as etoxazole; mitochondrial ATP synthase inhibitors such as propargite; uncouplers of oxidative phosphorylation via disruption of the proton gradient such as chlorfenapyr; nicotinic acetylcholine receptor (nAChR) channel blockers such as the nereistoxin analog cartap; chitin biosynthesis inhibitors such as the benzoylureas flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, and teflubenzuron, and buprofezin; dipteran moulting disrupters such as cyromazine; ecdysone receptor agonists such as the dibenzoylhydrazines methoxyfenozide and tebufenozide; octopamine receptor agonists such as amitraz; mitochondrial complex III electron transport inhibitors such as hydramethylnon and bifenazate; mitochondrial complex I electron transport inhibitors such as pyridaben;Voltage-dependent sodium channel blockers, such as indoxacarb; acetyl-CoA carboxylase inhibitors, such as tetronic acids and tetramic acids spirodiclofen, spirotetramat and spirotetramat; mitochondrial complex II electron transport inhibitors, such as β-ketonitriles fenpyroximate and cyflumetofen; ryanodine receptor modulators, such as anthranilic diamides chlorantraniliprole and cyantraniliprole, diamides, such as flubendiamide, and ryanodine receptor ligands, such as ryanodine; compounds for which the target site responsible for biological activity is unknown or uncharacterized, such as azadirachtin and acetamiprid; microbial disruptors of the insect midgut membrane, such as Bacillus thuringiensis and its δ-endotoxins and Bacillus sphaericus; and biological agents, including nucleopolyhedrovirus (NPV) and other naturally occurring or genetically modified insecticidal viruses.

[0699] Other examples of biologically active compounds or agents that can be formulated with the compounds of the present disclosure are: fungicides such as benzothiadiazole, dimethomorph, amisulbrom, aminopyrifen, indaziflam, anilazine, azaconazole, azoxystrobin, benalaxyl (including benalaxyl-M), carboxin, benomyl, benthiavalicarb (including benthiavalicarb-isopropyl), benzovindiflupyr, bethoxazin, binapacryl, biphenyl, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, carboxin, cyclopropiconazole, captafol, captan, carbendazim, chloroneb, chlorothalonil, chlozolinate, copper hydroxide, copper oxychloride, copper sulfate, clove leaf oil, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dichlobentiazox, fenarimol, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, enestroburin, diniconazole (including diniconazole-M), edifenphos, dipymetitrone, dithianon, dithiolane, dodemorph, dodine, econazole, etaconazole, ethion, enoxastrobin,Also known as enestroburin, epoxiconazole, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, enaminostrobin, fenarimol, fenbuconazole, furametpyr, fenhexamide, fenoxanil, fenpiclonil, fenpicoxamid, fenpropidine, fenpropimorph, amisulbrom, triphenyltin acetate, triphenyltin hydroxide, ferbam, ferimzone, flupoxam, picoxystrobin, fluazinam, flubeneteram, fludioxonil, flubendiamide, fluindapyr, flumorph, fluopicolide, fluxapyroxad, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, fluthianil, flutolanil, flutriafol, fluzasole, captan, fthalide,Also known as phthalide, fenpiclonil, furalaxyl, fludioxonil, hexaconazole, hymexazole, guazatine, imazalil, imibenconazole, iminoctadine albesilate, iminoctadine triacetate, inpyrfluxam, thiodicarb, tebuconazole, ipfentrifluconazole, ipflufenoquin, isopropylthianil, iprobenfos, iprodione, propineb, isoflucypram, isoprothiolane, isopyrazam, isothianil, kasugamycin, kresoxim-methyl, lancotrione, mancozeb, mandipropamid, mandestrobin, mancopper, mapanipyrin, chlorfluzuron, dimethomorph, meptyldinocap, metalaxyl (including metalaxyl-M / mefenoxam), metconazole, methasulfocarb, mancozeb, metconazole, metyltetraprole, metrafenone, myclobutanil, naftitine, ferric methanearsonate, fluotrimazole, octhilinone, flutolanil, orysastrobin, oxadixyl, oxathiapiprolin, oxolinic acid, oxpoconazole, oxycarboxin, oxytetracycline, penconazole, pencycuron, flutolanil, penthiopyrad, perfurazoate, phosphorous acid (including its salts, e.g., fosetyl-aluminm), picoxystrobin, piperalin, polyoxin, thiabendazole, prochloraz, procymidone, propamocarb, propiconazole, zineb, proquinazid, prothiocarb, prothioconazole, flutolanil, Pyraoxystrobin, pyribencarb, pyrapropoyne, pyraclostrobin, pyraziflumid, pyrazophos, pyribenzamine, pyributacarb, pyridachlometyl, pyrifenox, pyriofenone, perisoxazole, pyrimethanil, pyrifenox, pyrrolnitrin, pyroquilon, fluquinconazole, quinmethionate, quinofumelin, quinoxyfen, quintozene, silthiofam, sedaxane, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, isobutyl ethyl oxalinic acid, teclofthalam, tecloftalam, tecnazene, terbinafine, fluconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiophanate-methyl, validamycin, valifenalate (also known as valifenal), vinclozoline, zineb, ziram, zoxamide, and 1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone; nematicides such as fluopyram, spirotetramat, thiodicarb, fosthiazate, abamectin, iprodione, flufenerim, dimethyl disulfide, thiazosulfan, 1,3-dichloropropene (1,3-D), metam (sodium and potassium), dazomet, chloropicrin, fenamiphos, ethoprophos, cadusaphos, terbufos, imicyafos, methomyl, carbofuran, tioxazafen, Bacillus firmus, and Pasteuria nishizawae; bactericides such as streptomycin;Acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, chinomethionat, etoxazole, quinoxyfen, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben, and tebufenpyrad.;

[0700] In certain instances, combinations of the compounds of the present disclosure with other biologically active (especially invertebrate pest control) compounds or agents (i.e., active ingredients) can result in enhanced effects. Reducing the amount of active ingredient released into the environment while ensuring effective pest control has always been desirable. Such combinations can be advantageously used to reduce crop production costs and the environmental burden when enhanced invertebrate pest control occurs at application rates that achieve an agronomically satisfactory level of invertebrate pest control.

[0701] The compounds and compositions of the present disclosure can be applied to plants that have been genetically transformed to express a protein that is toxic to invertebrate pests (such as Bacillus thuringiensis δ-endotoxin). Such application can provide a broader spectrum of plant protection and is advantageous for resistance management. The combination of the exogenously applied invertebrate pest control compounds of the present disclosure with the expressed toxin protein can provide enhanced effects.

[0702] General references for these agricultural protectants (i.e., insecticides, fungicides, nematicides, acaricides, herbicides, and biological agents) include The Pesticide Manual, 13th Edition, edited by C.D.S. Tomlin, British Crop Protection Council, Farnham, Surrey, U.K., 2003 and The BioPesticide Manual, 2nd Edition, edited by L.G. Copping, British Crop Protection Council, Farnham, Surrey, U.K., 2001.

[0703] The compounds of the present disclosure can be combined or formulated together with polynucleotides including, but not limited to, DNA, RNA, and / or chemically modified nucleotides that affect the amount of a specific target by reducing, interfering with, inhibiting, or silencing genetically derived transcripts that exhibit insecticidal effects.

[0704] For embodiments in which one or more of these different admixture components are used, the weight ratio of these different admixture components (total amount) to the compound of formula 1 is typically between about 1:3000 and about 3000:1. Notably, weight ratios between about 1:300 and about 300:1 (e.g., ratios between about 1:30 and about 30:1). One of ordinary skill in the art can readily determine the biologically effective amount of the active ingredient necessary for the desired biological activity profile through simple experimentation. It will be apparent that the inclusion of these additional components can expand the invertebrate pest control profile beyond that of the compound of formula 1 alone.

[0705] Table A lists specific combinations of the compound of formula 1 with other invertebrate pest control agents, exemplifying the mixtures, compositions, and methods of the present disclosure. The first column of Table A lists the specific invertebrate pest control agents (e.g., "abamectin" in the first row). The second column of Table A lists the mode of action (if known) or chemical class of the invertebrate pest control agent. The third column of Table A lists one or more embodiments of the weight ratio range of the rate at which the invertebrate pest control agent can be applied relative to the compound of formula 1 (e.g., by weight, abamectin is "50:1 to 1:50" relative to the compound of formula 1). Thus, for example, the first row of Table A specifically discloses that the combination of the compound of formula 1 with abamectin can be applied at a weight ratio between 50:1 and 1:50. The remaining rows of Table A will be similarly constructed. Further notable is that Table A lists specific combinations of the compound of formula 1 with other invertebrate pest control agents, exemplifying the mixtures, compositions, and methods of the present disclosure, and including additional embodiments of the weight ratio range of the application rate.

[0706] Table A

[0707]

[0708]

[0709]

[0710] Notable is the composition of the present disclosure, wherein at least one additional biologically active compound or reagent is selected from the invertebrate pest control agents listed in Table A above.

[0711] The weight ratio of the compound including the compound of formula 1, its N-oxide or salt to the additional invertebrate pest control agent is typically between 1000:1 and 1:1000, with one embodiment between 500:1 and 1:500, another embodiment between 250:1 and 1:200, and another embodiment between 100:1 and 1:50.

[0712] Examples of specific compositions of compounds containing Formula 1 (Compound No. (Cmpd.No.) refers to the compounds in Index Table A) and additional invertebrate pest control agents are listed in Tables B1 to B6 below.

[0713] Table B1

[0714]

[0715]

[0716] Table B2

[0717] Table B2 is the same as Table B1, except that each mention of Compound 8 in the column header "Cmpd.No." is replaced by a mention of Compound 14. For example, the first mixture in Table B2 is designated B2-1 and is a mixture of Compound 14 and the additional invertebrate pest control agent abamectin.

[0718] Table B3

[0719] Table B3 is the same as Table B1, except that each mention of Compound 8 in the column header "Cmpd.No." is replaced by a mention of Compound 19. For example, the first mixture in Table B3 is designated B3-1 and is a mixture of Compound 19 and the additional invertebrate pest control agent abamectin.

[0720] Table B4

[0721] Table B4 is the same as Table B1, except that each mention of Compound 8 in the column header "Cmpd.No." is replaced by a mention of Compound 78. For example, the first mixture in Table B4 is designated B4-1 and is a mixture of Compound 78 and the additional invertebrate pest control agent abamectin.

[0722] Table B5

[0723] Table B5 is the same as Table B1, except that each mention of Compound 8 in the column header "Cmpd.No." is replaced by a mention of Compound 3. For example, the first mixture in Table B5 is designated B5-1 and is a mixture of Compound 3 and the additional invertebrate pest control agent abamectin.

[0724] Table B6

[0725] Table B6 is the same as Table B1, except that each reference to Compound 8 in the column heading "Cmpd. No." is replaced with a reference to Compound 86. For example, the first mixture in Table B6 is designated B6-1 and is a mixture of Compound 86 and the additional invertebrate pest control agent abamectin.

[0726] The specific mixtures listed in Tables B1 to B6 typically combine the compounds of Formula 1 with other invertebrate pest agents at the ratios specified in Table A.

[0727] The following Tables C1 to C6 list specific mixtures containing a compound of Formula 1 (the compound number (Cmpd. No.) refers to the compound in Index Table A) and an additional invertebrate pest control agent. Tables C1 to C19 further list the typical specific weight ratios of the mixtures in Tables C1 to C19. For example, the first weight ratio entry in the first row of Table C1 specifically discloses a mixture of Compound 1 from Index Table A and abamectin applied at a weight ratio of 100 parts of Compound 1 to 1 part of abamectin.

[0728] Table C1

[0729]

[0730]

[0731] Table C2

[0732] Table C2 is the same as Table C1, except that each reference to Compound 8 in the column heading "Cmpd. No." is replaced with a reference to Compound 14. For example, the first weight ratio entry in the first row of Table C2 specifically discloses a mixture of Compound 14 and abamectin applied at a weight ratio of 100 parts of Compound 1 to 1 part of abamectin.

[0733] Table C3

[0734] Table C3 is the same as Table C1, except that each reference to Compound 8 in the column heading "Cmpd. No." is replaced with a reference to Compound 19. For example, the first weight ratio entry in the first row of Table C3 specifically discloses a mixture of Compound 19 and abamectin applied at a weight ratio of 100 parts of Compound 1 to 1 part of abamectin.

[0735] Table C4

[0736] Table C4 is the same as Table C1, except that each mention of Compound 8 in the column heading "Cmpd. No." is replaced with a mention of Compound 78. For example, the first weight ratio entry in the first row of Table C4 specifically discloses a mixture of Compound 78 and abamectin applied at a weight ratio of 100 parts of Compound 1 to 1 part of abamectin.

[0737] Table C5

[0738] Table C5 is the same as Table C1, except that each mention of Compound 8 in the column heading "Cmpd. No." is replaced with a mention of Compound 3. For example, the first weight ratio entry in the first row of Table C5 specifically discloses a mixture of Compound 3 and abamectin applied at a weight ratio of 100 parts of Compound 1 to 1 part of abamectin.

[0739] Table C6

[0740] Table C6 is the same as Table C1, except that each mention of Compound 8 in the column heading "Cmpd. No." is replaced with a mention of Compound 86. For example, the first weight ratio entry in the first row of Table C6 specifically discloses a mixture of Compound 86 and abamectin applied at a weight ratio of 100 parts of Compound 1 to 1 part of abamectin.

[0741] Examples of specific compositions containing the compound of Formula 1 (Compound No. (Cmpd. No.) refers to the compound in Index Table A) and additional fungicides are listed in Tables D1 to D6 below.

[0742] Table D1

[0743]

[0744]

[0745] Table D2

[0746] Table D2 is the same as Table D1, except that each mention of Compound 8 in the column heading "Cmpd. No." is replaced with a mention of Compound 14. For example, the first mixture in Table D2 is designated D2-1 and is a mixture of Compound 14 and the additional fungicide thiabendazole.

[0747] Table D3

[0748] Table D3 is the same as Table D1, except that each mention of Compound 8 in the column heading "Cmpd. No." is replaced with a mention of Compound 19. For example, the first mixture in Table D3 is designated D3-1 and is a mixture of Compound 19 and the additional fungicide thiabendazole.

[0749] Table D4

[0750] Table D4 is the same as Table D1, except that each mention of compound 8 in the column heading "Cmpd. No." is replaced by a mention of compound 78. For example, the first mixture in Table D4 is designated D4-1 and is a mixture of compound 78 and the additional fungicide thiabendazole.

[0751] Table D5

[0752] Table D5 is the same as Table D1, except that each mention of compound 8 in the column heading "Cmpd. No." is replaced by a mention of compound 3. For example, the first mixture in Table D5 is designated D5-1 and is a mixture of compound 3 and the additional fungicide thiabendazole.

[0753] Table D6

[0754] Table D6 is the same as Table D1, except that each mention of compound 8 in the column heading "Cmpd. No." is replaced by a mention of compound 86. For example, the first mixture in Table D6 is designated D6-1 and is a mixture of compound 86 and the additional fungicide thiabendazole.

[0755] In agricultural and non-agricultural applications, invertebrate pests are controlled by applying a biologically effective amount of one or more of the compounds of the present disclosure, usually in the form of a composition, to the pest environment, including the infested agricultural and / or non-agricultural sites, to the area to be protected, or directly to the pest to be controlled.

[0756] Accordingly, the present disclosure includes a method for controlling invertebrate pests in agricultural and / or non-agricultural applications, the method comprising contacting the invertebrate pest or its environment with a biologically effective amount of one or more of the compounds of the present disclosure or with a composition comprising at least one such compound or with 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 the compounds of the present disclosure and a biologically effective amount of at least one additional biologically active compound or agent include granular compositions, wherein the additional active compound is present on the same granule as the compound of the present disclosure or on granules separate from those of the compound of the present disclosure.

[0757] To effect contact with the compounds or compositions of the disclosure to protect field crops from invertebrate pests, the compound or composition is typically applied to crop seeds before planting, to the leaves of crop plants (e.g., leaves, stems, flowers, fruits), or to the soil or other growth medium before or after planting the crop.

[0758] One embodiment of the contacting method is by spraying. Alternatively, granular compositions comprising the compounds of the disclosure can be applied to plant leaves or soil. The compounds of the disclosure can also be effectively delivered by plant uptake by contacting the plants with compositions comprising the compounds of the disclosure applied as a soil drench, granular formulations into the soil, plug tray treatments or transplant dips as liquid formulations. Of note is the composition of the disclosure in the form of a soil drench liquid formulation. Also of note is a method for controlling invertebrate pests, which method comprises contacting the invertebrate pest or its environment with a biologically effective amount of the compounds of the disclosure or with a composition comprising a biologically effective amount of the compounds of the disclosure. Further of note is such a method wherein the environment is soil and the composition is applied to the soil as a soil drench formulation. Further of note is that the compounds of the disclosure are also effective by topical application to the locus of infestation. Other contacting methods include applying the compounds or compositions of the disclosure by direct spraying and residual spraying, air spraying, gels, seed coating, microencapsulation, systemic uptake, baits, ear tags, boluses, sprayers, fumigants, aerosols, dusts and many other methods. One embodiment of the contacting method is a size-stable fertilizer granule, stick or tablet comprising the compounds or compositions of the disclosure. The compounds of the disclosure can also be impregnated into materials for making invertebrate pest control devices (e.g., insect-proof nets).

[0759] The compounds of the disclosure can be used to treat all plants, plant parts and seeds. Plant and seed varieties and cultivars can be obtained by conventional breeding and propagation methods or by genetic engineering methods. Genetically modified plants or seeds (transgenic plants or seeds) are those in which a heterologous gene (transgene) has been stably integrated into the plant or seed genome. The transgene defined by the specific location of the transgene in the plant genome is called a transformation or transgenic event.

[0760] Genetically modified plant and seed cultivars that can be processed according to this disclosure include those resistant to one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, low temperature, soil salinization, etc.), or those with other desired characteristics. Plants and seeds can be genetically modified to exhibit traits such as herbicide tolerance, insect resistance, modified oil characteristics, or drought tolerance. Useful genetically modified plants and seeds, including single gene transformation events or combinations of transformation events, are listed in Table Z. Additional information on the genetic modifications listed in Table Z can be obtained from the following databases:

[0761] http: / / www2.oecd.org / biotech / byidentifier.aspx

[0762] http: / / www.aphis.usda.go

[0763] http: / / gmoinfo.jrc.ec.europa.eu

[0764] The following abbreviations are used in subsequent Table Z: tol. for tolerance, res. for resistance, SU for sulfonylureas, ALS for acetolactate synthase, HPPD for 4-hydroxyphenylpyruvate dioxygenase, and NA for not available.

[0765] Table Z

[0766]

[0767]

[0768]

[0769]

[0770]

[0771]

[0772]

[0773]

[0774]

[0775]

[0776] *Argentina, **Poland, #Eggplant

[0777] Treatment of genetically modified plants and seeds with the compounds disclosed herein can result in enhanced effects. For example, a reduction in application rate, an expanded spectrum of activity, an increase in tolerance to biotic / abiotic stress, or an enhancement of storage stability can be greater than expected from the additive effects of simply applying the compounds disclosed herein on genetically modified plants and seeds.

[0778] The compounds disclosed herein can also be used in seed treatment agents to protect seeds from invertebrate pests. In the context of this disclosure and the claims, treating seeds means contacting the seeds with a biologically effective amount of the compounds disclosed herein, which are typically formulated into the compositions disclosed herein. The seed treatment agent protects the seeds from invertebrate soil pests and generally can also protect the roots and other plant parts in contact with the soil of the seedlings developed from the germinated seeds. The seed treatment agent can also provide protection to the leaves by translocating the compounds disclosed herein or a second active ingredient in the developing plant. Seed treatment can be applied to all types of seeds, including those that will germinate to form genetically transformed plants expressing specific traits. Representative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis toxins, or those expressing herbicide resistance, such as glyphosate acetyltransferase providing glyphosate resistance. Seed treatment with the compounds disclosed herein can also increase the vigor of the plants grown from the treated seeds.

[0779] One method of seed treatment is to spray or dust the seeds with the compounds disclosed herein (i.e., as a formulated composition) prior to sowing the seeds. Compositions formulated for seed treatment typically contain a film-forming agent or an adhesive. Thus, typically the seed coating compositions disclosed herein contain a biologically effective amount of a compound of formula 1, its N-oxide or salt, and a film-forming agent or an adhesive. Seed coating can be carried out by spraying a flowable suspension concentrate directly onto a tumbling bed of seeds and then drying the seeds. Alternatively, other formulation types such as wettable powders, solutions, suspension emulsions, emulsifiable concentrates, and emulsions in water can be sprayed onto the seeds. This method is particularly useful for applying film coatings to seeds. Those skilled in the art can use various coating machines and methods. Suitable methods include those listed in P. Kosters et al., Seed Treatment: Progress and Prospects, 1994 BCPC Monograph No. 57 and the references listed therein.

[0780] The compounds of formula 1 and their compositions, alone or in combination with other insecticides and fungicides, are particularly useful for seed treatment of crops including, but not limited to, maize or corn, soybeans, cotton, cereals (e.g., wheat, oats, barley, rye, and rice), potatoes, vegetables, and oilseed rape.

[0781] Other insecticides that can be formulated with the compound of formula 1 to provide a mixture useful for seed treatment include abamectin, acetamiprid, alphamethrin, amitraz, avermectin, azadirachtin, bensultap, bifenthrin, buprofezin, carbaryl, carbofuran, cartap hydrochloride, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, ethofenprox, emamectin benzoate, endosulfan, esfenvalerate, ethiprole, ethofenprox, etoxazole, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flonicamid, flubendiamide, flufenoxuron, fluvalinate, formetanate hydrochloride, fosthiazate, flucycloxuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, metaflumizone, methiocarb, methomyl, methoprene, methoxyfenozide, nitenpyram, nithiazine, novaluron, spinetoram, spinosad, spirodiclofen, spirotetramat, spirotetramat, sulfoxaflor, tebufenozide, tetramethrin, thiacloprid, thiamethoxam, thiodicarb, dimehypo, tralomethrin, triazamate, triflumuron, Bacillus thuringiensis δ-endotoxin, all strains of Bacillus thuringiensis and all isolates of nuclear polyhedrosis virus.

[0782] Fungicides that can be formulated with the compound of formula 1 to provide a mixture useful for seed treatment include amisulbrom, azoxystrobin, boscalid, carbendazim, carboxin, cymoxanil, cyproconazole, difenoconazole, dimethomorph, fluazinam, fludioxonil, fluquinconazole, fluopicolide, fluoxastrobin, flutriafol, fluxapyroxad, ipconazole, iprodione, metalaxyl, metalaxyl-M, metconazole, myclobutanil, paclobutrazol, sedaxane, picoxystrobin, prothioconazole, pyraclostrobin, pyraclonil, silthiofam, tebuconazole, thiabendazole, thiophanate-methyl, simeconazole, tricyclazole, trifloxystrobin, and triticonazole.

[0783] Compositions containing the compound of formula 1 useful for seed treatment may further contain bacteria such as Bacillus pumilus (e.g., strain GB34) and Bacillus firmus (e.g., isolate 1582), rhizobium inoculants / boosters, isoflavones, and chito-oligosaccharides.

[0784] The treated seeds generally contain the compounds of the present disclosure in an amount of from about 0.1 g to 1 kg per 100 kg of seeds (i.e., from about 0.0001 wt% to 1 wt% of the seeds before treatment). A flowable suspension formulated for seed treatment generally contains from about 0.5% to about 70% of the active ingredient, from about 0.5% to about 30% of the film-forming binder, from about 0.5% to about 20% of the dispersant, from 0% to about 5% of the thickener, from 0% to about 5% of the pigment and / or dye, from 0% to about 2% of the defoamer, from 0 to about 1% of the preservative, and from 0% to about 75% of the volatile liquid diluent.

[0785] The compounds of the present disclosure can be incorporated into bait compositions that are eaten by invertebrate pests or used in devices such as traps, bait stations, etc. Such bait compositions can be in the form of granules that contain (a) an active ingredient, i.e., a biologically effective amount of a compound of Formula 1, its N-oxide or salt; (b) one or more food materials; optionally (c) an attractant, and optionally (d) one or more wetting agents. It is noted that the granules or bait compositions contain between about 0.001% - 5% of the active ingredient, about 40% - 99% of the food material and / or attractant; and optionally about 0.05% - 10% of the wetting agent, which can be effective in controlling soil invertebrate pests at very low application rates, particularly at doses of the active ingredient that are lethal by ingestion rather than by direct contact. Some food materials can serve as both a food source and an attractant. Food materials include carbohydrates, proteins, and lipids. Examples of food materials are vegetable powders, sugars, starches, animal fats, vegetable oils, yeast extracts, and milk solids. Examples of attractants are flavor enhancers and flavorings such as fruit or plant extracts, spices, or other animal or plant components, pheromones, or other agents known to attract the target invertebrate pests. Examples of wetting agents (i.e., water retention agents) are ethylene glycol and other polyols, glycerol, and sorbitol. It is noted that bait compositions (and methods of using such bait compositions) for controlling invertebrate pests selected from the group consisting of ants, termites, and cockroaches. A device for controlling invertebrate pests can comprise the bait composition of the present invention and a housing adapted to contain the bait composition, wherein the housing has at least one opening sized to allow invertebrate pests to pass through the opening, enabling the invertebrate pests to access the bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a location where invertebrate pests are likely or known to be active.

[0786] The compounds of the present disclosure can be applied without other adjuvants, but the most common application is in the form of formulations that contain one or more active ingredients with suitable carriers, diluents, and surfactants and may optionally be combined with food depending on the intended end use. One method of application involves spraying an aqueous dispersion or refined oil solution of the compounds of the present disclosure. Combinations with spray oils, spray oil concentrates, sticker-spreader agents, adjuvants, other solvents, and piperonyl butoxide generally enhance the efficacy of the compounds. For non-agricultural uses, such sprays can be applied from spray containers such as cans, bottles, or other containers, either by means of a pump or by releasing them from a pressurized container such as a pressurized aerosol spray can. Such spray compositions can take various forms, such as sprays, mists, foams, smokes, or dusts. Thus, depending on the circumstances, such spray compositions may further contain propellants, foaming agents, etc. Of note are spray compositions that contain a biologically effective amount of the compounds or compositions of the present disclosure and a carrier. One embodiment of such a spray composition contains a biologically effective amount of the compounds or compositions of the present disclosure 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 are spray compositions (and methods of using such spray compositions dispensed from a spray container) for controlling 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, midges, etc., including individually or in combination.

[0787] One embodiment of the present disclosure relates to a method for controlling invertebrate pests, the method comprising diluting a pesticidal composition of the present disclosure (a compound of formula 1 formulated with a surfactant, a solid diluent, and a liquid diluent, or a formulated mixture of a compound of formula 1 and at least one other pesticidal agent) with water, and optionally adding adjuvants to form a diluted composition, and contacting the invertebrate pest or its environment with an effective amount of the diluted composition.

[0788] Although spray compositions formed by diluting a pesticidal composition of the invention at a sufficient concentration with water can provide adequate efficacy against invertebrate pests, separately formulated adjuvant products can also be added to the spray tank mixture. These additional adjuvants are commonly referred to as "spray adjuvants" or "tank-mix adjuvants" and include any substance that is mixed in the spray tank to improve the performance of the pesticidal agent or to alter the physical characteristics of the spray mixture. Adjuvants can be surfactants, emulsifiers, petroleum-based crop oils, crop-derived seed oils, acidifying agents, buffers, thickeners, or defoamers. Adjuvants are used to enhance efficacy (e.g., bioavailability, adhesion, penetration, coverage uniformity, and protection durability), or to minimize or eliminate spray application problems associated with incompatibility, foaming, drift, evaporation, volatilization, and degradation. To obtain optimal performance, adjuvants are selected with respect to the characteristics, formulation, and target (e.g., crop, insect pest) of the active ingredient.

[0789] Among spray adjuvants, oils (including crop oils, crop oil concentrates, vegetable oil concentrates, and methylated seed oil concentrates) are most commonly used to improve the efficacy of pesticidal agents, which may be achieved by promoting more uniform and consistent spray deposition. In cases where phytotoxicity that may be caused by oils or other water-immiscible liquids is important, spray compositions prepared from the compositions disclosed herein will generally be free of oil-based spray adjuvants. However, in cases where phytotoxicity caused by oil-based spray adjuvants is not commercially important, spray compositions prepared from the compositions of the invention may also contain oil-based spray adjuvants, which can potentially further increase control of invertebrate pests, as well as rainfastness.

[0790] Products identified as "crop oils" typically contain 95% to 98% paraffin or naphtha-based petroleum and 1% to 2% of one or more surfactants used as emulsifiers. Products identified as "crop oil concentrates" generally consist of 80% to 85% emulsifiable petroleum-based oil and 15% to 20% nonionic surfactant. Products correctly identified as "vegetable oil concentrates" generally consist of 80% to 85% vegetable oil (i.e., seed oil or fruit oil, most commonly from cotton, flaxseed, soybeans, or sunflowers) and 15% to 20% nonionic surfactant. Adjuvant performance can be improved by replacing vegetable oil with methyl esters of fatty acids typically derived from vegetable oils. Examples of methylated seed oil concentrates include Concentrate (UAP-Loveland Products, Inc.) and Premium MSO Methylated Spray Oil (Helena Chemical Company).

[0791] The amount of adjuvant added to the spray mixture generally does not exceed about 2.5% by volume, and more typically the amount is from about 0.1% to about 1% by volume. The application rate of the adjuvant added to the spray mixture is generally between about 1 L and 5 L per hectare. Representative examples of spray adjuvants include: (Syngenta) 47% methylated rapeseed oil in liquid hydrocarbon, (Helena Chemical Company) polyether-modified heptamethyltrisiloxane, and (BASF) 17% surfactant blend in 83% paraffinic mineral oil.

[0792] Non-agricultural applications include protecting animals from invertebrate parasitic pests by administering to the animals to be protected (especially vertebrates, more particularly warm-blooded vertebrates (e.g., mammals or birds) and most particularly mammals) a parasitically effective (i.e., biologically effective) amount of the compounds disclosed herein (typically in the form of a composition formulated for veterinary use). Thus, it is noted that a method for protecting animals, which method comprises administering to the animal a parasitically effective amount of the compounds disclosed herein. As mentioned in this disclosure and the claims, the terms "parasiticidal" and "parasitically" refer to the observable effects on invertebrate parasitic pests to protect the animals from the pests. The parasiticidal effect typically relates to a reduction in the occurrence or activity of the target invertebrate parasitic pests. Such effects on the pests include necrosis, death, growth retardation, reduced mobility or ability to remain on or in the host animal, reduced feeding, and reproductive inhibition. These effects on invertebrate parasitic pests prevent (including preventing, reducing or eliminating) parasitic infestation or infection of the animals. Examples of invertebrate parasitic pests controlled by administering to the animals to be protected a parasitically effective amount of the compounds disclosed herein include ectoparasites (arthropods, acarines, etc.) and endoparasites (worms, such as nematodes, trematodes, cestodes, acanthocephalans, etc.). In particular, the compounds disclosed herein are effective against ectoparasites including: flies such as the horn fly (Haematobia (Lyperosia) irritans), the stable fly (Stomoxys calcitrans), blackflies (Simulium species), tsetse flies (Glossina species), the head fly (Hydrotaea irritans), the autumn house fly (Musca autumnalis), the house fly (Musca domestica), the lesser house fly (Morellia simplex), horse flies (Tabanus species), the cattle grub (Hypoderma bovis), the common cattle grub (Hypoderma lineatum), the greenbottle fly (Lucilia sericata), the sheep blowfly (Lucilia cuprina), bluebottles (Calliphora species), Protophormia species, the sheep nasal bot fly (Oestrus ovis), midges (Culicoides species), the horse louse fly (Hippobosca equina), the horse bot fly (Gastrophilus intestinalis), the red horse bot fly (Gastrophilus haemorrhoidalis), and the nasal bot fly (Gastrophilus nasalis);Lice, such as Bovicola (Damalinia) bovis, Bovicola equi, Haematopinus asini, Felicola subrostratus, Heterodoxus spiniger, Lignonathus setosus, and Trichodectes canis; sheep ked, such as Melophagus ovinus; mites, such as Psoroptes species, Sarcoptes scabei, Chorioptes bovis, Demodex equi, Cheyletiella species, Notoedres cati, Trombicula species, and Otodectes cyanotis; ticks, such as Ixodes species, Boophilus species, Rhipicephalus species, Amblyomma species, Dermacentor species, Hyalomma species, and Haemaphysalis species; and fleas, such as Ctenocephalides felis and Ctenocephalides canis.

[0793] Non-agronomic applications in the veterinary sector are by conventional means, such as enteral administration in the form of, for example, tablets, capsules, drinks, infusion products, granules, pastes, boluses, feeding programs, or suppositories; or parenteral administration such as by injection (including intramuscular, subcutaneous, intravenous, intraperitoneal injection) or implants; nasal administration; topical administration, for example in the form of dipping or immersion, spraying, washing, powder coating, or application to a small area of the animal and by articles (such as collars, ear tags, tail bands, limb bands, or reins) containing the compounds or compositions of the present disclosure.

[0794] Typically, the antiparasitic compositions according to the present disclosure comprise a mixture of a compound of formula 1, its N-oxide or salt with one or more pharmaceutically or veterinarily acceptable carriers, said one or more pharmaceutically or veterinarily acceptable carriers comprising excipients and auxiliaries selected with respect to the intended route of administration (e.g., oral, topical or parenteral administration such as injection) and according to standard practices. Additionally, suitable carriers are selected on the basis of their compatibility with one or more active ingredients in the composition, including considerations such as stability with respect to pH and moisture content. Thus, it is noted that a composition for protecting animals against invertebrate parasitic pests, said composition comprising an antiparasitically effective amount of a compound of the present disclosure and at least one carrier.

[0795] For parenteral administration, including intravenous injection, intramuscular injection and subcutaneous injection, the compounds of the present disclosure can be formulated in the form of a suspension, solution or emulsion in an oily or aqueous medium and can contain adjuvants such as suspending agents, stabilizers and / or dispersing agents. Pharmaceutical compositions for injection include aqueous solutions of active ingredients in water-soluble form (e.g., salts of active compounds), preferably in a physiologically compatible buffer containing other excipients or auxiliaries, as known in the field of pharmaceutical formulations.

[0796] For oral administration in the form of solutions (the most readily absorbed form), emulsions, suspensions, pastes, gels, capsules, tablets, pills, powders, granules, rumen-retentive and feed / water / lick blocks, the compounds of the present disclosure can be formulated with binders / fillers known in the art for oral administration compositions, such as sugars (e.g., lactose, sucrose, mannitol, sorbitol), starches (e.g., corn 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), disintegrants (e.g., cross-linked polyvinylpyrrolidone, agar, alginic acid) and dyes or pigments can be added. Pastes and gels typically also contain binders (e.g., gum arabic, alginic acid, bentonite, cellulose, xanthan gum, colloidal magnesium aluminum silicate) to help keep the composition in contact with the oral cavity and not be easily expelled.

[0797] If the antiparasitic composition is in the form of a feed concentrate, the carrier is typically selected from high-performance feeds, feed grains or protein concentrates. In addition to the antiparasitic active ingredient, such compositions containing feed concentrates can also contain additives that promote animal health or growth, improve the meat quality of animals for slaughter or are otherwise useful for animal husbandry. These additives can include, for example, vitamins, antibiotics, chemotherapeutics, bacteriostatic agents, fungistatic agents, anticoccidials and hormones.

[0798] The compounds of the present disclosure have been found to have good pharmacokinetic and pharmacodynamic properties, thus providing systemic availability through oral administration and uptake. Accordingly, after uptake by the animal to be protected, the compounds of the present disclosure at a therapeutically effective concentration in the bloodstream protect the treated animal from blood-sucking pests such as fleas, ticks and lice. It is thus noted that a composition in a form suitable for oral administration for protecting animals from invertebrate parasitic pests (i.e., comprising, in addition to a therapeutically effective amount of the compounds of the present disclosure, a carrier selected from one or more binders and fillers suitable for oral administration and a feed concentrate carrier).

[0799] Formulations for topical application typically are in the form of powders, creams, suspensions, sprays, emulsions, foams, pastes, aerosols, ointments, salves or gels. More typically, the topical formulation is a water-soluble solution, which may be in concentrated form and diluted before use. Parasiticidal compositions suitable for topical application typically comprise a compound of the present disclosure and one or more topically suitable carriers. When the parasiticidal composition is topically applied to the exterior of the animal as a line or spot (i.e., "spot-on" treatment), the active ingredient migrates to the surface of the animal to cover most or all of its outer surface area. The treated animal is thus particularly protected from invertebrate pests that feed on the animal's epidermis such as ticks, fleas and lice. Formulations for topical application generally comprise at least one organic solvent to facilitate the transport of the active ingredient on the skin of the animal and / or its penetration into the animal's epidermis. Solvents commonly used as carriers in such formulations include propylene glycol, paraffin wax, aromatic compounds, esters such as isopropyl myristate, ethylene glycol ethers and alcohols such as ethanol and n-propanol.

[0800] The application rate required for effective control (i.e., "biologically effective amount") will depend on factors such as the species of invertebrate to be controlled, the life cycle of the pest, the life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, environmental humidity, temperature. Under normal circumstances, an application rate of about 0.01 kg to 2 kg of active ingredient per hectare is sufficient to control pests in an agroecosystem, but as little as 0.0001 kg / ha may be sufficient, or as much as 8 kg / ha may be required. For non-agronomic applications, effective use amounts will be between about 1.0 mg / square meter and 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. A person skilled in the art can readily determine the biologically effective amount required for the desired level of invertebrate pest control.

[0801] Typically for veterinary use, a compound of formula 1, its N-oxide or salt is administered to an animal to be protected from invertebrate parasitic pests in a parasitically effective amount. A parasitically effective amount is the amount of the active ingredient required to achieve an observable effect (reduction in the appearance or activity of the target invertebrate parasitic pest). Those skilled in the art will understand that the parasitically effective dose can vary depending on the various compounds and compositions of the present disclosure, the desired parasitical effect and duration, the species of the target invertebrate pest, the animal to be protected, the mode of application, etc., and the amount required to achieve a specific result can be determined by simple experimentation.

[0802] For oral administration to warm-blooded animals, the daily dose of the compounds of the present disclosure is typically from about 0.01 mg / kg to about 100 mg / kg of the animal body weight, more typically from about 0.5 mg / kg to about 100 mg / kg. For topical (e.g., dermal) administration, dips and sprays typically contain from about 0.5 ppm to about 5000 ppm, more typically from about 1 ppm to about 3000 ppm of the compounds of the present disclosure.

[0803] Specific compounds of formula 1 prepared by the methods and variations as described in Schemes 1-11 and Synthesis Examples 1-2 above are shown in Index Tables A and B below. 1 H NMR data are shown in Index Table C. For mass spectrometry (MS) data, the reported values are the molecular weights of the highest isotope abundance parent ions (M+1) formed by adding H + (with a molecular weight of 1) to the molecule as observed by mass spectrometry using atmospheric pressure chemical ionization (AP + . The following abbreviations are used in the subsequent index tables: Cmpd means compound, t is tertiary, c is cyclo, Me is methyl, Et is ethyl, Pr is propyl, i-Pr is isopropyl, Bu is butyl, c-Pr is cyclopropyl, c-Pn is cyclopentyl, c-Hx is cyclohexyl, t-Bu is tert-butyl, Ph is phenyl, OMe is methoxy, SMe is methylthio, and SO2Me means methylsulfonyl. The wavy line in the structural fragment indicates the attachment point of the fragment to the rest of the molecule. The abbreviation “Ex.” stands for “Example” and is followed by a number, which indicates in which synthesis example the compound was prepared.

[0804] Index Table A

[0805]

[0806]

[0807]

[0808]

[0809]

[0810] Index Table B

[0811]

[0812]

[0813]

[0814] **[α] 25 = +153.54° [C = 0.30%, MEOH]

[0815] Index Table C

[0816]

[0817]

[0818]

[0819] * 1 The H NMR data are shown in Index Table D.

[0820] Index Table D

[0821]

[0822] a 1 The H NMR data are in ppm at the low field of tetramethylsilane. Couplings are designated by (s) - singlet, (d) - doublet, (t) - triplet, (m) - multiplet, (dd) - doublet of doublets, (dt) - doublet of triplets, (br s) - broad singlet, (br t) - broad triplet.

[0823] The following tests demonstrate the pesticidal efficacy of the compounds of the present disclosure. "Pesticidal efficacy" means inhibition (including mortality) of the development of invertebrate pests that results in a significant reduction in feeding. However, the pest control protection provided by the compounds is not limited to these species. See Index Tables A and B for compound descriptions.

[0824] Biological example

[0825] Formulation and spraying methodology for Tests A - H

[0826] Using a solution containing 10% acetone, 90% water and 300 ppm Activator Solutions of nonionic surfactants (Loveland Products, Loveland, Colorado, USA) were used to formulate test compounds. The formulated compounds were applied as 1 mL of liquid via an atomizing nozzle positioned 1.27 cm (0.5 inches) above the top of each test unit. The test compounds were sprayed at a specified rate and each test was repeated three times.

[0827] Test A

[0828] To evaluate control of Plutella xylostella, test units consisted of small open containers with mustard plants 12 to 14 days old inside. These were pre-infested with approximately 50 newly hatched larvae which were distributed into the test units via corncob grits using an inoculum. After being distributed into the test units, the larvae were moved onto the test plants.

[0829] Test compounds were formulated and sprayed at 250 ppm. After spraying the formulated test compounds, each test unit was allowed to dry for 1 hour and then a black masking lid was placed on top. The test units were kept in a growth chamber at 25 °C and 70% relative humidity for 6 days. Plant feeding damage was then visually evaluated based on the leaves consumed and the mortality of the larvae was assessed.

[0830] Among the compounds of formula 1 tested at 250 ppm, the following provided very good to excellent levels of control efficacy (40% or less feeding damage and / or 100% mortality): 1, 3, 18, 19, 20, 21, 22, 23, 29, 30, 32, 33, 34, 36, 39, 45, 48, 50, 51, 53, 55, 59, 60, 78, 89, 92, 100, 103, 104, 105, 118, 120, 123, 125, 130, 133, 147, 155, 162, 166, 171, 172, 175.

[0831] Test B

[0832] To evaluate control of Peregrinus maidis (corn planthopper) by contact and / or systemic means, test units consisted of small open containers with corn (Zea mays) plants 3 to 4 days old inside. White sand was added to the top of the soil and then the test compounds were applied.

[0833] Prepare the test compound and spray at 250 ppm and / or 50 ppm and / or 10 ppm. After spraying the formulated test compound, allow the test unit to dry for 1 h, and then infest with approximately 15 - 20 nymphs (18 to 21 days old). Place a black shielding cover on top of each test unit and maintain the test units in a growth chamber at 22 °C - 24 °C and 50% - 70% relative humidity for 6 days. Then visually evaluate the insect mortality in each test unit.

[0834] Among the compounds of formula 1 tested at 250 ppm, the following resulted in at least 80% mortality: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 21, 22, 23, 25, 26, 30, 31, 32, 33, 34, 36, 37, 38, 39, 49, 67, 69, 70, 75, 76, 77, 78, 79, 81, 82, 83, 85, 86, 88, 89, 90, 92, 93, 94, 95, 96, 98, 103, 104, 105, 106, 108, 109, 110, 111, 112, 113, 114, 120, 123, 125, 127, 130, 138, 139, 147, 156, 157, 158, 159, 161, 163, 166, 168, 169, 170, 172, 173, 174, 175.

[0835] Among the compounds of formula 1 tested at 50 ppm, the following resulted in at least 80% mortality: 1, 2, 3, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 25, 26, 29, 30, 31, 32, 33, 34, 36, 37, 38, 39, 40, 41, 43, 45, 46, 48, 49, 50, 51, 55, 56, 57, 62, 63, 64, 65, 67, 69, 70, 76, 77, 78, 79, 83, 85, 86, 88, 89, 90, 92, 93, 94, 95, 96, 98, 103, 104, 105, 106, 108, 109, 110, 111, 112, 113, 114, 120, 123, 125, 127, 130, 138, 139, 147, 156, 157, 158, 159, 161, 163, 166, 168, 169, 170, 172, 173, 174, 175.

[0836] Among the compounds of formula 1 tested at 10 ppm, the following resulted in at least 80% mortality: 22, 30, 32, 33, 38, 41, 43, 45, 46, 48, 49, 50, 51, 62, 69, 70, 78, 89, 92, 93, 94, 95, 96, 98, 103, 106, 109, 110, 111, 112, 113, 114, 123, 125, 127, 130, 147, 156, 159, 163, 169, 172, 173, 174.

[0837] Test C

[0838] To evaluate control of the potato leafhopper by contact and / or systemic means, test units consisted of small open containers with 5 - to 6 - day - old Soleil bean plants (first leaves emerged) inside. White sand was added to the top of the soil, and one first leaf was excised before application of the test compound.

[0839] The test compounds were formulated and sprayed at 250 ppm. After spraying the formulated test compounds, the test units were dried for 1 hour, and then they were post - infested with 5 potato leafhoppers (18 - to 21 - day - old adults). A black cover was placed on top of the test units, and the test units were kept in a growth chamber at 20 °C and 70% relative humidity for 6 days. Then the insect mortality in each test unit was visually evaluated.

[0840] Among the compounds of formula 1 tested at 250 ppm, the following resulted in at least 80% mortality: 4, 8, 9, 11, 14, 21, 32, 33, 36, 37, 69.

[0841] Test D

[0842] To evaluate control of the green peach aphid by contact and / or systemic means, test units consisted of small open containers with 12 - to 15 - day - old radish plants inside. This was pre - infested (leaf - cutting method) by placing 30 - 40 aphids from a leaf cut from a cultured plant onto the leaf of the test plant. As the leaf dehydrated, the aphids moved onto the test plant. After pre - infestation, the soil of the test units was covered with a layer of sand.

[0843] The test compounds were formulated and sprayed at 250 ppm and / or 50 ppm. After spraying the formulated test compounds, each test unit was dried for 1 hour, and then a black cover was placed on top. The test units were kept in a growth chamber at 19 °C - 21 °C and 50% - 70% relative humidity for 6 days. Then the insect mortality in each test unit was visually evaluated.

[0844] Among the compounds of formula 1 tested at 250 ppm, the following resulted in at least 80% mortality: 1, 2, 3, 5, 7, 8, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 25, 29, 30, 34, 36, 37, 38, 39, 48, 54, 67, 68, 69, 70, 71, 72, 74, 77, 78, 79, 81, 83, 86, 87. 1, 2, 3, 5, 7, 8, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 25, 29, 30, 34, 36, 37, 38, 39, 48, 54, 67, 68, 69, 70, 71, 72, 74, 77, 78, 79, 81, 83, 86, 87, 88, 89, 90, 91, 93, 94, 95, 96, 97, 103, 104, 118, 123, 125, 127, 130, 147, 159, 163.

[0845] Among the compounds of formula 1 tested at 50 ppm, the following resulted in at least 80% mortality: 2, 3, 7, 8, 13, 14, 15, 16, 17, 18, 19, 20, 21, 29, 34, 39, 48, 54, 67, 69, 71, 74, 78, 86, 89, 90, 91, 93, 94, 95, 103, 104, 118, 123, 125, 127, 130, 147, 159.

[0846] Test E

[0847] To evaluate the control of Aphis gossypii by contact and / or systemic means, the test unit consisted of a small open container with 5-day-old okra plants inside. This was pre-infested with 30 - 40 insects on one leaf according to the leaf-disc method, and the soil of the test unit was covered with a layer of sand.

[0848] The test compounds were formulated and sprayed at 250 ppm and / or 50 ppm. After spraying, the test units were maintained in a growth chamber at 19 °C and 70% relative humidity for 6 days. Then the insect mortality of each test unit was visually evaluated.

[0849] Among the compounds of formula 1 tested at 250 ppm, the following resulted in at least 80% mortality: 1, 2, 3, 7, 8, 9, 11, 12, 14, 16, 17, 19, 20, 21, 22, 29, 32, 33, 34, 36, 37, 38, 39, 41, 45, 49, 50, 51, 52, 54, 56, 57, 59, 60, 62, 64, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 83, 84, 85, 86, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 100, 102, 103, 104, 105, 106, 109, 111, 112, 113, 118, 123, 125, 127, 130, 133, 147, 148, 154, 156, 157, 158, 159, 160, 161, 163, 166, 169, 171, 172, 174, 175, 176.

[0850] Among the compounds of formula 1 tested at 50 ppm, the following resulted in at least 80% mortality: 1, 3, 8, 9, 11, 12, 14, 16, 17, 19, 20, 21, 22, 29, 32, 33, 34, 36, 37, 38, 39, 45, 50, 51, 54, 67, 68, 69, 70, 71, 73, 74, 76, 78, 83, 85, 86, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 100, 102, 103, 104, 105, 106, 109, 111, 112, 113, 118, 123, 125, 127, 130, 133, 147, 148, 154, 156, 157, 158, 159, 160, 161, 163, 166, 169, 171, 172, 174, 175, 176.

[0851] Test F

[0852] To evaluate control of Bemisia tabaci by contact and / or systemic means, test units consisted of small open containers with cotton plants 12 to 14 days old inside. Before spray application, two cotyledons were removed from the plants, leaving one true leaf for analysis. Adult whiteflies were allowed to lay eggs on the plants and were then removed from the test units. Cotton plants infested with at least 15 eggs were submitted for spray testing.

[0853] Prepare the test compound and spray it at 250 ppm and / or 50 ppm. After spraying, allow the test unit to dry for 1 hour. Then remove the cylinder and place the unit in a growth chamber and maintain it at 28 °C and 50%-70% relative humidity for 13 days. Then visually evaluate the insect mortality of each test unit.

[0854] Among the compounds of formula 1 tested at 250 ppm, the following resulted in at least 70% mortality: 1, 3, 12, 13, 14, 15, 17, 19, 29, 36, 37, 39, 67, 69, 71, 78, 88, 89, 90, 91, 92, 93, 94, 95, 108, 109, 117, 118, 120, 123, 125, 127, 133, 134, 147, 155, 156, 168, 172.

[0855] Among the compounds of formula 1 tested at 50 ppm, the following resulted in at least 70% mortality: 1, 13, 14, 19, 69, 71, 78, 88, 89, 90, 91, 92, 93, 94, 95, 108, 109, 117, 118, 120, 123, 125, 127, 133, 134, 147, 155, 156, 168, 172.

[0856] Test G

[0857] To evaluate the control of Frankliniella occidentalis by contact and / or systemic means, the test unit consists of a small open container with a 5- to 7-day-old Soleil bean plant inside.

[0858] Prepare the test compound and spray it at 250 ppm. After spraying, allow the test unit to dry for 1 hour and then add approximately 60 thrips (adults and nymphs) to each unit. Place a black covering lid on top and maintain the test unit at 25 °C and 45%-55% relative humidity for 6 days. Then visually evaluate the plant damage and insect mortality of each test unit.

[0859] Among the compounds of formula 1 tested at 250 ppm, the following provided a very good to excellent level of control efficacy (30% or less plant damage and / or 100% mortality): 1, 19, 29, 32, 33, 36, 41, 50.

[0860] Additional example

[0861] Control efficacy and vapor pressure

[0862] The control efficacy and vapor pressure values of Compounds 8 and A are shown in Additional Table 1.

[0863] Appendix Table 1

[0864]

[0865] CMA represents Aphis gossypii; GPA represents Myzus persicae; CPH represents Laodelphax striatellus; PLH represents Empoasca fabae.

[0866] The test protocol for the control efficacy of the two compounds is as described in the biological example section.

[0867] The procedure for obtaining the vapor pressure values of the two compounds is as follows:

[0868] A solution of the test compound was prepared at a concentration of 50 μg / mL in acetonitrile and then analyzed by gas chromatography / mass spectrometry (GC / MS). The linear correlation of the retention time with the known vapor pressure values of the standard compound was used to obtain an estimated value of the vapor pressure of the test compound by using interpolation. The detection and interpretation of the retention time of the subject compound by mass spectrometry were confirmed.

[0869] Surprisingly, the results showed that Compound 8 of the present disclosure showed significantly higher control efficacy against species of CMA, GPA, and CPH as low as 2 ppm and PLH at 250 ppm than Compound A. The results also showed that the vapor pressure of Compound 8 was significantly lower than that of Compound A, almost 1000 times lower. It should be noted that the only structural difference between Compound 8 and A is that Compound 8 of Formula 1 has R as a 5-membered heterocyclic triazol-1-yl 4 , while Compound A has R as F 4 , which excludes Compound A from the scope of the present disclosure. While not bound by this theory, it is contemplated that R 4 as a heterocycle makes the compound less volatile, which may at least partially explain the higher control efficacy.

Claims

1. A compound selected from the compounds of formula 1, its N-oxide or salt, wherein R 1 is F; A is N or CR 3 ; R 2 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; R 3 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; R 4 Selected from U-31 to U-35 and U-44 to U-48 Each R v is independently H, cyano, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 cyanoalkyl, C1-C6 hydroxyalkyl, C4-C 10 alkylcycloalkyl, C4-C 10 cycloalkylalkyl, C3-C6 cycloalkenyl, C3-C6 halocycloalkenyl, C2-C6 alkoxyalkyl, C4-C 10 cycloalkoxyalkyl, C3-C 10 alkoxyalkoxyalkyl, C2-C6 alkylthioalkyl, C2-C6 alkylsulfinylalkyl, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-C 10 cycloalkylalkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C2-C6 alkoxyalkoxy, C2-C6 alkylcarbonyloxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C3-C6 cycloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C6 cycloalkylsulfonyl, C1-C6 alkylamino, C2-C6 dialkylamino, C1-C6 haloalkylamino, C2-C6 halodialkylamino or C3-C6 cycloalkylamino; r is 1, 2, 3, 4 or 5; R 5 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; Q is a six-membered aromatic ring containing ring members selected from carbon atoms and up to 2 nitrogen atoms, each ring being optionally substituted on the carbon atom ring members with up to 5 substituents independently selected from one or more R w ; and s is the number of these substituents; R w independently is H, cyano, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 cyanoalkyl, C1-C6 hydroxyalkyl, C4-C 10 alkylcycloalkyl, C4-C 10 cycloalkylalkyl, C3-C6 cycloalkenyl, C3-C6 halocycloalkenyl, C2-C6 alkoxyalkyl, C4-C 10 cycloalkoxyalkyl, C3-C 10 alkoxyalkoxyalkyl, C2-C6 alkylthioalkyl, C2-C6 alkylsulfinylalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-C 10 cycloalkylalkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C2-C6 alkoxyalkoxy, C2-C6 alkylcarbonyloxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C3-C6 cycloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C3-C6 cycloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C6 cycloalkylsulfonyl, C1-C6 alkylamino, C2-C6 dialkylamino, C1-C6 haloalkylamino, C2-C6 halodialkylamino or C3-C6 cycloalkylamino; or two Rs on adjacent carbon atoms w may together form an -OCF2O-, -OCH2O-, -OCF2S-, -OCH2CH2)-, OCF2CF2O- cyclic ether ring; s is 1, 2, 3, 4 or 5.

2. The compound according to claim 1, Wherein: A compound of formula 1, wherein A is CR 3 ; R 2 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; R 3 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; Each R v independently is H, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or C1-C6 haloalkoxy; r is 1, 2, 3, 4 or 5; R 5 is H, halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, C3-C4 halocycloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; Q is a six-membered aromatic ring having from 0 to 2 N's on the ring, each ring optionally being substituted on the carbon atom ring members with up to 5 substituents independently selected from R w ; R w independently is cyano, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl; s is 1, 2, 3, 4 or 5.

3. The compound according to claim 2, wherein: R 2 is H, a halogen or a C1-C4 alkyl group; R 3 is H, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; r is 1 or 2; R 5 is H, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; R w is a C1-C6 haloalkoxy group, a C1-C6 haloalkyl group, a C2-C6 haloalkenyl group, a C2-C6 haloalkynyl group, a C1-C6 haloalkylthio group, a C1-C6 haloalkylsulfinyl group, or a C1-C6 haloalkylsulfonyl group; s is 1 or 2.

4. The compound according to claim 3, wherein: R 2 is H; R 3 is H or a halogen; R v is H; R 5 is H or a halogen; Q is a phenyl, pyridyl, pyrimidinyl or pyrazinyl ring, each ring optionally being substituted on a ring carbon atom member with up to 5 substituents independently selected from R w ; R w is OCF3, SCF3, CF3, CF2CF3, SOCF3 or SO2CF3.

5. The compound according to claim 3, wherein: R 2 is a C1-C4 alkyl group; R 3 is H or a halogen; R v is H; r is 2; R 5 is H; Q is a phenyl, pyridyl, pyrimidinyl or pyrazinyl ring, each ring optionally being substituted on a ring member carbon atom with up to 5 substituents independently selected from R w ; R w is OCF3, SCF3, CF3, CF2CF3, SOCF3 or SO2CF3.

6. The compound according to claim 1, wherein The compound is selected from the group consisting of: 3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine; 3-Chloro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine; 3-Fluoro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine; 3-Fluoro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine; 3-Chloro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine; 3-Fluoro-4-[fluoro[4-(trifluoromethyl)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine; 3-Fluoro-4-[fluoro[4-[(trifluoromethyl)sulfinyl]phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine; 3-Chloro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine; and 3-Bromo-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine.

7. The compound according to claim 6, wherein, The compound is selected from the group consisting of: 3-Fluoro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine; 3-Chloro-4-[fluoro[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine; 3-Chloro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine; 3-Fluoro-4-[methoxy[4-(trifluoromethoxy)phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine; 3-Fluoro-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine; and 3-Bromo-4-[fluoro[4-[(trifluoromethyl)thio]phenyl]methyl]-5-(2H-1,2,3-triazol-2-yl)pyridine.

8. A composition comprising the compound according to claim 1 and at least one additional component selected from the group consisting of surfactants, solid diluents, and liquid diluents, said composition optionally further comprising at least one additional biologically active compound or agent.

9. The composition according to claim 8, wherein, The at least one additional biologically active compound or agent is selected from the group consisting of: abamectin, acephate, acequinocyl, acetamiprid, alphamethrin, alanidipine, amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, benfuracarb, bensultap, bifenthrin, bifenazate, bistrifluron, borate, broflanilide, buprofezin, carbaryl, cartap, chlordimeform, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezine, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cyenopyrafen, cyflumetofen, cyhalothrin, beta-cyhalothrin, cyhalodiamide, deltamethrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dichlorantraniliprole, dieldrin, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, dioxabenzofurole, emamectin, endosulfan, esfenvalerate, ethiprole, ethofenprox, etoxazole, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, flometoquin, flonicamid, flubendiamide, flucythrinate, flufenerim, flupyradifurone, fluvalinate, fluvalinate, formetanate, fosthiazate, halofenozide, heptaflumethrin, flucycloxuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidal soap, isofenphos-methyl, lufenuron, malathion, meperfluthrin, metaflumizone, metaldehyde, methidathion, methiocarb, methoprene, methoxychlor, methoxyfenozide, metofluthrin, monofluthrin, nicotine, N-[1,1-dimethyl-2-(methylthio)ethyl]-7-fluoro-2-(3-pyridyl)-2H-indazole-4-carboxamide, N-[1,1-dimethyl-2-(methylsulfinyl)ethyl]-7-fluoro-2-(3-pyridyl)-2H-indazole-4-carboxamide, N-[1,1-Dimethyl-2-(methylsulfonyl)ethyl]-7-fluoro-2-(3-pyridinyl)-2H-indazole-4-carboxamide, N-(1-methylcyclopropyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide, N-[1-(difluoromethyl)cyclopropyl]-2-(3-pyridinyl)-2H-indazole-4-carboxamide, nitenpyram, nithiazine, flucycloxuron, novaluron, methomyl, permethrin, phosalone, phosmet, pirimicarb, profenofos, profluazol, fenpyroximate, pyrethrins, pyridaben, pyridalyl, pyflubumide, pymetrozine, pyrifluquinazon, pyridaben, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulprofos, sulfoxaflor, tebufenozide, pyrimidifen, chlorfluazuron, tefluthrin, tetrachlorantraniliprole, tetrachlorvinphos, tetramethrin, dimefluthrin, thiacloprid, thiamethoxam, thiodicarb, bisultap, thiazosulfuron, tolfenpyrad, tetrabromomethrin, triazamate, trichlorfon, triflumezopyrim, triflumuron, Bacillus thuringiensis δ-endotoxin, entomopathogenic bacteria, entomopathogenic viruses, and entomopathogenic fungi., 10. A composition for protecting animals against invertebrate parasitic pests, comprising a parasitically effective amount of the compound according to claim 1 and at least one carrier.

11. A method for controlling invertebrate pests, which method comprises contacting the invertebrate pests or their environment with a biologically effective amount of the compound according to claim 1.

12. The method according to claim 11, wherein The invertebrate pests include stink bugs from the family Pentatomidae.

13. A seed treatment method, which comprises treating seeds with an amount of the compound according to claim 1 from about 0.0001% to 1% by weight of the seeds before treatment.

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