MX2008013305A - Five-membered heterocyclic invertebrate pest control agents. - Google Patents

Five-membered heterocyclic invertebrate pest control agents.

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Publication number
MX2008013305A
MX2008013305A MX2008013305A MX2008013305A MX2008013305A MX 2008013305 A MX2008013305 A MX 2008013305A MX 2008013305 A MX2008013305 A MX 2008013305A MX 2008013305 A MX2008013305 A MX 2008013305A MX 2008013305 A MX2008013305 A MX 2008013305A
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Mexico
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carbon atoms
alkyl
optionally substituted
compound
cyano
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MX2008013305A
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Spanish (es)
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Thomas Martin Stevenson
Jeffrey Keith Long
Dominic Ming-Tak Chan
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Du Pont
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Publication of MX2008013305A publication Critical patent/MX2008013305A/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/30—Oxygen or sulfur atoms
    • C07D233/32—One oxygen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/18—Oxygen atoms
    • C07D263/20—Oxygen atoms attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D291/00—Heterocyclic compounds containing rings having nitrogen, oxygen and sulfur atoms as the only ring hetero atoms
    • C07D291/02—Heterocyclic compounds containing rings having nitrogen, oxygen and sulfur atoms as the only ring hetero atoms not condensed with other rings
    • C07D291/04—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D419/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms
    • C07D419/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D419/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Disclosed are compounds of Formula (1), including all geometric and stereoisomers, <i>N</i>-oxides, and salts thereof wherein G is O or NR3; U is C(=O), S(=O), C(=S), or S(O)2; Z is N or CR2; R1 is cyano; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C4-C7 alkylcycloalkyl or C4-C7 cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from R17; R3 is H, cyano or -CHO; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C4-C7 alkylcycloalkyl, C4-C7 cycloalkylalkyl, phenyl, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-C9 dialkylaminocarbonyl each optionally substituted with one or more substituents independently selected from R18; Q is a 5- or 6-membered saturated or unsaturated heterocycle optionally substituted; or Q is C(O)NR12R13, C(S)NR12R13, S(O)2NR14R15 or R16; and R2, R12, R13, R14, R15, R16, R17, R18, A1, A2, A3, A4 and n are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound or a composition of the invention.

Description

HETEROCICLIC AGENTS OF FIVE MEMBERS FOR THE CONTROL OF INVERTEBRATE PESTS FIELD OF THE INVENTION This invention relates to some five-membered heterocyclic derivatives, their N-oxides, salts and compositions suitable for agronomic and non-agronomic uses including the uses listed below as well as methods of their use to control pests. of invertebrates such as arthropods in agronomic and non-agronomic environments.
BACKGROUND OF THE INVENTION The control of invertebrate pests is very important to obtain a high efficiency of a harvest. Damage by invertebrate pests to growing and stored agronomic crops can cause a significant reduction in productivity and therefore result in increased costs for the consumer. The control of invertebrate pests in the field, in greenhouse crops, in ornamental crops and nurseries, in stored foods and fiber products, live cattle, home, grass, wood products and public and animal health is also important. Many products are commercially available for these purposes but the need continues for new compounds that are more effective, less expensive, less toxic, Ref.: 195825 environmentally safer and have different modes of action. PCT Patent Publication No. 93/22298 describes oxazolidine derivatives and pharmaceutically acceptable salts thereof as antihyperlipidemics. Japanese Patent Publication 03176476 discloses imidazolidinones as chiral auxiliaries useful for producing penem and carbapenem antibiotics. The patent of E.U.A. 4186129 describes oxazoli.dinones useful as neuroleptics and phosphodiesterase inhibitors.
SUMMARY OF THE INVENTION This invention relates to compounds of formula 1 which include all geometric isomers and stereoisomers, N-oxides and salts thereof and compositions containing them as well as their use to control invertebrate pests: wherein G is O or NR3; U is C (= 0), S (= 0), C (= S) or S (0) 2; Z is N or CR2; A1 is CR4 OR N; A2 is CR5 or N; A3 is CR6 or N; A4 is CR7 or N; Q is a saturated or unsaturated 5- or 6-membered heterocycle optionally substituted with one or more substituents that are independently selected from halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 atoms of carbon, halocycloalkyl of 3 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, haloalkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, haloalkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 carbon atoms, haloalkylsulfonyl of 1 to 6 carbon atoms, alkylamino of 1 to 6 carbon atoms, dialkylamino of 2 to 8 carbon atoms , cyano, nitro, C (0) NR8R9, C (0) OR10, phenyl and pyridinyl, each phenyl or pyridinyl is optionally substituted with one or more substituents that are independently selected from R11; or Q is C (0) NR12R13, C (S) NR12R13, S (0) 2NR1R15 OR R16; R1 is cyano, alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms or cycloalkylalkyl from 4 to 7 carbon atoms, each optionally substituted with one or more substituents that are independently selected from R17; each R2 is independently H, halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 atoms of carbon, haloalkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, haloalkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 carbon atoms, haloalkylsulfonyl of 1 to 6 carbon atoms, alkylamino of 1 to 6 carbon atoms, dialkylamino of 2 to 8 carbon atoms, alkoxycarbonyl of 2 to 4 carbon atoms, alkylaminocarbonyl of 2 to 4 carbon atoms, dialkylaminocarbonyl of 3 to 9 carbon atoms, cyano or nitro; R3 is H, cyano or -CHO; or alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms, cycloalkylalkyl of 4 to 7 carbon atoms, phenyl, alkylcarbonyl of 1 to 6 carbon atoms, alkoxycarbonyl of 1 to 6 carbon atoms, alkylaminocarbonyl of 2 to 6 carbon atoms or dialkylaminocarbonyl of 3 to 9 carbon atoms, each optionally substituted with one or more substituents that are independently selected from R18; R4, R5, R6 and R7 are independently selected from H, halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, halocycloalkyl of 3 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy from 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, haloalkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, haloalkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 atoms carbon, haloalkylsulfonyl of 1 to 6 carbon atoms, alkylamino of 1 to 6 carbon atoms, dialkylamino of 2 to 8 carbon atoms, cyano and nitro; or R6 and R7 are taken together to form a fused aromatic ring, the fused aromatic ring contains as ring member in addition to the bridgehead atoms A3 and A4, 3 atoms which are selected from 1 to 2 carbon atoms, 0 to 2 nitrogen atoms, 0 to 1 oxygen atom and 0 to 1 sulfur atom, or 4 atoms which are selected from 2 to 4 carbon atoms and 0 to 2 nitrogen atoms; each R8, R12 and R14 is independently H, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms, cycloalkylalkyl of 4 to 7 carbon atoms, alkylcarbonyl of 2 to 7 carbon atoms, alkoxyalkyl of 2 to 6 carbon atoms or alkoxycarbonyl of 2 to 7 carbon atoms; each R9, R10, R13 and R15 is independently H; or alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms or cycloalkylalkyl of 4 to 7 carbon atoms, each optionally substituted with one or more substituents that are independently selected from R19; each R11, R23 and R24 is independently halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, haloalkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, haloalkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 carbon atoms, haloalkylsulfonyl of 1 to 6 carbon atoms, alkylaminosulfonyl of 1 to 6 carbon atoms, alkylamino of 1 to 8 carbon atoms, dialkylamino of 2 to 8 carbon atoms, alkoxycarbonyl of 2 to 4 carbon atoms, cyano or nitro; R16 is halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, halocycloalkyl of 3 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy from 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, haloalkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, haloalkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 atoms carbon, haloalkylsulfonyl of 1 to 6 carbon atoms, alkylamino of 1 to 6 carbon atoms, dialkylamino of 2 to 8 carbon atoms, cyano or nitro; each R17 and R18 is independently halogen, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 atoms carbon, cyano or nitro; each R19 is independently halogen, alkyl 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 carbon atoms, alkylcarbonyl of 2 to 6 carbon atoms carbon, alkoxycarbonyl 2 to 6 carbon atoms, trimethylsilyl, cyano, nitro or Q1; each Q1 is independently a phenyl or a saturated or unsaturated 5 or 6 membered heterocycle, each optionally substituted with one or more substituents that are independently selected from halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, halocycloalkyl of 3 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, haloalkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, haloalkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 carbon atoms, haloalkylsulfonyl of 1 to 6 carbon atoms, alkylamino of 1 to 6 carbon atoms, dialkylamino of 2 to 8 carbon atoms, cyano, nitro, C (O) R20R21. C (0) OR22., Phenyl or pyridinyl, each phenyl or pyridinyl is optionally substituted with one or more substituents that are independently selected from R23; each R20 is independently H, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms , alkylcycloalkyl of 4 to 7 carbon atoms, cycloalkylalkyl of 4 to 7 carbon atoms, alkylcarbonyl of 2 to 7 carbon atoms or alkoxycarbonyl of 2 to 7 carbon atoms; each R21 and R22 is independently H; or alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms, cycloalkylalkyl of 4 to 7 carbon atoms, phenyl or pyridinyl; each phenyl or pyridinyl is optionally substituted with one or more substituents that are independently selected from R24; and n is 1, 2, 3 or 4; and with the proviso that R16 is different from methoxy. This invention also provides a composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of formula 1, an N-oxide or a salt thereof and at least one additional component that is selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, the composition optionally further comprises a biologically effective amount of at least one additional biologically active compound or agent. This invention further provides a spray composition for controlling an invertebrate pest that comprises a biologically effective amount of a compound of formula 1, an N-oxide or a salt thereof or the composition described therein and a propellant. This invention also provides a bait composition for controlling an invertebrate pest that comprises a biologically effective amount of a compound of formula 1, an N-oxide or a salt thereof or the composition described therein, one or more food materials. , optionally an attractant and optionally a humectant. The invention further provides a trap device for controlling an invertebrate pest comprising the bait composition and a housing adapted to receive the bait composition, wherein the housing has at least one opening that is sized to allow the pest. of invertebrates pass through the opening so that the invertebrate pest has access to the bait composition from a location outside the housing and wherein the housing is further adapted to be placed at or near the site of potential or known activity for the plague of invertebrates. This invention also provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of formula 1, an N-oxide or a salt thereof (e.g. composition described herein). This invention also relates to said method wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of formula 1, an N-oxide or a salt thereof and at least an additional component that is selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, the composition additionally and optionally comprises a biologically effective amount of at least one additional biologically active compound or agent. This invention also provides a method for protecting a seed of an invertebrate pest comprising contacting the seed with a biologically effective amount of a compound of formula 1, an N-oxide or a salt thereof (e.g. as a composition). described herein). This invention also relates to the treated seed. This invention further provides a method for protecting an animal from an invertebrate parasitic pest comprising administering to the animal an effective parasiticidal amount of a compound of formula 1, an N-oxide or a salt thereof (e.g. as a composition described in I presented) .
DETAILED DESCRIPTION OF THE INVENTION As used herein, the terms "comprising", "comprising", "including", "including", "having", "having", "containing" or "containing", or any other variation thereof, is intended to cover non-exclusive inclusion. For example, a composition, a mixture, a method, method, article or apparatus comprising a list of elements is not necessarily limited to said elements only but may include other elements that are not expressly included or inherent in the list. said composition, mixture, process, method, article or apparatus. Furthermore, unless it is narrowly established in the opposite direction, the conjunction "or" refers to one or inclusive and not only to one or exclusive. For example, a condition A or B is satisfied by any of the following: A is true (or is present) and B is false (or is not present), A is false (or is not present) and B is true (is present) and both A and B are true (or are present). In addition, the indefinite articles "a" and "one" that precede an element or component of the invention are intended not to be limiting with respect to the number of instances (i.e., of the times the element or component is present). Therefore, "a" or "an" should be understood to include one or at least one and the singular word form of the element or component also includes the plural unless the number evidently means singular. As referred to in this description, the term "invertebrate pest" includes arthropods, gastropods and nematodes of economic importance as pests. The term "arthropods" includes insects, mites, spiders, scorpions, centipedes, millipedes, moisture cochineal and symphilans. The term "gastropod" includes snails, slugs, and other insects of the stylomatofora genus. The term "helminths" includes worms from the filma of nematelmint, platyhelmint and acanthocephala such as: round worms, earthworms and phytophagous nematodes (Nematoda), trematodes (Trematoda), cestodes (Cestoda) and horned head worms. In the context of this description, the term "Invertebrate pest control" means inhibition of invertebrate pest development (which includes mortality, reduction in feeding and / or mating disruption) and related expressions are defined analogously. The term "agronomic" refers to the production of field crops such as for food and fiber and includes the growth of corn, soybeans and other legumes, rice, cereal (for example, wheat, oats, barley, rye, rice, corn), vegetables with leaves (eg lettuce, cabbage and other cabbage crops), vegetables with fruits (eg tomatoes, peppers, eggplant, cruciferous and cucurbit), potatoes, beets, grapes, cotton, tree fruits (eg of the type of apple, of the type of walnut and citrus), small fruits (berries, cherries) and other specialty harvests (for example cañola, sunflower, olive). The term "non-agronomic" refers to other horticultural crops (for example greenhouse, nursery or other ornamental plants that do not grow in the field), residential and commercial structures in urban and industrial areas, weeds (for example grass farm , pasture, golf course, residential land, field for recreational sports, etc.), wood products, stored product, agroforestry and vegetation administration, public health (human) and animal health (for example domesticated animals such as pets, livestock in foot and poultry, non-domesticated animals such as wild-type animals.) As mentioned in the foregoing the term "alkyl" used alone or in compound words such as "alkylthio" or "haloalkyl" includes straight or branched chain alkyl , such as methyl, ethyl, n-propyl, i-propyl or the different butyl, pentyl or hexyl isomers The term "alkenyl" includes straight or branched chain alkenes such as ethenyl, 1-propenyl, 2-propenyl and the different isomers of butenyl, pentenyl and hexenyl. The term "alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. The term "alkynyl" includes straight or branched chain alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different isynyl, pentynyl and hexynyl isomers. The term "alkynyl" also includes portions that comprise multiple triple bonds such as 2,5-hexadienyl. The term "alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and different isomers of butoxy, pentoxy and hexyloxy. The term "alkylthio" includes branched or straight chain alkylthio portions such as methylthio, ethylthio and different isomers of propylthio, butylthio, pentylthio and hexylthio. The term "alkylsulfinyl" includes both enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" include CH3S (0) -, CH3CH2S (0) -, CH3CH2CH2S (O) -, (CH3) 2CHS (O) - and the different isomers of butylsulfinyl, pentylsulfinyl and hexylsulfinyl. Examples of "alkylsulfonyl" include CH3S (0) 2-, -CH3CH2S (O) 2-, CH3CH2CH2S (0) 2-, (CH3) 2CHS (O) 2- and the different isomers of butylsulfonyl, pentylsulfonyl and hexylsulfonyl. The term "alkylamino", "dialkylamino" and the like are defined analogously to the previous examples. The term "cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "alkylcycloalkyl" denotes an alkyl substitution in a cycloalkyl moiety and includes, for example, ethyl cyclopropyl, i-propylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. The term "cycloalkylalkyl" denotes cycloalkyl substitution in an alkyl moiety. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl and other cycloalkyl portions attached to straight or branched chain alkyl groups. The term "halogen" alone or in compound words such as "haloalkyl" or when used in descriptions such as "alkyl substituted with halogen" includes fluorine, chlorine, bromine or iodine. In addition, when used in compound words such as "haloalkyl" or when used in descriptions such as "alkyl substituted with halogen" the alkyl may be partially or completely substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" or "alkyl substituted with halogen" include F3C-, ClCH2-, CF3CH2- and CF3CC12-. The terms "halocycloalkyl", "haloalkoxy", "haloalkylthio" and the like are defined analogously to the term "haloalkyl". Examples of "haloalkoxy" include CF30-, CC13CH20-, HCF2CH2CH20- and CF3CH20-. Examples of "haloalkylthio" include CC13S-, CF3S-, CC1CH2S- and C1CH2CH2S-. Examples of "haloalkylsulfinyl" include CF3S (0) -, CC13S (0) -, CF3CH2S (0) - and CF3CF2S (0) -. Examples of "haloalkylsulfonyl" include CF3S (0) 2-, CC13S <; 0) 2-, CF3CH2S (0) 2- and CF3CF2S (0) 2-. The term "alkylcarbonyl" denotes straight or branched chain alkyl portions attached to a C portion (= 0). Examples of "alkylcarbonyl" include CH3C (= 0) -, CH3CH2CH2C (= 0) - and (CH3) 2CHC (= 0) -. Examples of "alkoxycarbonyl" include CH3OC (= 0) -, CH3CH2OC (= 0), CH3CH2CH2OC (= 0) -, (CH3) 2CH0C (= 0) - and the different butoxy- or pentoxycarbonyl isomers. The total number of carbon atoms in a substituent group is indicated by the prefix "of iaj carbon atoms" where i and j are integers from 1 to 9. For example, alkylsulfonyl of 1 to 4 carbon atoms indicates methylsulfonyl to butyl sulfonyl; 2 carbon atoms alkoxyalkyl denotes CH3OCH2; 3-carbon-alkoxyalkyl denotes, for example, CH3CH (OCH3), CH3OCH2CH2 or CH3CH2OCH-; and C 4 -alkoxyalkyl refers to the different isomers of an alkyl group substituted with an alkoxy group containing a total of 4 carbon atoms, examples include CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2. When a compound is substituted with a substituent having a subscript indicating the number of substituents that may exceed 1, said substituents (when exceeding 1) are independently selected from the group of defined substituents, for example (R2) n < n is 1, 2, 3 or 4. When a group contains a substituent which can be hydrogen, for example R2, then when this substituent is taken as hydrogen, it is recognized that this is equivalent to the group when it is not substituted. The term "heterocycle", "heterocyclic ring" or "heterocyclic ring system" denotes rings or ring systems in which at least one atom in the ring is not a carbon, for example nitrogen, oxygen or sulfur. Typically, a heterocyclic ring contains a maximum of 4 nitrogen atoms, a maximum of 2 oxygen atoms and a maximum of 2 sulfur atoms. The heterocyclic ring can be attached through any available carbon or nitrogen by replacement of the hydrogen in the carbon or nitrogen. The heterocyclic ring can be a saturated, partially unsaturated or completely unsaturated ring. When a completely unsaturated heterocyclic ring satisfies the Hückel rule, the ring is also referred to as a "heteroaromatic ring" or "aromatic heterocyclic ring". The term "aromatic ring" or "aromatic ring system" denotes carbocycles and completely unsaturated heterocycles in which at least one ring in the polycyclic ring system is aromatic (where aromatic indicates that the Hückel rule for the system is satisfied) of ring). The term "fused bicyclic ring system" denotes a ring system containing two fused rings in which any ring may be saturated, partially unsaturated or completely unsaturated. The term "fused heterobicyclic ring system" denotes a ring system containing two fused rings in which at least one atom in the ring is not carbon and which may be aromatic or non-aromatic, as defined above. The term "optionally substituted" in relation to the heterocyclic rings refers to groups which are unsubstituted and have at least one substituent other than hydrogen that does not eliminate the biological activity presented by the unsubstituted analogue. As used herein, the following definitions will apply, unless otherwise indicated. The term "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted" or with the term "(not) substituted." Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position in the group and each substitution is independent from each other. When Q or Q1 is a 5- or 6-membered nitrogen containing heterocycle, it may be attached to the remainder of formula 1 through any carbon or nitrogen atom in the available ring, unless otherwise indicated. One skilled in the art recognizes that "pyridinyl" and "pyridyl" are equivalent alternative names for an organic radical formed by removing a hydrogen atom from a pyridine ring to form a point of attachment; in this manner, "pyridinyl" and "pyridyl" are used herein as synonyms. As indicated in the above, Q1 can be (in addition) phenyl optionally substituted with one or more substituents that are selected from a group of substituents as defined in the summary of the invention. An example of phenyl optionally substituted with one more substituents is the ring that is illustrated as Ul in group 1, wherein R v is any substituent as defined in the summary of the invention for Q 1 and R is an integer from 0 to 5 As indicated in the above, Q or Q1 can be (in addition) saturated or unsaturated heterocycles of 5 or 6 members optionally substituted with one or more substituents that are selected from the group of substituents as defined in the summary of the invention. Examples of 5 or 6-membered unsaturated aromatic heterocycles optionally substituted with one or more substituents include the U-2 to U-61 rings illustrated in group 1 wherein R v is any substituent as defined in the summary of the invention for Q or Q1 and r is an integer from 0 to 4. Note that some U groups can only be substituted with less than 4 Rv groups (for example U-2 to U-5, U-7 to U-48 and U-52 to U-61). Although the Rv groups are shown in structures U-1 through U-61, it is noted that they do not need to be present since they are optional substituents. Note that when Rv is H when it is attached to an atom, this is equal to whether that atom is unsubstituted. The nitrogen atoms that require substitution to fill their valence are substituted with H or Rv. Note that when the point of union between (Rv) r and group U is illustrated in a floating manner, (Rv) r can be attached to any available carbon atom or nitrogen atom of group U. Group 1 U-l U-2 U-3 U-4 U-5 U-6 U-7 U-8 U-9 U-10 U-21 U-22 U-23 U-24 U-25 U-26 U-27 U-28 U-29 U-30 U-31 U-32 U-33 U-34 U-35 U-36 U-37 U-38 U-39 U-40 U-41 U-42 U-43 U-44 U-45 U-46 U-47 U-48 U-49 U-50 U-51 U-52 U-53 U-54 U-55 U-56 U-57 U-58 U-59 U-60 U-61 Note that when Q or Q1 is a saturated or unsaturated 5- or 6-membered unsaturated heterocycle, optionally substituted with one or more substituents that are selected from the group of substituents as defined in the summary of the ntion for Q or Q1 , one or two carbon members in the ring of the heterocycle optionally may be in oxidized form of a carbonyl moiety. Examples of unsaturated, saturated or non-aromatic 5- or 6-membered heterocycles include rings Q-1 to Q-35 as illustrated in group 2, wherein R v is any substituent as defined in the summary of the ntion for Q 1 . Note that when the point of union between (Rv) r and the group Q or Q1 is illustrated as floating, (Rv) r can be attached to any available carbon atom or nitrogen atom of group U. Note that when the point of attachment in the group Q or Q1 is illustrated as floating, the group Q or Q1 can be linked to the rest of the formula 1 through any available carbon or nitrogen of the group Q or Q1 by substitution of a hydrogen atom. Optional substituents can be attached to any available carbon or nitrogen by substituting a hydrogen atom. Note that when Q or Q1 comprises a ring that is selected from Q-28 to Q-35, Q2 is selected from O, S or N. Note that when Q2 is N, the nitrogen atom can complete its valence by substitution either with H or substituents as defined in the summary of the ntion for Q or Q1.
Q-ll Q-12 Q-13 Q-14 Q-15 Q-31 Q-32 Q-33 Q-34 Q-35 The compounds of this ntion can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereoisomers, atropisomers and geometric isomers. A person skilled in the art will appreciate that a stereoisomer can be more active and / or can show beneficial effects when its concentration increases in relation to another of one or several stereoisomers or when it is separated from the other one or more stereoisomers. Additionally, a person skilled in the art knows how to separate, increase the concentration and / or selectively prepare said stereoisomers. Accordingly, the present ntion comprises compounds which are selected from the formula I, N-oxides and agriculturally suitable salts thereof. The compounds of the ntion may be present as a mixture of stereoisomers, individual stereoisomers or as an optically active form. A person skilled in the art will appreciate that not all nitrogen containing heterocycles can form N-oxides since nitrogen requires a solitary pair available for oxidation to the oxide; a person skilled in the art will recognize those heterocycles containing nitrogen which can form N-oxides. A person skilled in the art will also recognize that tertiary amines can form N-oxides. The synthesis methods for the preparation of the N-oxides of heterocycles and tertiary amines are very well known to those skilled in the art and include the oxidation of heterocycles and tertiary amines with peroxyacids such as peracetic acid and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as tert-butyl hydroperoxide, sodium perborate and dioxiranes such as dimethyldioxirane. These methods for the preparation of N-oxides have been widely described and have been reviewed in the literature, see, for example, T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamano Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3 pp 18-20, A. J. Boulton and A. McKillop, Eds. , Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp. 149-161, A. R. Katritzky, Ed., Academic Press; . Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp. 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press. The salts of the compounds of the invention include acid addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric. The salts of the compounds of the invention also include those which are formed with organic bases (for example pyridine or triethylamine) or inorganic bases (for example hydrides, hydroxides or carbonates - sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic portion for example when Q1 is phenyl substituted with C (O) OR22 and R22 is H. Thus, the present invention comprises compounds which are selected from formula 1, N-oxides and salts thereof. The embodiments of the present invention, as described in the summary of the invention, include: Mode 1. A compound of formula 1 wherein G is 0. Modality 2. A compound of formula 1 wherein G is NR3. Modality 3. A compound of formula 1, wherein R3 is H or cyano; or alkyl of 1 to 4 carbon atoms optionally substituted with one or more substituents that are selected from halogen. Modality 4. A compound of formula 3, wherein R3 is CH3, CH2CH3 or CH2CF3. Modality 5. A compound of formula 1, wherein U is C (= 0). Modality 6. A compound of formula 1, wherein Z is CR2. Modality 7. A compound of formula 1, wherein each R 2 is independently selected from H, halogen or haloalkyl of 1 to 2 carbon atoms. Modality 8. A compound of the mode 7, wherein each R2 is independently H, halogen or CF3. Modality 9. A compound of formula 1, wherein A1 is CR4. Mode 10. A compound of formula 1, wherein A2 is CR5. Mode 11. A compound of formula 1, wherein A3 is CR6. Mode 12. A compound of formula 1, wherein A4 is CR7. Modality 13. A compound of formula 1, wherein R4 and R5 are independently selected from H, halogen, alkyl of 1 to 3 carbon atoms, haloalkyl of 1 to 3 carbon atoms, cyano and nitro. Modality 14. A compound of formula 1, wherein R6 and R7 are independently selected from H, halogen, alkyl of 1 to 3 carbon atoms, haloalkyl of 1 to 3 carbon atoms, cyano and nitro; or R6 and R7 are taken together to form a fused aromatic ring, the fused aromatic ring contains as ring member, in addition to the bridgehead atoms A3 and A4, 4 atoms which are selected from 3 to 4 carbon atoms and 0 to 1 nitrogen atoms. Modality 15. A compound of the embodiment 14, wherein R6 and R7 are independently selected from H, halogen, alkyl of 1 to 3 carbon atoms, haloalkyl of 1 to 3 carbon atoms, cyano and nitro. Modality 16. A compound of mode 14, wherein R6 and R7 are taken together to form a fused aromatic ring, the fused aromatic ring contains as ring member in addition to the bridgehead atoms A3 and A4, 4 atoms that are they select from 3 to 4 carbon atoms and 0 to 1 nitrogen atoms.
Modality 17. A compound of mode 14 or 16, wherein the fused aromatic ring contains 4 carbon atoms as ring members in addition to the bridgehead atoms A3 and A4. Modality 18. A compound of formula 1, wherein Q is a pyridinyl ring, a pyrimidinyl ring, a triazinyl ring, a pyrazolyl ring, a triazolyl ring, an imidazolyl ring, an oxazolyl ring, an isoxazolyl ring, a thiazolyl ring or a isothiazolyl ring, each ring is optionally substituted with one or more substituents that are independently selected from halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, halocycloalkyl of 3 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, haloalkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms , haloalkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 carbon atoms, haloalkylsulfonyl of 1 to 6 carbon atoms, alkylamino of 1 to 6 carbon atoms, dialkylamino of 2 to 8 carbon atoms, cyano, nitro, C (0) NR8R9, C (0) OR10, phenyl and pyridinyl, each phenyl and pyridinyl optionally substituted with one or more substituents that are independently selected from R11; or Q is C (-0) NR12R13, S (0) 2NR14R15 or R16. Modality 19. A compound of mode 18, wherein Q is a pyridinyl ring, a pyrimidinyl ring, a triazinyl ring, a pyrazolyl ring, a triazolyl ring, an imidazolyl ring, an oxazolyl ring, an isoxazolyl ring, a thiazolyl ring or an isothiazolyl ring, each ring is optionally substituted with one or more substituents that are independently selected from halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, halocycloalkyl of 3 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, alkyl thio of 1 to 6 carbon atoms, haloalkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, haloalkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 carbon atoms, haloalkylsulfonyl of 1 to 6 carbon atoms alkylamino of 1 to 6 carbon atoms, dialkylamino of 2 to 8 carbon atoms, cyano, nitro, C (0) NR8R9, C (0) OR10, phenyl and pyridinyl, each phenyl and pyridinyl optionally substituted with one or more Substituents that are independently selected from R11; Modality 20. A compound of mode 19, wherein Q is a pyrazolyl ring, a triazolyl ring or an imidazolyl ring, each ring is linked through nitrogen and is optionally substituted with one or more substituents that are independently selected from halogen, alkyl of 1 to 4 carbon atoms, haioalkyl of 1 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, halocycloalkyl of 3 to 6 carbon atoms, alkoxy of 1 to 4 carbon atoms, haloalkoxy of 1 to 4 carbon atoms, alkylamino of 1 to 4 carbon atoms, dialkylamino of 2 to 4 carbon atoms, cyano, nitro, C (0) NR8R9, C (0) OR10, phenyl and pyridinyl, each phenyl and pyridinyl optionally substituted with one or more substituents that are independently selected from R11; Modality 21. A compound of mode 20, wherein Q is a pyrazolyl ring, a triazolyl ring or an imidazolyl ring, each ring is linked through a nitrogen and is optionally substituted with one or more substituents that are independently selected from halogen , alkyl of 1 to 4 carbon atoms, haioalkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, haloalkoxy of 1 to 4 carbon atoms, cyano, nitro, C (0) NR8R9, C. { . 0) OR10. Modality 22. A compound of mode 21, wherein Q is a pyrazolyl ring, a triazolyl ring or an imidazolyl ring, each ring is linked through a nitrogen and optionally substituted with one or more substituents that are independently selected from halogen, alkyl of 1 to 3 carbon atoms and haloalkyl of 1 to 3 carbon atoms. Modality 23. A compound of mode 22, wherein Q is a triazolyl ring or an imidazolyl ring, each ring is linked through nitrogen and is optionally substituted with one or more substituents that are independently selected from halogen, alkyl from 1 to 3 carbon atoms and haloalkyl of 1 to 3 carbon atoms. Modality 24. A compound of formula 1, wherein each R 8 is independently H, alkyl of 1 to 6 carbon atoms, alkylcarbonyl of 2 to 7 carbon atoms or alkoxycarbonyl of 2 to 7 carbon atoms. Modality 25. A compound of the modality 24, wherein each R8 is H. Modality 26. A compound of formula 1, wherein each R9 is independently H; or alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, alkynyl of 2 to 4 carbon atoms, cycloalkyl of 3 to 4 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms or cycloalkylalkyl of 4 to 7 carbon atoms, each optionally substituted with one or more substituents that are selected from R19. Modality 27. A compound of mode 26, wherein each R9 is independently alkyl of 1 to 4 carbon atoms optionally substituted with one or more substituents that are selected from R19. Modality 28. A compound of mode 27, wherein each R9 is independently alkyl of 1 to 4 carbon atoms optionally substituted with a Q1 and optionally substituted with one or more substituents that are selected from halogen, alkyl of 1 to 4 carbon atoms. carbon, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms and cyano. Mode 29. A compound of formula 1, wherein each R10 is independently H; or alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, alkynyl of 2 to 4 carbon atoms, cycloalkyl of 3 to 4 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms or cycloalkylalkyl of 4 to 7 carbon atoms, each optionally substituted with one or more substituents that are selected from R19. Modality 30. A compound of the embodiment 29, wherein each R 10 is independently alkyl of 1 to 4 carbon atoms optionally substituted with one or more substituents that are selected from R 19. Modality 31. A compound of mode 30, wherein each R 10 is independently alkyl of 1 to 4 carbon atoms optionally substituted with a Q 1 and optionally substituted with one or more substituents that are selected from halogen, alkyl of 1 to 4 carbon atoms. carbon, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms and cyano. Modality 32. A compound of formula 1, wherein each R19 is independently selected from halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, cyano, nitro and Q1. Modality 33. A compound of the embodiment 32, wherein each R19 is independently selected from halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms and cyano. Mode 34. A compound of mode 18, where Q is C (= 0) NR12R13. Modality 35. A compound of formula 1, wherein R12 is H, alkyl of 1 to 6 carbon atoms, alkylcarbonyl of 2 to 7 carbon atoms or alkoxycarbonyl of 2 to 7 carbon atoms. Modality 36. A compound of the embodiment 35, wherein R12 is H. Modality 37. A compound of the formula 1, wherein R13 is H; or alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, alkynyl of 2 to 4 carbon atoms, cycloalkyl of 3 to 4 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms or cycloalkylalkyl of 4 to 7 carbon atoms, each optionally substituted with one or more substituents that are selected from R19. Modality 38. A compound of the modality 37, where R13 is H; or alkyl of 1 to 4 carbon atoms optionally substituted with one or more substituents that are selected from R19. Mode 39. A compound of mode 38, wherein R13 is H; or alkyl of 1 to 4 carbon atoms optionally substituted with one of Qx and optionally substituted with one or more substituents which are selected from halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfinyl of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, alkylcarbonyl of 2 to 4 carbon atoms, alkoxycarbonyl of 2 to 4 carbon atoms and cyano. Mode 40. A compound of the mode 39, wherein R13 is H; or alkyl of 1 to 4 carbon atoms optionally substituted with a Q1 and optionally substituted with one or more of fluorine. Modality 41. A compound of formula 1, wherein each R19 is independently selected from halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfinyl of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, alkylcarbonyl of 2 to 4 carbon atoms, alkoxycarbonyl of 2 to 4 carbon atoms, cyano, nitro and Q1. Modality 42. A compound of mode 41, wherein each R19 is independently selected from halogen and Q1. Modality 43. A compound of formula 1, wherein each Q1 is independently selected from phenyl, pyridinyl and thiazolyl, each optionally substituted with one or more substituents that are independently selected from halogen, alkyl of 1 to 3 carbon atoms, haloalkyl of 1 to 3 carbon atoms, cyano, phenyl and pyridinyl. Modality 44. A compound of mode 43, wherein Q 1 is phenyl, pyridinyl or thiazolyl. Modality 45. A compound of mode 18, where Q is R16. Modality 46. A compound of mode 18, where Q is S (0) 2NR14R15. Modality 47. A compound of formula 1, wherein R 14 is H, alkyl of 1 to 6 carbon atoms, alkylcarbonyl of 2 to 7 carbon atoms or alkoxycarbonyl of 2 to 7 carbon atoms. Modality 48. A compound of the embodiment 47, wherein R14 is H. Modality 49. A compound of formula 1, wherein R15 is H; or alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, alkynyl of 2 to 4 carbon atoms, cycloalkyl of 3 to 4 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms or cycloalkylalkyl of 4 to 7 carbon atoms, each optionally substituted with one or more substituents that are selected from R19. Modality 50. A compound of the modality 49, wherein R15 is H; or alkyl of 1 to 4 carbon atoms optionally substituted with one or more substituents that are selected from R19. Mode 51. A compound of mode 50, wherein R15 is H; or alkyl of 1 to 4 carbon atoms optionally substituted with one or more substituents which are selected from halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfinyl from 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, alkylcarbonyl of 2 to 4 carbon atoms, alkoxycarbonyl of 2 to 4 carbon atoms, cyano and at most one of Q1. Modality 52. A compound of the mode 51, wherein R15 is H; or alkyl of 1 to 4 carbon atoms optionally substituted with one or more of fluorine and at most one of Q1. Modality 53. A compound of formula 1, wherein Q is different from R16. Modality 54. A compound of formula 1, wherein R16 is halogen, haloalkyl of 1 to 3 carbon atoms, dialkylamino of 2 to 4 carbon atoms, cyano or nitro. Modality 55. A compound of formula 1, wherein R 1 is alkyl of 1 to 3 carbon atoms optionally substituted with one or more substituents that are independently selected from R 17. Modality 56. A compound of the embodiment 55, wherein R 1 is alkyl of 1 to 3 carbon atoms substituted with one or more of halogen. Modality 57. A compound of the 56 modality, where R1 is CF3. Modality 58. A compound of formula 1, wherein n is 1 or 2. Modality 59. A compound of formula 1, wherein at most three of A1, A2, A3 and A4 are N. Modality 60. A compound of the embodiment 59, where at most two of A1, A2, A3 and A4 are N. Modality 61. A compound of the modality 60, where at most one of A1, A2, A3 and A4 are N. Modality 62. A compound of the embodiment 61, wherein A1, A2, A3 and A4 are each different from N. Modality 63. A compound of formula 1, wherein, when Z is CH and one of R2 is attached to the phenyl ring at position 4, R2 is different from alkoxy of 1 to 6 carbon atoms. Modality 64. A compound of formula 1, wherein, when U is C (= 0) and G is NR3, then R3 is different from H. The embodiments of this invention, which include modalities 1 to 64 above as well as any other The modality described herein can be combined in any way and the descriptions of the variables in the modalities relate not only to the compounds of formula 1 but also to the initial compounds and intermediate compounds. In addition, the embodiments of this invention, which include the above embodiments 1 to 64 as well as any other modalities described herein and any combination thereof, pertain to the compositions and methods of the present invention. The combinations of embodiments 1 to 64 are illustrated by: Modality A. A compound of formula 1, wherein Q is a pyridinyl ring, a pyrimidinyl ring, a triazinyl ring, a pyrazolyl ring, a triazolyl ring, an imidazolyl ring, a oxazolyl ring, isoxazolyl ring, thiazolyl ring or isothiazolyl ring, each ring is optionally substituted with one or more substituents that are independently selected from halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, halocycloalkyl of 3 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, haloalkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, haloalkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 carbon atoms, haloalkylsulfonyl of 1 to 6 carbon atoms, alkylamino of 1 to 6 carbon atoms, dialkylamino of 2 to 8 carbon atoms, cyano, nitro, C (0) NR8R9, C (0) OR10, phenyl and pyridinyl, each phenyl and pyridinyl, is optionally substituted with one or more substituents that are independently selected of R11; or Q is C (0) NR12R13, S (0) 2NR14R15 or R16. Z is CR2; R1 alkyl of 1 to 3 carbon atoms optionally substituted with one or more substituents that are independently selected from R17; each R2 independently selects from H, halogen or haloalkyl of 1 to 2 carbon atoms; R3 is H or cyano; or alkyl of 1 to 4 carbon atoms optionally substituted with one or more substituents that are selected from halogen; R4 and R5 are independently selected from halogen, alkyl of 1 to 3 carbon atoms, haloalkyl of 1 to 3 carbon atoms, cyano and nitro; R6 and R7 are independently selected from halogen, alkyl of 1 to 3 carbon atoms, haloalkyl of 1 to 3 carbon atoms, cyano and nitro; or R6 and R7 are taken together to form a fused aromatic ring, the fused aromatic ring contains as ring members, in addition to the bridgehead atoms A3 and A4, four atoms which are selected from 3 to 4 carbon atoms and to 1 nitrogen atom; each R8 is independently H, alkyl of 1 to 6 carbon atoms, alkylcarbonyl of 2 to 7 carbon atoms or alkoxycarbonyl of 2 to 7 carbon atoms; each R9 and R10 is independently H; or alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, alkynyl of 2 to 4 carbon atoms, cycloalkyl of 3 to 4 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms or cycloalkylalkyl of 4 to 7 carbon atoms, each optionally substituted with one or more substituents that are selected from R19; R12 and R14 are independently H, alkyl of 1 to 6 carbon atoms, alkylcarbonyl of 2 to 7 carbon atoms or alkoxycarbonyl of 2 to 7 carbon atoms; R13 and R15 are independently H; or alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, alkynyl of 2 to 4 carbon atoms, cycloalkyl of 3 to 4 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms or cycloalkylalkyl of 4 to 7 carbon atoms, each optionally substituted with one or more substituents that are selected from R19; R16 is halogen, haloalkyl of 1 to 3 carbon atoms, dialkylamino of 2 to 4 carbon atoms, cyano or nitro; each R19 is independently selected from halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, cyano, nitro and Q1; Q1 is independently selected from phenyl, pyridinyl and thiazolyl, each optionally substituted with one or more substituents that are independently selected from halogen, alkyl of 1 to 3 carbon atoms, haloalkyl of 1 to 3 carbon atoms, cyano, phenyl and pyridinyl; and n is 1 or 2; with the proviso that at most one of A1, A2, A3 and A4 is N. Mode B. A compound of mode A, wherein R1 is alkyl of 1 to 3 carbon atoms substituted with halogen; and U is C (= 0). Mode C. A compound of mode B, wherein Q is a pyrazolyl ring, a triazolyl ring or an imidazolyl ring, each ring optionally is linked through nitrogen and optionally substituted with one or more substituents that are independently selected from halogen, alkyl of 1 to 4 carbon atoms, haloalkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, haloalkoxy of 1 to 4 carbon atoms, cyano, nitro, C (0) NR8R9, C (0) OR10; or Q is C (0) NR12R13; R1 is CF3; R6 and R7 are independently selected from H, halogen, alkyl of 1 to 3 carbon atoms, haloalkyl of 1 to 3 carbon atoms, cyano and nitro; or R6 and R7 are taken together to form a fused aromatic ring, the fused aromatic ring contains 4 carbon atoms as ring members in addition to the bridgehead atoms A3 and A4; each R8 is H; each R9 and R10 is independently alkyl of 1 to 4 carbon atoms optionally substituted with one of Q1 and optionally substituted with one or more substituents that are selected from halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, carbon, alkylthio of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms and cyano; R12 is H; R13 is H; or alkyl of 1 to 4 carbon atoms optionally substituted with one or more substituents that are selected from R19; and each R19 is independently selected from halogen and Q1. Modality D. A compound of the C mode, wherein each R2 is independently H, halogen or CF3; and R3 is CH3 CH2CH3 or CH2CF3. Mode E. A compound of mode D, where G is 0; and with the proviso that A1, A2, A3 and A4 are each different from N. Specific embodiments include compounds of formula 1 which are selected from the group consisting of: 4- [5- (3,5-dichlorophenyl) - 2-Oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide; 4- [5- (3,5-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2-methyl-N- (2,2,2-trifluoroethyl) benzamide; 4- [5- (3,5-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -1,2,3-oxazolidinyl-3-yl] -2-methyl-N- (2-pyridinylmethyl) benzamide; 2-Nitro-5- [2-oxo-5-phenyl-5- (trifluoromethyl) -3-oxazolidinyl] benzonitrile; 4- [5- (3,5-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide; 4- [5- (3,5-dichlorophenyl) 3-methyl-2-oxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide; 4- t5- (3,4-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide; 4- [5- (3,5-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2- (1 H-1,2,4-triazol-1-yl) -benzonitrile; 4- [5- (3,5-dichlorophenyl) -2,2-dioxido-5- (trifluoromethyl) -1,2,3-oxazolidinyl-3-yl] -2-methyl-N- (2-pyridinylmethyl) benzamide; and 4- [5- (3,5-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2-methyl-N- [1- (2-pyridinyl) ethyl] benzamide. Additional specific embodiments include any combination of the compounds of formula 1 that are selected from the group immediately above. It is to be noted that the compounds of this invention are characterized by favorable metabolic and / or residual soil patterns and show activity to control a spectrum of agronomic and non-agronomic invertebrate pests. It is particularly noticeable, for reasons of the spectrum of elimination of invertebrate pests and the economic importance, the protection of agronomic crops from the damage or prejudices caused by invertebrate pests when controlling the invertebrate pests, which are considered modalities of the invention. The compounds of this invention, due to their favorable displacement properties or to their systemicity in plants, also protect the leaves and other parts of the plant which are not in direct contact with a compound of formula 1 or a composition comprising the compound. Also to be noted as embodiments of the present invention are compositions for controlling an invertebrate pest comprising a biologically effective amount of a compound of any of the preceding embodiments as well as any other modalities described herein and any combination thereof, and At least one additional component that is selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, the compositions optionally further comprise a biologically effective amount of at least one additional biologically active compound or agent. The embodiments of the invention further include methods for controlling an invertebrate pest that comprises contacting the invertebrate pest or its environment with a biologically effective amount of a compound of any of the preceding embodiments (e.g., as a composition described in FIG. I presented) . The embodiments of the invention also include a composition comprising a compound of any of the preceding embodiments in the form of a liquid drainage formulation for the soil. The embodiments of the invention further include methods for controlling an invertebrate pest comprising contacting the soil with a liquid composition such as a soil drain comprising a biologically effective amount of a compound according to any of the preceding claims. The embodiments of the invention also include a spray composition for controlling an invertebrate pest that comprises a biologically effective amount of a compound of any of the preceding embodiments and a propellant. The embodiments of the invention further include a bait composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of any of the preceding embodiments, one or more food materials, optionally an attractant and optionally a humectant. The embodiments of the invention also include a device for controlling an invertebrate pest comprising the bait composition and a housing adapted to receive the bait composition, wherein the housing has at least one opening having a size to allow the invertebrate pest pass through the opening so that the invertebrate pest can access the bait composition from a location outside the housing, and wherein the housing is further adapted to be placed at or near the site of potential activity or known for the invertebrate plague. The compounds of formula 1 can be prepared by one or more of the following methods and variations as described in Reaction Schemes 1 to 14. The definitions of R1, R2, A1, A2, A3, A4, G, U, Q , Z and n in the compounds of the following formulas 1 to 24 are as defined in the above in the summary of the invention. The formulas la and Ib are subsets of formula 1 and formula 2a is a subset of formula 2. As shown in Reaction Scheme 1, a compound of formula 1 can be prepared by treating an amine of formula 2 with an appropriate reagent of formula 3 (wherein L is a leaving group of nucleophilic reaction such as halogen or imidazole) in the presence of a base (e.g. triethylamine), N, N-diisopropylethylamine or sodium acid carbonate). Also useful as a base are the polymer-supported acid scavengers such as the N-linked, -diisopropylethylamine and 4- (dimethylamino) pyridine polymer equivalents, for example the N - [(4-ethenylphenyl) -methyl)] N polymer. -methyl-4-pyridinamine with dietenylbenzene and ethenylbenzene (CAS Registration No. 82942-26-5, hereinafter identified as "PS-DMAP"). The method of Reaction Scheme 1 can be carried out with a wide variety of reagents of formula 3 such as 1,1'-carbonyldiimidazole, phosgene, trichloromethyl chloroformate, triphosgene (ie, when U is C (= 0)) , thiophosgene, 1,1'-thiocarbonyldiimidazole (ie, when U is C (= S)), thionyl chloride (ie, when U is S (= 0)) and sulphuryl chloride (ie, when U is S (0) 2) · Reaction scheme 1 The reaction can be carried out neat or in a solvent such as dichloromethane, chloroform, tetrahydrofuran, acetonitrile, or 1,2-dichloroethane. The temperatures for this reaction can vary from 0 to 90SC. The method of Reaction Scheme 1 is illustrated in Step F of Example 1, Step D of Example 2 and in Example 3. The compounds of Formula 2a (Formula 2 wherein G is O) can be worked through the opening of the ring of an appropriate epoxide of formula 4 by treatment with an amine of formula 5 in a solvent such as methanol, ethanol, chloroform, tetrahydrofuran, acetonitrile or 1, 2-dic 1-oroethane at temperatures ranging from 25 to 90 ° C, as shown in reaction scheme 2. The method of reaction scheme 2 is illustrated in step E of example 1 and step C of example 2.
Reaction Scheme 2 Epoxides of formula 4 can be prepared from ketones of formula 6 by treatment with a sulfonium ylide, which is typically generated in situ by reacting a trimethoxyalfoxonium halide of formula 7 with an appropriate base such as hydride. of sodium, potassium hydride or sodium terbutoxide in a suitable solvent such as dimethyl sulfoxide, N, N-dimethyl formamide or tert-butanol, as shown in Reaction Scheme 3. The method of Reaction Scheme 3 is illustrated in step D example 1. The trimethylsulfoxonium halides of formula 7 are commercially available.
Reaction Scheme 3 7 X is halogen As illustrated in Reaction Scheme 4, ketones of formula 6 can be obtained by treating compounds of formula 8 with metallic lithium, an organolithium reagent such as n-butyl-lithium, sec-butyl-lithium or tert-butyl-lithium or an alkylmagnesium halide such as methyl bromide bromide or ethyl chloride at temperatures typically between -78 ° C and room temperature, to form the lithium or Grignard intermediate, respectively. This intermediate is then reacted with a reagent of formula 9 wherein L1 is a leaving group such as Cl, Br, OCH3 or OCOCF3 to provide the ketone of formula 6. The reaction is carried out in an organic solvent, preferably tetrahydrofuran or diethyl ether. The method of Reaction Scheme 4 is illustrated in step C of example 1.
Reaction Scheme 4 Alternatively, compounds of formula la (formula 1 wherein G s 0 and U is C (= 0)) can be prepared from oxazole idinones of formula 10 by reacting with aromatic halide intermediates of formula 11 (wherein L2 is a leaving group such as F or Cl) as illustrated in Reaction Scheme 5.
Reaction Scheme 5 In this reaction, the oxazolidinone of formula 10 is contacted with a base such as sodium hydride or potassium terbutoxide and then further treated with a compound of formula 11, typically in a solvent (eg, N, N-dimethylformamide) or dimethyl sulfoxide). The method of Reaction Scheme 5 is illustrated in step B of example 4. Alternatively, when formula 11 is an aryl bromide, (ie, L2 is Br) the reaction can be carried out with two equivalents of a base such as potassium carbonate and in the presence of a copper (I) catalyst such as copper (I) iodide (typically 3-5 mol%) and trans-cyclohexanediamine (to solubilize Cul) using the method described in Organic Letters 2003, 5, 963-965. As shown in Reaction Scheme 6, compounds of formula I can also be prepared by a copper-mediated N-arylation reaction of an oxazolidinone of formula 10 with a compound of formula 12, wherein M is a group such as boronic acid, boronic ester, biaryl bismuth, trialkylstannane or trialkylsiloxane. The reaction can be carried out of a solvent such as dichloromethane, chloroform or tetrahydrofuran and in the presence of a copper salt such as copper (II) acetate and a base (for example triethylamine or pyridine) as shown in the Scheme of Reaction 6. For general procedures for this type of reaction see Law, SV; Thomas, A. W. Angewandte Chemie, International Edition 2003, 42, 5400-5449.
Reaction Scheme 6 The oxazolidinones of formula 10 can be prepared by the reaction of aminoalcohols of formula 13 with triphosgene or triphosgene substitutes resulting in carbonylation (for example diphosgene, phosgene (bis (trichloromethyl) carbonate) or 1,1'-carbonyldiimidazole). The reaction is carried out in a suitable organic solvent such as dichloromethane, 1,2-dichloroethane or tetrahydrofura or in the presence of a base such as triethylamine, sodium acid carbonate or sodium carbonate, as shown in Reaction Scheme 7 .
Reaction Scheme 7 The aminoalcohols of formula 13 can be prepared by the reduction of cyanohydrins of formula 14 with a reducing agent such as lithium tetrahydroaluminate in a suitable organic solvent such as diethyl ether or tetrahydrofuran, as shown in Reaction Scheme 8. The methods of Reaction Schemes 7 and 8 are illustrated in Step A of Example 4.
Reaction Scheme 8 The cyanohydrins of formula 14 can be prepared from the corresponding ketones (ie, formula 6) via one of a variety of cyanation methods well known in the art (see, eg, North M. Science of Synthesis 2004, 19, 235-284). Compounds of formula Ib (ie, formula 1 wherein G is NR3 and U is C (= 0)) can be prepared by reduction of the imide of formula 15 with sodium borohydride in a suitable solvent such as methanol and then reduce the resulting 5-hydroxy intermediate with sodium borohydride and trifluoroacetic acid. Methods for the reduction of ketones and alcohols are well documented in the art, see, for example Mehrotra, M. M., et al .; Journal of Medicinal Chemistry 2004, 47, 2037-2061 and Johnson, M. R.; Rickborn, B .; Journal of Organic Chemistry 1970, 35, 1041-1045. The method of Reaction Scheme 9 is illustrated in Example 5, Steps E and F as well as in Example 6, Steps B and C.
Reaction Scheme 9 Ib As shown in Reaction Scheme 10, compounds of formula 15 can be prepared from cyclization of ureas of formula 16 by treatment with aqueous hydrochloric acid according to the general method described by Cook, A. H .; Hunter, G. D .; Journal of the Chemical Society 1952, 3789-3796. For compounds of formula 15 wherein R3 is different from H, then the treatment of the cyclized intermediate (wherein R3 is H) with L3-R3 (wherein L3 is a leaving group) in the presence of a suitable base such as sodium hydride to provide the compounds of formula 15. The second step of the method of Reaction Scheme 10 is illustrated in Example 6, Step A.
Reaction Scheme 10 As shown in Reaction Scheme 11, compounds of formula 16 can be obtained by reacting o-aminonitrile of formula 17 with isocyanates of formula 18, according to the general method of Van Dort, M. E .; Jung, Y.-W .; Bioorganic & Medicinal Chemistry Letters 2004, 24 (21), 5285-5288.
Reaction Scheme 11 The compounds of formula 17 can be obtained by converting ketones of formula 6 to the corresponding imines, followed by the addition of a cyanide source (for example HCN) to the imine intermediates, followed by the addition of cyanide, which is well documented in the technique (see, for example, Organic Reaction 2002, 59, 1-714 and Koos, M .; Mosher, H. S .; Tetrahedron 1993, 49, 1541-1546) The method shown in the Reaction Scheme 12 is particularly useful for the preparation of the imines 20 when R1 is CF3.
Reaction Scheme 12 As shown in the foregoing, a ketone of formula 6 is first treated with lithium bis (trimethylsilyl) amide which results in the formation of imine intermediate 19, which is then solved in methanol to provide a stable imine in accordance with the general method of Gosselin, F. et al Organic Letter 2005, 7, 355-358. Alternatively, compounds of formula 15 can be prepared by heating the compounds of formula 21 with amines of formula 5 (see reaction scheme 13) in the presence of a catalyst such as 4- (dimethylamino) pyridine or trifluoroacetic acid. The cyclised hydantoins that are then formed can be treated with L3-R3 in the presence of a base such as sodium hydride to form compounds of formula 15. As reference see Pozzo, A. D. et al.; Tetrahedron 1998, 6019-6028. The method of reaction scheme 13 is illustrated in example 5, step D.
Diagram of reaction 13 As shown in reaction scheme 14, compounds of formula 21 can be obtained by reacting keto esters of formula 22 with benzyl carbamate, after dehydration to form imines of formula 23 followed by addition of Grignard intermediates 24 which can be derived from compounds of formula 8, as previously described for the method of the reaction scheme 4. As a general reference see Dessipri, E.; tirrell, D. A.; Macramolecules 1994, 27, 5463-5470. The method of reaction scheme 14 is illustrated in example 5, steps A-C.
Reaction scheme 14 A person skilled in the art will recognize that the compounds of formula 1 and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation and reduction reactions to add substituents or modify existing substituents. It is also recognized that some reagents and reaction conditions described in the above for preparing compounds of formula 1 may not be compatible with some functionalities present in the intermediates. In these cases, the incorporation of protection / deprotection sequences or interconversions between functional groups in the synthesis will help to obtain the desired products. The use and selection of protecting groups will be apparent to a person skilled in chemical synthesis (see, for example, Greene, T. W., Wuts, P.M. Protective Groups in Organic Synthesis, 2nd ed., Wiley: New York, 1991). A person skilled in the art will recognize that, in some cases, after the introduction of a given reagent and as shown in any individual reaction scheme, it may be necessary to perform additional routine synthesis steps not described in detail in order to complete the synthesis of the compounds of formula 1. A person skilled in the art will also recognize that it may be necessary to perform a combination of steps illustrated in the above reaction schemes in an order different from that implied by the particular sequence presented to prepare the compounds of formula 1 Without further elaboration, it is considered that a person skilled in the art using the preceding description can use the present invention to its full extent. Therefore, the following examples are considered as illustrative only and not limiting of the description in any way. The NMR spectra ?? they are reported in downfield ppm from tetramethylsilane; 19 F NMR spectra are reported in ppm using trichlorofluoromethane as a reference; "s" means singlet, "d" means doublet, "t" means triplet, "m" means multiplet, "dd" means double of doublets, "dt" means triplet double, "brs" means broad singlet and "brt a" "It means broad triplet. EXAMPLE 1 Preparation of 4- [5- (3,5-dichlorophenyl) -2 -oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2-methyl-N- (2,2,2-trifluoroethyl) benzamide Step A : Preparation of 4- (acetylamino) -2-methyl-N- (2,2,2-trifluoroethyl) benzamide To a stirred solution of 4- (acetylamino) -2-methylbenzoic acid (Aldrich 1.9 g, 9.8 mmol) in 9 of tetrahydrofuran at room temperature is added 1,1'-carbonyldiimidazole (1.65 g, 10.1 mmol). After 18 h 2, 2, 2-trifluoroethanamine (1.6 g, 16.0 mmol) is added followed by a catalytic amount of 4- (dimethylamino) pyridine (also known as N, -dimethyl-4-pyridinamine). After 24 h, water is added to the reaction mixture and the resulting precipitate is collected by filtration and dried to provide the title compound as 2.1 g of a white powder. RM XH (DMSO-d6): d 10.01 (s, 1H), 8.80 (t, 1H), 7.46 (d, 1H), 7.45 (s, 1H), 7.31 (d, 1H), 4.02 (m, 2H) , 2.31 (s, 3H), 2.05 (s, 3H). Step B: Preparation of 4-amino-2-methyl-N- (2, 2, 2-trifluoroethyl) benzamide A 4- (acetylamino) -2-methyl-N- (2, 2,2-trifluoroethyl) benzamide (ie, the product from step A) is added concentrated hydrochloric acid and the reaction mixture is heated at 100 ° C for 2 h. The reaction mixture is cooled using an external ice / water bath and an aqueous solution of sodium hydroxide (50% by weight, 20 ml) is added until the reaction mixture is neutralized which causes a solid to precipitate. The solid is filtered, washed with water and dried in a vacuum oven at 60 ° C overnight to give the title compound as 0.89 g of a white powder. XH NMR (DMSO-de): d 8.42 (t, 1H), 7.18 (d, 1H), 6.38 (s, 1H), 6.39 (d, 2H), 5.43 (broad s, 2H), 3.96 (m, 2H) ), 2.57 (s, 3H). Step C: Preparation of 1- (3,5-dichlorophenyl) -2,2,2-trifluoroethanone To a stirred suspension of l-bromo-3,5-dichlorobenzene (aldrich, 15.0 g, 65.1 mmol) between 300 ml of anhydrous ether at -70 ° C are added dropwise N-butyl-lithium (2.5 M in hexane, 26.0 ml, 65.0 mmol) for 30 minutes. After 5 minutes, methyl trifluoroacetate (9.17 g, 71.6 mmol) in 7 ml of ether is added dropwise over 45 minutes. After an additional 45 minutes the reaction mixture is heated to 0 ° C and then poured into a saturated solution of aqueous potassium dihydrogen phosphate (50 g in 200 ml of water) and stirred for 30 minutes at room temperature. The layers are separated and the organic layer is washed with 100 ml of saturated sodium chloride, dried with MgSO 4 and concentrated under reduced pressure to give the title compound as 13.0 g of a yellow oil. X H NMR (CDC13): d 7.74 (s, 2H), 7.44 (s, 1H). 19 F NMR (CDCl 3): d-76.82. Step D: Preparation of 2- (3,5-dichlorophenyl) -2- (trifluoromethyl) oxirane Sodium hydride (60%, 0.36 g, 9.0 mmol) is added to a stirred solution of trimethylsulfoxonium iodide. { 1.88 g, 8.5 mmol) in 17 ml of dimethyl sulfoxide under a nitrogen atmosphere. After stirring for 0.5 hours the solution is added dropwise over 5 minutes to a solution of 1- (3,5-dichlorophenyl) -2,2,2-trifluoroethanone (ie the product of step C) (1.7 g. , 7.0 mmol) in tetrahydrofuran. The resulting yellow suspension is stirred for 5 minutes and then the reaction mixture is partitioned between 100 ml of ether and 50 ml of water. The organic layer is separated and the aqueous layer is extracted with 70 ml of ether. The combined ether extracts are washed with 40 ml of water and dried with MgSO4. The ether solution is filtered and the solvent is concentrated under reduced pressure to provide the title compound as 1.71 g of an orange oil. The crude product (70-80% by XH NMR) is used without purification. X H NMR (CDC13): d 7.42 (m, 3H), 3.43 (d, 1H), 2.91 (m, 1H). 19 F NMR (CDC13): d-74.57. Step E: 4- [[2- (3,5-dichlorophenyl) -2-hydroxy-3,3,3-trifluoropropyl] amino] -2-methyl-N- (2,2,2-trifluoroethyl) -benzamide One 0.82 g solution of 2-. { 3,5-dichlorophenyl) -2- (trifluoromethyl) oxirane (ie, the product of step D) and 4-amino-2-methyl-N- (2,2,2-trifluoroethyl) benzamide. { that is, the product of step B) (0.42 g, 1.7 mmol) in 8 ml of anhydrous ethanol is heated at 75 ° C for 18 h. After cooling, the solvent is concentrated under reduced pressure. The residue is purified by medium pressure chromatography on silica gel using ethyl acetate-hexanes (2: 3) as eluent to give the title compound as 0.36 g of a whitish vitreous solid. RM XH (CDC13): d 7.51 (s, 2H), 7.37 (s, 1H), 7.18 (d, 1H), 6.42 (m, 2H), 6.30 (s, 1H), 6.29 (d, 1H), 5.13 (s, 1H), 3.96 (m, 2H), 3.74 (dd, 1H), 3.62 (dd, 1H), 2.00 (s, 3H). 19 F NMR (CDCl 3): d-72.80, -78.47. Step Fj 4- [5- (3,5-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2-methyl-N- (2,2,2-trifluoroethyl) enamide A solution of 4 - [[2- (3,5-dichlorophenyl) -2-hydroxy-3,3,3-trifluoropropyl] amino] -2-methyl-N- (2,2,2-trifluoroethyl) -benzamide (ie the product of stage E) (0.28 g, 0.57 mmol), 1,1 '-carbonyldiimidazole (0.15 g, 0.93 mmol) and PS-DMAP (Riley Co., 1.4 mmol / g) (0.085 g, 0.12 mmol) in 7 ml of dichloromethane is stirred at room temperature for 5 h. More 1, 1'-carbonyldiimidazole (0.05 g, 0.31 mmol) is added. After stirring for 22 h, more 1,1'-carbonyldiimidazole (0.047 g, 0.28 mmol) and PS-DMAP (0.10 g, 0.14 mmol) are added. After stirring for 4 h the reaction mixture is concentrated under reduced pressure and the resulting residue is dissolved in 60 ml of ethyl acetate, washed with water (30 ml, 3 times), filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian) and concentrated under reduced pressure to provide a solid. The crude solid is purified by medium pressure silica gel chromatography using ethyl acetate / hexanes (2: 3) as eluent to give the title product, a compound of the present invention as 0.20 g of an off-white solid. RN XH (CDC13): d 7.48 (m, 3H), 7.41 (d, 1H), 7.37 (d, 1H), 7.31 (s, 1H), 6.38 (broad s, 1H), 4.62 (d, 1H), 4.30 (d, 1H), 4.07 (m, 2H), 2.43 (s, 3H). NMR 19F (CDC13): d -72.79, -81.57. EXAMPLE 2 Preparation of 4- (5- (3,5-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2-methyl-N- (2-pyridylmethyl) benzamide Step A: Preparation of - (acetylamino) -2-methyl-N- (2-pyridinylmethyl) benzamide A mixture of 4- (acetylamino) -2-methylbenzoic acid (5.0 g, 25.9 mmol), 2-pyridinomethanamine (2.94 g, 2.8 ml, 27. 2 mmoles) and N '- (ethylcarbonimidoyl) -N, N-dimethyl-1,3-propanediamine monohydrochloride (5.2 g, 27.1 mmol) in 250 ml of dichloromethane is stirred at room temperature overnight. Water is then added to the reaction mixture and the two resulting layers are separated. The dichloromethane layer is passed through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian) and concentrated under reduced pressure. The resulting amber oil is triturated with dichloromethane, N-butyl chloride and hexanes to give the title compound as 5.5 g of a light yellow solid. 1 H NMR (CDCl 3): d 8.53 (d, 1H), 7.92 (broad s, 1H), 7.69 (m, 1H), 7.42-7.16 (m, 6H), 4.72 (d, 2H), 2.42 (s, 3H ), 2.15 (s, 3H). Step B: Preparation of 4-amino-2-methyl-N- (2-pyridinylmethyl) benzamide A mixture of 4- (acetylamino) -2-methyl-N- (2-pyridinylmethyl) benzamide (ie, the product of the Step A) (5.5 g, 19.4 mmol) and 100 ml of concentrated hydrochloric acid is stirred and heated at reflux for 1 h. After cooling ice is added and the pH is adjusted to 10 by adding aqueous sodium hydroxide (50% by weight). The reaction mixture is filtered to collect the solid precipitate, which is washed with water and dried to give the title compound as 4.02 g of a light yellow solid. XH NMR (DMSO-de): d 8.49 (d, 1H), 8.41 (broad s, 1H), 7.76 (m, 1H), 7.31. { d, 1H), 7.22-7.27 (m, 2H), 6.36-6.40 (m, 2H), 5.36 (s, 2H), 4.47 < s, 2H), 2.28 (s, 3H).
Step C: Preparation of 4- [[2- (3,5-dichlorophenyl) -2-hydroxy-3,3,3-trifluoropropyl] amino] -2-methyl-N- (2-pyridinylmethyl) benzamide A solution of 0.75 g of 2- (3,5-dichlorophenyl) -2- (trifluoromethyl) oxirane (ie the product of example 1, step D) and 4-amino-2-methyl-N- (2-pyridinylmethyl) benzamide (is say, the product of step B) (0.39 g, 1.7 mmol) in 6 ml of anhydrous ethanol is heated at 65 ° C for 70 h. The reaction mixture is concentrated under reduced pressure and the residue is purified by medium pressure chromatography on silica gel using ethyl acetate / hexanes (6: 8) as eluent to give 0.28 g of the title compound as a whitish glassy solid. XH NMR (CDC13): d 8.50 (d, 1H), 7.70 (t, 1H), 7.52 (s, 2H), 7.40 (s, 1H), 7.31 (m, 2H), 7.21 (m, 1H), 7.08 (broad t, 1H), 6.37 (s, 1H), 6.36 (d, 1H), 5.02 (broad s, 1H), 4.68 (d, 2H), 3.88 (t, 1H), 3.81 (dd, 1H), 3.61 (dd, 1H), 2.39 (S, 3H). 19 F NMR (CDCl 3): d-78.43. Step D: Preparation of 4- [5- (3,5-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl-2-methyl-N- (2-pyridinylmethyl) benzamide) Combine and stir at room temperature environment for 5 h 4- [[2- (3,5-diclofenyl) -2-hydroxy-3,3,3-trifluoropropyl] -amino-2-methyl-N- (2-pyridinylmethyl) benzamide (i.e. the product from step C) (0.21 g, 0.42 mmole), 1,1'-carbonyldiimidazole (0.13 g, 0.79 mmole), PS-DMAP (Riley Co., 0.065 g, 0.12 mmole) and 7 ml of dichloromethane. More 1, 1'-carbonyldiimidazole (0.05 g, 0.31 mmol) is added. After stirring for 22 h, more 1, 1'-carbonyldiimidazole (0.15 g, 0.92 mmol) and PS_DMAP (0.31 g, 0.43 mmol) are added. After stirring for 24 h, the reaction mixture is concentrated under reduced pressure and purified by medium pressure chromatography on silica gel using ethyl acetate / hexanes (6: 8) as eluent to give the title product, a compound of the present invention as 0.20 g of a whitish vitreous solid. XH NMR (CDC13): d 8.52 (d, 1H), 7.71 (t, 1H), 7.54-7.20 (m, 9H), 4.73 (d, 2H), 4.63 (d, 1H), 4.30 (d, 1H) 2.51 (s, 3H). 19 F NMR (CDCl 3): d-81.52. EXAMPLE 3 Preparation of 4- [5- (3,5-dichlorophenyl) -2-oxide-5- (trifluoromethyl) -1,2,3-oxathiazolidin-3-yl] -2-methyl-N- (2-pyridinylmethyl) ) benzamide To a stirred solution of 4- [[2- (3,5-dichlorophenyl) -2-hydroxy-3,3,3-trifluoropropyl] amino] -2-methyl-N- (2-pyridinylmethyl) benzamide (is say, the product of Example 2, Step C) (0.11 g, 0.22 mmol), triethylamine (0.096 g, 0.95 mmol) and 4- (dimethylamino) pyridine (0.022 g, 0.018 mmol) in 2 mL of dichloromethane is added dropwise to chloride. of thionyl (0.043 g, 0.36 mmol). After stirring for 1 h at room temperature, more thionyl chloride (0.026 g, 0.22 mmol) is added. After stirring an additional 1 h, the reaction mixture is concentrated under reduced pressure and the crude product is purified by medium pressure chromatography on silica gel using ethyl acetate / hexane (3: 6) as eluent to provide the title product. (mixture of diastereomers 1: 1), a compound of the present invention as 0.04 g of an off-white solid. X H NMR (CDCl 3): d 8.50 (m, 1H), 7.69 (broad t, 1H), 7. 49 (m, 4H), 7.33 (m, 1H), 7.22 (m, 2H), 6.93 (m, 2H), 4.73 (d, 1H), 4.41 (d, 1H), 4.70 (d, 0.5H), 4.56 (d, 0.5H), 4.38 (d, 0.5H), 4.20 (d, 0.5H), 2.50 (s, 1.5H), 2.47 (s, 1.5H). 19 F NMR (CDCl 3): d -76.31, -79.67. EXAMPLE 4 Preparation of 2-nitro-5- [2-oxo-5-phenyl-5- (trifluoromethyl) -3-oxazolidinyl] benzonitrile Step A: Preparation of 5-phenyl-5- (trifluoromethyl) -2-oxazolidione A cold solution (less than 20SC) of lithium tetrahydroaluminate (10.0 ml, 1.0 M solution in diethyl ether) is added a solution of -hydroxy-a- (trifluoromethyl) benzeneacetonitrile (Aldrich, 2.01 g, 10.0 mmol) in 10 ml of anhydrous diethyl ether . The resulting suspension is stirred at room temperature for 3 h. To the reaction mixture are added sequentially 0.38 ml of water, an aqueous solution of sodium hydroxide (15% by weight, 0.38 ml) and an additional 1.14 ml of water. The reaction mixture is filtered through a glass frit and the filtrate is concentrated under reduced pressure to provide 1.89 g of a white solid. The white solid (1.23 g, 6.0 mmol) is dissolved in 15 ml of dichloromethane and added to 15 ml of a saturated and stirred aqueous solution of sodium hydrogen carbonate. Then a solution of triphosgene bis (trichloromethyl) carbonate (0.63 g, 2.17 mmol) in 5 ml of dichloromethane is added dropwise over several minutes. The reaction mixture is stirred at room temperature for 1 h. The solvent phases are separated and the organic phase is washed with water, 1 N aqueous hydrochloric acid and a saturated aqueous solution of sodium chloride. The organic extracts are dried with MgSO 4, filtered and the solvent is concentrated under reduced pressure to provide 1.35 g of the title compound as a white solid. X H NMR (CDC13): d 7.5-7.4 (m, 5H), 5.95 (broad s, 1H), 4.26 (d, 1H), 3.93 (d, 1H). Step B: Preparation of 2-nitro-5- [2-oxo-5-phenyl-5- (trifluoromethyl) -3-oxazolidinyl] benzonitrile To a stirred solution of 5-phenyl-5- (trifluoromethyl) -2-oxazolidinone ( that is, the product of Etap A). { 0.97 g, 4.2 mmol) in 20 mL of N, -dimethylformamide under a nitrogen atmosphere is added sodium hydride in one portion (60%, 0.21 g, 5.2 mmol). After 0.33 h, 5-chloro-2-nitrobenzonitrile (1.15 g, 6.3 mmol) is added to the reaction mixture. The reaction mixture is stirred for 16 h, diluted with water, extracted with 100 ml of ether and 100 ml of ethyl acetate. The combined organic extracts are washed with water (75 ml, 4 times), dried over MgSO, filtered and concentrated under reduced pressure to give a solid which is purified by chromatography on silica gel and by trituration with 20% ether. hexanes to provide the title product, a compound of the present invention, as 0.235 g of a white solid. RM XH (CDC13): d 8.4 (m, 1H), 8.1 (m, 1H), 8.07 (s, 1H), 7.6-7.45 (m, 5H), 4.75 (d, 1H), 4.41 (d, 1H) . EXAMPLE 5 Preparation of 4- [4- (3,5-dichlorophenyl) -2-oxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide Step A: Preparation of the ester ethyl 3,3,3-trifluoro-2-hydroxy-N- [(2-phenylmethoxy) carbonyl] alanine A solution of 3,3,3-trifluoro-2-oxopropionic acid ethyl ester (Alfa Chem. Co. , 12.0 g, 70.6 mmol) and benzyl carbamate (9.78 g, 64.8 mmol) in 55 ml of methylene chloride are stirred for 66 h at room temperature under nitrogen. The solvent is removed under reduced pressure. 100 ml of hexane is added to the crude mixture, and the resulting suspension allowed to stand overnight. The solid is collected by vacuum filtration, washed with hexane and air dried to provide 20.4 g of the title compound as a white solid. RM XH (CDC13): d 7.35 (m, 5H), 5.98 (s, 1H), 5.35 (s, 1H), 5.23 (s, 2H), 4.36 (m, 2H), 1.30 (t, 3H). Step B: Preparation of ethyl 3, 3, 3-trifluoro-2- [[(phenylmethoxy) -carbonyl] imino] propanoate To a solution of 3-ethyl ester., 3, 3-trifluoro-2-hydroxy-N- [(phenylmethoxy) carbonyl] alanine (ie, the product of Step A) (15.4 g, 48 mmol) and pyridine (7.9 g, 50 mmol) in 200 ml of anhydrous diethyl ether at ice bath temperature are added dropwise to trifluoroacetic anhydride (10.75 g, 51.1 mmol). The resulting suspension is warmed to room temperature and stirred for 1.5 h. The reaction mixture is filtered to remove a white solid. The filtrate is concentrated in vacuo to provide a suspension. 150 ml of hexane is added to the suspension which is filtered again to remove a white solid. The filtrate is concentrated in vacuo to provide the title compound as 14.2 g of a colorless oil. NMR X (CDCI3): d 7.41 <; m, 5H), 5.33 (s, 2H), 4.31 (c, 2H), 1.30 (t, 3H).
Step C: Preparation of 3,5-dichloro-a- [[(phenylmethoxy) -carbonyl] amino] -a- (trifluoromethyl) benzene-ethyl acetate To a solution of 3, 3, 3 - 1 rif luoro- 2 - [[ (f -methylmethoxy) carbonyl] imino] ethyl clothingnoate (i.e., the product from step B) (7.36 g, 24.3 mmol) in 10 ml of desired anhydrous tert-furane with a dry ice bath, a solution is added of bromide of 3, 5 -di c 1 gold f eni Imagnes io (Aldrich Chem. Co., 0.5 M in tetrahydrofuran, 50 ml, 25 mmol) for 45 minutes. The turbid reaction mixture is stirred for 1 h and then heated to room temperature. To this yellow solution is added 37 ml of 1 M hydrochloric acid. The volume of tetrahydrofuran is removed under vacuum. The residue is partitioned between 170 ml of ethyl acetate and 100 ml of water. The aqueous layer is extracted with 50 ml of ethyl acetate. The combined organic layers are filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian), and concentrated under reduced pressure to provide 11.1 g of the title compound as a yellow oil. R XH (CDC13): d 7.34 (m, 8H), 6.10 (s, 1H), 5.07 (s, 2H), 4.28 (m, 2H), 1.21 (t, 3H). 19 F NMR (CDCl 3): d-71.03.
Step D: Preparation of 4- [4- (3,5-dichlorophenyl) -2,5-dioxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide A solution of Ethyl 3, 5-dichloro-a- [[(phenylmethoxy) carbonyl] amino] -a- (trifluoromethyl) benzene acetate (i.e., the product of step C) (1.11 g, 2.5 mmol), 4-amino-2 -methyl-N- (2-pyridinylmethyl) benzamide (i.e., the product of Step B of Example 2) (0.474 g, 1.95 mmol), 4- (dimethylamino) pyridine (68 mg, 0.55 mmol) in N-methyl -2-pyrrolidinone (NMP) is heated at 200 aC by microwave irradiation for 350 sec. Another test is carried out with 0.99 g of the product of step C, 0.44 g of the product of step B of Example 2, and 71 mg of 4-dimethylaminopyridine in 2 ml of NMP under the same conditions. The reaction mixtures of the tests are combined and diluted with 100 ml of ethyl acetate, washed with water (50 ml, three times), filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian). and concentrated under reduced pressure to provide a dark oil. This is purified by medium pressure silica gel chromatography using ethyl acetate / hexanes (45% -85%) as eluent to provide 0.84 g of the title compound as a tan solid. H NMR (DMSO-d6): d 10.65 (s, 1H), 8.99. { t, 1H), 8.52 (d, 1H), 7.89 (broad s, 3H), 7.80 (dt, 1H), 7.54 (d, 1H), 7.39 (d, 1H), 7.32-7.27 (m, 3H), 4.54 (d, 2H), 2.39 (s, 3H). Step E: Preparation of 4- [4- (3,5-dichlorophenyl) -5-hydroxy-2-oxo-4- (trifluoromethyl) -1-imidazolidinyl j -2-methyl-N- (2-pyridinylmethyl) -enganamide A a suspension of 4- [4- (3,5-dichlorophenyl) -2,5-dioxo-4-. { trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide (ie, the product of step D), (0.66 g, 1.23 mmol) in 18 ml of methanol at bath temperature with ice Sodium borohydride (0.275 g, 7.3 mmol) is added in small batches for 3 minutes. The resulting orange solution is stirred at room temperature for 18 hours. The solvent is removed under vacuum and the residue is partitioned between 50 ml of ethyl acetate and 50 ml of water. The aqueous layer is extracted with 35 ml of ethyl acetate. The combined organic layers are filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian) and concentrated under reduced pressure to provide 0.59 g of the title compound as a tan solid. X H NMR (DMSO-d 6): d 9.17 (s, 1 H), 8.78 (t, 1 H), 8.52 (d, 1 H), 7.79. { dt, 1H), 7.5 (t, 1H), 7.61 (m, 3H), 7.52 (d, 1H), 7.45 (d, 1H), 7.37 (d, 1H), 7.27 (dd, 1H), 6.91 (d , 1H), 6.12 (d, 1H), 4.52 (d, 2H), 2.39 (s, 3H).
Stage F: Preparation of 4- [4- (3, 5-dichlorophenyl) -2-oxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl- - (2-pyridinylmethyl) enamide To a solution of 4- [4- (3,5-dichlorophenyl) -5 -hydroxy-2-OXO-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide (ie, the product of Step E) (0.18 g, 0.33 mmole) in 4 My trifluoroacetic acid at ice bath temperature is added sodium borohydride (0.10 g, 2.6 mmol) in two batches. After the initial vigorous reaction ceases, the reaction mixture is stirred at room temperature. An additional batch of 0.048 g of sodium borohydride is added after 2 h. The reaction mixture is stirred for 18 h and then 5 ml of water are added. The reaction mixture is cooled with an external ice / water bath and then a sodium hydroxide solution (4.1 g of 50% aqueous solution and 10 ml of water) is added. The reaction mixture is extracted with ethyl acetate (25 ml, twice) and the combined organic layers are filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian) and concentrated under reduced pressure to provide a gummy solid. Another test is carried out using 90 mg of the product of step E, 2 ml of trifluoroacetic acid and 67 mg of sodium borohydride under similar conditions. The crude products from these two tests are combined and purified by medium pressure chromatography on silica gel using ethyl acetate / hexanes (45% -65%) as eluent to provide 0.18 g of the title compound, a compound of the present invention , like a whitish solid. RM XH (CDCl 3): d 8.51 (d, 1H), 7.70 (dt, 1H), 7.52-7.30 (m, 8H), 7.23 (dd, 1H), 6.65 (s, 1H), 4.74 (d, 2H) , 4.52 (d, 1H), 4.13 (d, 1H), 2.51 (s, 3H).
EXAMPLE 6 Preparation of 4- [4- (3,5-dichlorophenyl) -3-methi1-2 -oxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide Step A : Preparation of 4- [4- (3,5-dichlorophenyl) -3-methyl-2, 5-dioxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide A a solution of 4- [4- (3,5-dichlorophenyl) -2,5-dioxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide (i.e. product from step D of Example 5) (0.39 g, 0.73 mmol) in 4 ml of N, N-dimethylformamide was added sodium hydride (60% oil dispersion, 0.0335 g, 2.3 mmol). After stirring for 15 min, iodomethane (0.179 g, 1.26 mmol) is added. The reaction mixture is stirred for 45 min and then divided between 50 ml of ethyl acetate and 25 ml of water. The organic layer is washed with water (25 ml, twice) and filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian) and concentrated under reduced pressure to provide 0.39 g of the title compound as a vitreous solid. RM XH (DMSO-d6): d 9.00 (t, 1H), 8.53 (d, 1H), 7.93 (s, 1H), 7.80 (dt, 1H), 7.69 (s, 2H), 7.56 (s, 1H), 7.39 (m, 3H), 7.28 (dd, 1H), 4.56 (d, 2H), 3.00 (s) s, 3H), 2.40 (s, 3H). Step B: Preparation of 4- [4- (3,5-dichlorophenyl) -5-hydroxy-3-methyl-2-oxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2 - pyridinylmethyl) benzamide To a cloudy solution of 4- [4- (3,5-dichlorophenyl) -3-methyl-2,5-dioxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2 pyridinylmethyl) benzamide (the product of step A) (0.37 g, 0.67 mmol) in 10 ml of methanol is added sodium borohydride (0.167 g, 4.42 mmol) in small batches for 5 min. After stirring for 4.5 h, methanol was removed under vacuum and the residue was partitioned between 50 ml of ethyl acetate and 50 ml of water. The aqueous layer is extracted with 35 ml of ethyl acetate and the combined organic layers are filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian) and concentrated under reduced pressure to provide 0.32 g of the title compound. like a solid cinnamon. XH NMR (DMSO-d6): d '8.75 (t, 1H), 8.50 (d, 1H), 7.81 (s, 1H), 7.78 (dt 1H), 7.56 (d, 1H), 7.46-7.31 (m, 6H), 7.26 (dd, 1H), 5.81 (d, 1H), 4.51 (d, 2H), 2.97 (s, 3H), 2.34 (s, 3H). Step C: Preparation of 4- [4- (3,5-dichlorophenyl) -3-methyl-2-oxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) -enomamide A a cloudy solution of 4- [4- (3,5-dichlorophenyl) -5-hydroxy-3-methyl-2-oxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) ) benzamide (ie the product of step B) (0.25 g, 0.45 mmol) in 6 ml of trifluoroacetic acid is added sodium borohydride (0.14 g, 3.7 mmol) in batches for 3 min. After stirring for 1 h at room temperature an additional amount of sodium borohydride (0.104 g, 2.7 mmol) is added. After stirring for an additional 18 h, 10 ml of water are added. The reaction mixture is cooled with an external ice / water bath and then a solution of sodium hydroxide (6 ml of 50% aqueous solution and 20 ml of water) is added. The reaction mixture is extracted with ethyl acetate (50 ml, 1 time, 35 ml, 1 time) and the combined organic layers are filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by vary) and concentrated under reduced pressure to provide a gummy solid which is purified by medium pressure silica gel chromatography using ethyl acetate / hexanes (45% -65%) as eluent to provide the title compound, a compound of the present invention as 0.20 g of a white solid. XR NMR (CDClj): d 8.53 (d, 1H), 7.69 (dt, 1H), 7.51 (d, 1H), 7.45 (m, 2H), 7.34 (m, 4H), 7.22 (dd, 1H), 7.13 (broad t, 1H), 4.73 (d, 2H), 4.31 (d, 1H), 3.83 (d, 1H), 2.90 (s, 3H), 2.51 (s, 3H). By the methods described herein in conjunction with the methods known in the art, the following compounds of Tables 1 to 15 can be prepared. The following abbreviations are used in the tables that follow: CN means cyano, N02 denotes nitro, Ph means phenyl, Py means pyridinyl, Me means methyl, Et means ethyl, i-Pr means isopropyl and OMe means methoxy. As shown, (R2) m refers to the combination of (P ^ n) with the instance where Z is CR2, as specified for formula 1. Table 1 where m is l, 2, 3, 4 or 5. 3-Cl, 4-FHH CH2CF3 3-Cl, 4-FHH CH2-2-Py -Cl, 4-CF3 HH CH2CF3 3-Cl, 4-CF3 HH CH2-2-Py -Cl, 4-Br HH CH2CF3 3 -Cl, 4-Br HH CH2-2-Py 3-CF3 H H CH2CF3 3-CF3 H H CH2-2-Py -CF3, 5-CF3 H H CH2CF3 3-CF3, 5-CF3 H H CH2-2-Py 3-Br H H CH2CF3 3-Br H H CH2-2-Py-Br, 5-Br H H CH2CF3 3-Br, 5-Br H H CH2-2-Py 3-Cl N02 H CH2CF3 3-Cl N02 H CH2-2-Py -Cl, 4-Cl N02 H CH2CF3 3-Cl, 4-Cl N02 H CH2-2-Py-Cl, 5-Cl N02 H CH2CF3 3- Cl, 5-C1 N02 H CH2-2-Py 3-C1, 4-F N02 H CH2CF3 3-Cl, 4-F N02 H CH2-2-Py -Cl, 4-CF3 N02 H CH2CF3 3-Cl, 4-CF3 N02 H CH2-2-Py -Cl, 4-Br N02 H CH2CF3 3-Cl, 4-Br N02 H CH2-2-Py 3-CF3 N02 H CH2CF3 3-CF3 N02 H CH2-2-Py -CF3, 5-CF3 N02 H CH2CF3 3-CF3, 5-CF3 N02 H CH2-2-Py 3-Br N02 | H CH2CF3 3-Br N02 H CH2-2-Py-Br, 5-Br N02. H CH2CF3 3-Br, 5-Br N02 H CH2-2-Py 3-Cl CH3H CH2CF3 3-Cl CH3 H CH2-2-Py-Cl, 4-C1 CH3 H CH2CF3 3-Cl, 4-C1 CH3 H CH2-2-Py -Cl, 5-C1 CH3 H CH2CF3 3- Cl, 5-C1 CH3 H CH2-2-Py 3-Cl, 4-F CH3H CH2CF3 3-Cl, 4-F CH3 H CH2-2-Py-Cl, 4-CF3 CH3 H CH2CF3 3-Cl, 4-CF3 CH3 H CH2-2-Py -Cl, 4-Br CH3 H CH2CF3 3-Cl, 4-Br CH3 H CH2-2-Py 3-CF3 CH3 H CH2CF3 3-CF3 CH3 H CH2-2-Py -CF3, 5-CF3 CH3 H CH2CF3 3-CF3, 5-CF3 CH3 H CH2-2-Py 3-Br CH3 H CH2CF3 3-Br CH3 H CH2-2-Py-Br, 5-Br CH3 H CH2CF3 3-Br, 5-Br CH3 H CH2-2-Py 3-Cl Cl H CH2CF3 3-Cl Cl H CH2-2-Py-Cl, 4-Cl Cl H CH2CF3 3-Cl, 4-Cl Cl H CH2-2-Py-Cl, 5-Cl Cl H CH2CF3 3- Cl, 5-C1 Cl H CH2-2-Py 3-Cl, 4-Cl Cl H CH2CF3 3-Cl, 4-Cl Cl H CH2-2-Py-Cl, 4-CF3 Cl H CH2CF3 3-Cl, 4-CF3 Cl H CH2-2-Py -Cl, 4-Br Cl H CH2CF3 3-C1, 4-Br Cl H CH2-2-Py 3-CF3 Cl H CH2CF3 3-CFj Cl H CH2-2-Py -CF3, 5-CF3 Cl H CH2CF3 3-CF3, 5-CF3 Cl H CH2-2-Py 3-Br Cl H CH2CF3 3-Br Cl H CH2-2-Py-Br, 5-Br Cl H CH2CF3 3-Br, 5-Br Cl H CH2-2-Py 3-C1 CF3 H CH2CF3 3-C1 CF3 H CH2-2-Py-Cl, 4-C1 CF3 H CH2CF3 3-Cl, 4-C1 CF3 H CH2-2-Py -Cl, 5-C1 CF3 H CH2CF3 3- Cl, 5-C1 CF3 H CH2-2-Py 3-Cl, 4-F CF3 H CH2CF3 3-C1,, 4-F CF3 H CH2-2-Py-Cl, 4-CF3 CF3 H CH2CF3 3-Cl, 4-CF3 CF3 H CH2-2-Py -C1 , 4-Br CF3 H CH2CF3 3-C1, 4-Br CF3 H CH2-2-Py 3-CF3 CF3 H CH2CF3 3-CFj CF3 H CH2-2-Py -CF3, 5-CF3 CF3 H CH2CF3 3-CF3, 5-CF3 CF3 H CH2-2-Py 3-Br CF3 H CH2CF3 3-Br CF3 H CH2-2-Py-Br, 5-Br CF3: H CH2CF3 3-Br, 5-Br CF3 H CH2-2-Py 3-C1CNH CH2CF3 3-C1CNH CH2-2-Py -Cl, 4-C1CNH CH2CF3 3-Cl, 4-C1CNH CH2-2-Py -Cl, 5-C1CN H CH2CF3 3- Cl, 5-CI CN H CH2-2-Py 3-Cl, 4-F CN H CH2CF3 3-Cl, 4-F CN H CH2-2-Py-Cl, 4-CF3 CN H CH2CF3 3-Cl, 4-CF3 CN H CH2-2-Py -C1, 4-Br CN H CH2CF3 3-C1, 4-Br CN H CH2-2-Py 3-CF3 CN H CH2CF3 3-CF3 CN H CH2-2-Py -CF3, 5-CF3 CN H CH2CF3 3-CF3, 5-CF3 CN H CH2-2-Py 3-Br CN H CH2CF3 3-Br CN H CH2-2-Py-Br, 5-Br CN H CH2CF3 3-Br, 5-Br CN H CH2-2-Py 3-C1 OMe H CH2CF3 3-C1 OMe H CH2-2-Py -Cl, 4-C1 OMe H CH2CF3 '3-Cl, 4-C1 OMe H CH2-2-Py -Cl, 5-C1 OMe H CH2CF3 3 -Cl, 5-C1 OMe H CH2-2-Py 3-Cl, 4-F OMe H CH2CF3 3-Cl, 4-F OMe H CH2-2-Py-Cl, 4-CF3 OMe H CH2CF3 3-Cl, 4-CF3 OMe H CH2-2-Py -C1, 4-Br OMe H CH2CF3 3-C1, 4-Br OMe H CH2-2-Py 3-CF3 OMe H CH2CF3 3-CFj OMe H CH2-2-Py -CF3, 5-CF3 OMe H CH2CF3 3-CF3, 5-CF3 OMe H CH2-2-Py 3-Br OMe H CH2CF3 3-Br O and H CH2-2-Py 3-Br, 5-Br OMe H CH2CF3 3-Br, 5-Br OMe H CH2-2-Py 3-C1 H H CH 2 CH 3 3-C1 H H CH 2 CH 3 3-Cl, 4-C1 H H CH 2 CH 3 3-Cl, 4-C1 K H CH 2 CH 3 3-Cl, 5-C1 H H CH2CH3 3-Cl, 5-C1 H H CH2CH3 3-Cl, 4-F H H CH 2 CH 3 3-Cl, 4-F H H CH 2 CH 3 -Cl, 4-CF 3 H H CH 2 CH 3 3-Cl, 4-CF 3 H H CH 2 CH 3 3-C1, 4-Br H H CH 2 CH 3 3-C1, 4-Br H H CH 2 CH 3 3-CF3 H H CH2CH3 3-CF3 H H CH2CH3 -CF3, 5-CF3 H H CH2CH3 3-CFj, 5-CFj H H CH2CH3 3-Br H H CH 2 CH 3 3-Br H H CH 2 CH 3 3-Br, 5-Br H H CH 2 CH 3 3-Br, 5-Br H H CH 2 CH 3 3-C1 N02 H CH2CH3 3-C1 CN H CH2CH3 3-Cl, 4-C1 N02 H CH2CH3: 3-Cl, 4-C1CN H CH2CH3 3-Cl, 5-C1 N02H CH2CH3 3-Cl, 5-C1CN H CH2CH3 3-Cl, 4-F N02H CH2CH3 3-Cl, 4-F CN H CH2CH3-Cl, 4-CF3 N02 H CH2CH3 3-Cl, 4-CF3 CN H CH2CH3 3-C1, 4-Br N02 H CH2CH3 3-C1, 4-Br CN H CH2CH3 3-CF3 N02 H CH2CH3 3-CF3 CN H CH2CH3 -CF3, 5-CF3 N02 H CH2CH3 3-CF3, 5-CF3 CN H CH2CH3 3-Br N02 H CH2CH3 3-Br CN H CH2CH3 3-Br, 5-Br N02 H CH2CH3 3-Br, 5-Br CN H CH2CH3 3-C1 CH3 H CH2CH3 3-C1 OMe H CH2CH3 3-Cl, 4-C1 CH3H CH2CH3 3-Cl, 4-C1 OMe H CH2CH3 3-Cl, 5-C1 CH3H CH2CH3 3-Cl, 5-C1O and H CH2CH3 3-Cl, 4-F CH 3 H CH 2 CH 3 3-Cl, 4-F OMe H CH 2 CH 3 -Cl, 4-CF 3 CH 3 H CH 2 CH 3 3-Cl, 4-CF 3 OMe H CH 2 CH 3 3-C1, 4-Br CH3H CH2CH3 · 3-C1, 4-Br OMe H CH2CH3 3-CF3 CH3 H CH2CH3 3-CF3 OMe H CH2CH3 -CF3, 5-CF3 CH3 H CH2CH3 3-CF3, 5-CF3 O and H CH2CH3 3-Br CH3 H CH2CH3 3-Br OMe H CH2CH3 3-Br, 5-Br CH3 H CH2CH3 3-Er, 5-Br OMe H CH2CH3 3-Cl Cl H CH 2 CH 3 3-Cl, 4-Br Cl H CH 2 CH 3 3-Cl, 4-C1 Cl H CH2CH3 3-CF3 Cl H CH2CH3 3-Cl, 5-C1 Cl H CH 2 CH 3 3-CF 3, 5-CF 3 Cl H CH 2 CH 3 3-Cl, 4-F Cl H CH 2 CH 3 3-Br Cl H CH 2 CH 3 3-Cl, 4-CF3 Cl H CH 2 CH 3 3-Cl, 4-CF 3 Cl H CH 2 CH 3 3-Cl, 5-C1 CN Me CH2CF3 3-Cl, 5-C1 CN Me CH2-2-Py 3-Cl, 5-C1CN CH2OCH3CH2CF3 3-Cl, 5-C1CN CH2OCH3 CH2-2-Py 3-Cl, 5-C1 N02 Me CH2CF3 3-Cl, 5-C1 N02 Me CH2-2-Py 3-Cl, 5-C1 N02 CH2OCH3 CH2CF3 3-Cl, 5-C1 N02 CH2OCH3 CH2-2-Py 3-Cl, 5-C1 Cl and CH2CF3 3-Cl, 5-C1 Cl Me CH2-2-Py 3-Cl, 5-C1 Cl CH2OCH3 CH2CF3 3-Cl, 5-Cl Cl CH2OCH3 CH2-2-Py 3-Cl, 5-C1 CH3 Me CH2CF3 3-Cl, 5-C1 CH3 and CH2-2-Py 3-Cl, 5-C1 CH3 CH2OCH3 CH2CF3 3-Cl, 5-C1 CH3 CH2OCH3 CH2-2-Py Table 2 CN H H CH2CF3 CN H H CH2-2-Py H N02 H CH2CF3 H N02 H CH2-2-Py Me N02 H CH2CF3 Me N02 H CH2-2-Py CH2CH3 N02 H CH2CF3 CH2CH3 N02 H CH2-2-Py CH2CF3 N02 H CH2CF3 CH2CF3 N02 H CH2-2-Py CN N02 H CH2CF3 CN N02 H CH2-2-Py H CH3 H CH2CF3 H CH3 H CH2-2-Py I CH3 H CH2CF3 Me CH3 H CH2--2-Py CH2CH3 CH3 H CH2CF3 CH2CH3 CH3 H CH2-2-Py CH2CF3 CH3 H CH2CF3. CH2CF3 CH3 H CH2-2-Py CN CH3 H CH2CF3 CN CH3 H CH2-2-Py H Cl H CH2CF3 H Cl H CH2-2-Py Me Cl H CH2CF3 Me Cl H CH2-2-Py CH2CH3 Cl H CH2CF3 CH2CH3 Cl H CH2-2-Py CH2CF3 Cl H CH2CF3 CH2CF3 Cl H CH2-2-Py CN Cl H CH2CF3 CN Cl H CH2-2-Py H CF3 H CH2CF3 H CF3 H CH2-2-Py Me CF3 H CH2CF3 Me CF3 H CH2-2-Py CH2CH3 CF3 H CH2CF3 CH2CH3 CF3 H CH2-2-Py CH2CF3 CF3 H CH2CF3 CH2CF3 CF3 H CH2-2-Py CN CF3 H CH2CF3 CN CF3 H CH2-2-Py H CN H CH2CF3 H CN H CH2-2-Py I CN H CH2CF3 Me CN H CH2-2-Py CH2CH3 CN H CH2CF3 CH2CH3 CN H CH2-2-Py CH2CF3 CN H CH2CF3 CH2CF3 CN H CH2-2- Py CN CN H CH2CF3 CN CN H CH2-2- Py H OMe H CH2CF3 H OMe H CH2-2- Py Me OMe H CH2CF3 Me OMe H CH2-2- Py CH2CH3 OMe H CH2CF3 CH2CH3 OMe H CH2-2- Py CH2CF3 OMe H CH2CF3 CH2CF3 OMe H CH2-2- Py CN OMe H CH2CF3 CN OMe H CH2-2- Py H H H CH2CH3 H CF3 H CH2CH3 Me H H CH2CH3 Me CF3 H CH2CH3 CH2CH3 H H CH2CH3 CH2CH3 CF3 H CH2CH3 CH2CF3 H H CH2CH3 CH2CF3 CF3 H CH2CH3 CN H H CH2CH3 CN CF3 H CH2CH3 H N02 H CH2CH3 H CN H CH2CH3 Me N02 H CH2CH3 Me N02 H CH2CH3 CH2CH3 N02 H CH2CH3 CH2CH3 N02 H CH2CH3 CH2CF3 N02 H CH2CH3 CH2CF3 N02 H CH2CH3 CN N02 H CH2CH3 CN CN H CH2CH3 · H CH3 H CH2CH3 H CH3 H CH2CH3 I CH3 H CH2CH3 Me OMe H CH2CH3 CH2CH3 CH3 H CH2CH3 CH2CH3 OMe H CH2CH3 CH2CF3 CH3 H CH2CH3 CH2CF3 OMe H CH2CH3 CN CH3 H CH2CH3 CN OMe H CH2CH3 H C l H CH2CH3 CH2CF3 C l H CH2CH3 Me C l H CH2CH3 CN C l H CH2CH3 CH2CH3 Cl H CH2CH3 H CN Me CH2CF3 H CN Me CH2-2-Py I CN CH2OCH3 CH2CF3 Me CN CH2OCH3 CH2-2-Py H N02 Me CH2CF3 H N02 Me CH2-2-Py Me N02 CH2OCH3 CH2CF3 Me N02 CH2OCH3 CH2-2-Py H Cl Me CH2CF3 H Cl Me CH2-2-Py Me Cl CH2OCH3 CH2CF3 Me Cl CH2OCH3 CH2-2-Py H CH3 Me CH2CF3 H CH3 Me CH2-2-Py I CH3 CH2OCH3 CH2CF3 Me CH3 CH2OCH3 CH2-2-Py Table 3 where m is 1, 2, 3, 4, or 5. (R2) m R5 W (R2) m R5 W 3-C1, 5-C1 CF3 W-1 3-C1, 5-C1 H W-1 3-C1, 4-F CF3 W-l 3-C1, 4-F H W-l 3-Br, 5-Br CF3 W-4 3-Br, 5-Br H W-4 3-Br CF3 W-4 3-Br H W-4 3-Cl, 5-C1 CH3 W-1 3-Cl, 5-C1 N02 W-1 3-Cl, 4-F CH3 W-l 3-Cl, 4-F N02 W-l 3-Cl, 4-C1 CH3 W-l 3-Cl, 4-C1 N02 W-1 3-CF3 CH3 W-l 3-CF3 N02 W-1 3-Br, 5-Br CH3 W-l 3-Br, 5-Br N02 W-l 3-Br CH3 W-l 3-Br N02 W-l 3-C1 CH3 W-2 3-C1 N02 W-2 3-Cl, 4-C1 CH3 W-2 3-Cl, 4-C1 N02 W-2 3-Cl, 5-C1 CH3 W-2 3-Cl, 5-C1 N02 W-2 3-Cl, 4-F CH3 -2 3-Cl, 4-F N02 W-2-Cl, 4-CF3 CH3 W-2 3-Cl, 4-CF3 N02 W-2 3-C1, 4-Br CH3 W-2 3-C1, 4-Br N02 W-2 3-CF3 CH3 W-2 3-CF3 N02 W-2 -CF3, 5-CF3 CH3 W-2 3-CF3, 5-CF3 N02 W-2 3-Br CH3 W-2 3-Br N02 -2 3-Br, 5-Br CH3 W-2 3-Br, 5-Br N02 W-2 3-Cl, 5-C1 CH3 W-3 3-Cl, 5-C1 N02 W-3 3-Cl, 4-F CH3 W-3 3-Cl, 4-F N02 W-3 3-Cl, 4-C1 CH3 W-3 3-Cl, 4-C1 N02 W-3 3-CF3 CH3 W-3 3-CF3 N02 W-3 3-Br, 5-Br CH3 W-3 3-Br, 5-Br 02 W-3 3-Br CH3 W-3 3-Br N02 W-3 3-Cl, 5-C1 CH3 W-4 3-Cl, 5-C1 N02 W-4 3-Cl, 4-F CH3 W-4 3-Cl, 4-F N02 W-4 3-Cl, 4-C1 CH3 W-4 3-Cl, 4-C1 N02 W-4 3-CF3 CH3 W-4 3-CF3 N02 W-4 3-Br, 5-Br CH3 W-4 3-Br, 5-Br N02 W-4 3-Br CH3 W-4 3-Br N02 W-4 3-Cl, 5-C1 Cl W-l 3-Cl, 5-C1 OMe W-1 3-Cl, 4-F Cl W-l 3-Cl, 4-F OMe W-l 3-Cl, 4-C1 Cl W-l 3-Cl, 4-C1 OMe W-1 3-CF3 Cl W-l 3-CF3 OMe W-1 3-Br, 5-Br Cl W-l 3-Br, 5-Br OMe W-1 3-Br Cl W-l 3-Br OMe W-l 3-Cl Cl W-2 3-Cl OMe W-2 3-Cl, 4-C1 Cl W-2 3-Cl, 4-C1 OMe W-2 3-Cl, 5-C1 Cl W-2 3-Cl, 5-C1 OMe W-2 3-Cl, 4-F Cl W-2 3-Cl, 4-F OMe W-2 3-Cl, 4-CF3 Cl W-2 3-Cl, 4-CF3 OMe W-2 3-Cl, 4-Br Cl W-2 3-Cl, 4-Br OMe W-2 3-CF3 Cl W-2 3-CF3 OMe W-2 3-CF3, 5-CF3 Cl W-2 3-CF3, 5-CF3 OMe W-2 3-Br Cl W-2 3-Br OMe W-2 3-Br, 5-Br Cl W-2 3-Br, 5-Br OMe W-2 3-Cl, 5-C1 Cl W-3 3-Cl, 5-C1 OMe W-3 3-Cl, 4-F Cl W-3 3-Cl, 4-F OMe W-3 Table 4 W-l W-2 W-3 W-4 where m is l, 2, 3, 4, or 5.
(R2) »R3 R5 W (R2) m R3 R5 W-C1, 5-Cl HH Wl 3-C1, 5-Cl HH W-2 -C1, 5-Cl Me H Wl 3-C1, 5-Cl Me H W-2 -C1, 5-Cl CH2CH3 H Wl 3-C1, 5-Cl CH2CH3 H W-2 -C1, 5-Cl CH2CF3 H Wl 3-C1, 5-Cl CH2CF3 H W-2 -C1, 5 -Cl CN H Wl 3-C1, 5-Cl CN H W-2 -C1, 5-Cl H N02 Wl 3-C1, 5-Cl H N02 W-2 -C1, 5-Cl Me N02 Wl 3-C1 , 5-Cl Me N02 W-2 -C1, 5-Cl CH2CH3 N02 Wl 3-C1, 5-Cl CH2CH3 N02 W-2 -C1, 5-Cl CH2CF3 N02 Wl 3-C1, 5-Cl CH2CF3 N02 W- 2 -C1, 5-Cl CN N02 Wl 3-C1, 5-Cl CN N02 W-2 -C1, 5-Cl H CH3 Wl 3-C1, 5-Cl H CH3 W-2 -C1, 5-Cl Me CH3 Wl 3-C1, 5-Cl Me CH3 W-2 -C1, 5-Cl CH2CH3 CH3 Wl 3-C1, 5-Cl CH2CH3 CH3 W-2 -C1, 5-Cl CH2CF3 CH3 Wl. 3-C1, 5-Cl CH2CF3 CH3 W-2 -C1, 5-Cl CN CH3 Wl · 3-C1, 5-Cl CN CH3 W-2 3-Cl, 5-C1 H Cl Wl 3-C1 5-C1 H Cl W-2 3-C1, 5-C1 Me Cl Wl 3-C1 5-C1 Me Cl W-2 3-C1, 5-C1 CH2CH3 Cl Wl 3-C1 5-C1 CH2CH3 Cl W-2 3-C1 , 5-C1 CH2CF3 Cl Wl 3-C1 5-C1 CH2CF3 Cl W-2 3-C1, 5-C1CN Cl Wl 3-C1 5-C1CNC Cl W-2 3-C1, 5-C1 H CF3 Wl 3 -C1 5-C1 H CF3 W-2 3-C1, 5-C1 Me CF3 Wl 3-C1 5-C1 Me CF3 W-2 3-C1, 5-C1 CH2CH3 CF3 Wl 3-C1 5-C1 CH2CH3 CF3 W -2 3-C1, 5-C1 CH2CF3 CF3 Wl 3-C1 5-C1 CH2CF3 CF3 W-2 3-C1, 5-C1 CN CF3 Wl 3-C1 5-C1 CN CF3 W-2 3-C1, 5- C1 H CN Wl 3-C1 5-C1 H CN W-2 3-C1, 5-C1 Me CN Wl 3-C1 5-C1 Me CN W-2 3-C1, 5-C1 CH2CH3 CN Wl 3-C1 5 -C1 CH2CH3 CN W-2 3-C1, 5-C1 CH2CF3 CN Wl 3-C1 5-C1 CH2CF3 CN W-2 3-C1, 5-C1 CN CN Wl 3-C1 5-C1 CN CN W-2 3 -C1, 5-C1 H OMe Wl 3-C1 5-C1 H OMe W-2 3-C1, 5-C1 and OMe Wl 3-C1 5-C1 Me OMe W-2 3-C1, 5-C1 CH2CH3 OMe Wl 3-C1 5-C1 CH2CH3 OMe W-2 3-C1, 5-C1 CH2CF3 O e Wl 3-C1 5-C1 CH2CF3 OMe W-2 3-C1, 5-C1 CN OMe Wl 3-C1 5-C1 CN OMe W-2 3-C1, 5-C1 HH W-3 3-C1 5-C1 HH W-4 3-C1, 5-C1 Me H W-3 3-C1 5-C1 Me H W-4 3-C1, 5-C1 CH2CH3 H W-3 3-C1 5-C1 CH2CH3 H W-4 3 -C1, 5-C1 CH2CF3 H W-3 3-C1 5-C1 CH2CF3 H W-4 3-C1, 5-C1 CN H W-3 3-C1 5-C1 CN H W-4 3-C1, 5 -C1 H N02 W-3 3-C1 5-C1 H N02 W-4 3-C1, 5-C1 Me N02 W-3 3-C1 5-C1 Me N02 W-4 3-C1, 5-C1 CH2CH3 N02 W-3 3-C1 5-C1 CH2CH3 N02 W-4 3-C1, 5-C1 CH2CF3 N02 W-3 3-C1 5-C1 CH2CF3 N02 W-4 3-Br CH2CF3 CF3 W-2 |¾- -Brr CN CF3 W-2 3-Br H CN W-2 3-Br Me CN W-2 3-Br CH2CH3 CN W-2 3-Br CH2CF3 CN W-2 3-Br CN CN W-2 3-Br H OMe W-2 3-Br Me OMe -2 3-Br CH2CH3 OMe W-2 3-Br CH2CF3 OMe W-2 3-Br CN OMe W-2 3-Br CH2CF3 Cl W-2 3-Br CN Cl W-2 Table 5 2 W-4 W-5 W-6 Cl Me CH N W-5 Cl Me CH N W-6 CF3 Cl N CC1 W-5 CF3 Cl N CC1 W-6 CF3 H N CC1 W-5 CF3 H N CC1 W-6 CF3 Me N CC1 W-5 CF3 Me N CC1 W-6 Cl Cl NB CC1 W-5 Cl Cl NB CC1 W-6 Cl H N CDC1 W-5 Cl H N CDC1 W-6 Cl Me N CC1 W-5 Cl Me N CC1 W-6 Table 6 Br H Cl CH N W-2 Br H Cl CH N W-4 Br Me Cl CH N W-2 Br Me Cl CH M W-4 Cl H H CH N W-2 Cl H H CH N W-4 Cl Me H CH N W-2 Cl Me H CH N W-4 Cl H e CH N W-2 Cl H e CH N W-4 Cl Me Me CH N W-2 Cl Me e CH N W-4 Cl H Cl CH N W-2 Cl H Cl CH N W-4 Cl Me Cl CH N W-2 Cl Me Cl CH N W-4 Cl H H N CC1 W-2 Cl H H N CC1 W-4 Cl Me H N CC1 W-2 Cl Me H N CC1 W-4 Cl H Me N CC1 W-2 Cl H Me N CC1 W-4 Cl Me Me N CC1 W-2 Cl Me Me N CC1 W-4 Cl H Cl N CC1 W-2 Cl H Cl N CC1 W-4 Cl Me Cl N CC1 W-2 Cl Me Cl N CC1 W-4 Br H H CH N W-5 Br H H CH N W-6 Br Me H CH N W-5 Br Me H CH N W-6 Br H Me CH N W-5 Br H Me CH N W-6 Br Me Me CH N W-5 Br Me Me CH N W-6 Br H Cl CH N W-5 Br H Cl CH N W-6 Br Me Cl CH N W-5 Br Me Cl CH N W-6 Cl H H CH N W-5 Cl H H CH N W-6 Cl e H CH 'N W-5 Cl e H CH N W-6 ci H Me CH N W-5 Cl H Me CH; N W-6 Cl Me Me CH N W-5 Cl Me Me CH N W-6 Cl H Cl CH N W-5 Cl H Cl CH N W-6 Cl Me Cl CH N W-5 Cl Me Cl CH N W-6 Cl H H N CC1 W-5 Cl H H N CC1 W-6 Cl Me H N CC1 W-5 Cl e H N CC1 W-6 Cl H Me N CC1 W-5 Cl H Me N CC1 W-6 Cl Me Me N CC1 W-5 Cl Me Me N CC1 W-6 Cl H Cl N CC1 W-5 Cl H Cl N CC1 W-6 Cl Me Cl N CC1 W-5 Cl Me Cl N CC1 W-6 Table 7 Table 8 Cl Cl Me Me Cl H Cl CN H Me CN Me Cl CN Me Me CN H Cl N02 H Me N02 Me Cl N02 Me Me N02 H Cl 4 -morpholino H Me 4 -morpholino Me Cl 4-morpholino Me Me 4-morpholino H CN S02NHMe H N02 S02NHMe Me CN S02NHMe2 Me N02 S02NHMe2 H CN S02NMe2 H N02 S02NMe2 Me CN S02NMe2 Me N02 S02NMe2 H CN S02NHCH2CH2 = CH2 H N02 S02NHCH2CH2 = CH2 I CN S02NHCH2CH2 = CH2 Me N02 S02NHCH2CH2 = CH2 H CN S02NHCH2CF3 H N02 S02NHCH2CF3 Me CN SO2NHCH2CF3 Me N02 S02NHCH2CF3 H CN S02N (CH3) CH2CF3 H N02 S02N (CH3) CH2CF3 I CN S02N (CH3) CH2CF3 Me N02 S02N (CH3) CH2CF3 H CN S02NHCH2C = CH H N02 S02NHCH2C = CH I CN S02NHCH2C = CH Me N02 S02NHCH2C = CH H CN S02NCH2-2-Py H N02 S02NCH2-2-Py Me CN S02NHCH2-2-Py Me N02 S02NHCH2-2-Py H CN S02N (CH3) CH2-2-Py H N02 S02N (CH3) CH2-2-Py I CN S02N (CH3) CH2-2-Py Me NO2 S02N (CH3) CH2-2-Py H CN C (= S) NHMe H N02 C (= S) NHMe Table 9 CN C (0) NHCH2-2-Py N02 1H-1, 2,4-triazol-1-yl CN SO2NHCH2CF3 N02 4-morpholinyl CN S02NHCH2-2-Py H C (O) HEt CN 1-imidazoyl H C (0) NHCH 2 CF3 CN 1H-1, 2,4-triazol-l-yl H C (0) NHCH2-2-Py CN 4-morpholinyl H SO2NHCH2CF3 Me C (0) NHEt H S02NHCH2-2-Py Me C (0) NHCH2CF3 H 1 -imidazoyl Me C (0) NHCH2-2-Py H 1 H-1, 2,4-triazol-1-yl Me SO2NHCH2CF3 H 4 -morpholinyl Table 10 CF3 S (= 0) C (0) NHCH2CF3 H S (= 0) C (0) NHCH2CF3 CF3 S (0) 2 C (0) NHCH2CF3 H S (0) 2 C (0) NHCH2CF3 CF3 S (= 0) C (O) NHEt H S (= 0) C (O) NHEt CF3 S (0) 2 C (O) NHEt H S (0) 2 C (O) NHEt Cl S (= 0) 1 H-1,2,4-Me S (= 0) 1 H-1,2,4-triazol-triazol-1-yl 1-yl Cl S (0) 2 1 H -1,2, 4- Me S (0) 2 1 H-1, 2,4-triazol-triazol-1-yl 1-yl Cl S (= 0) C (0) NHCH 2-2-Py Me S (= 0) C (0 ) NHCH2-2-Py Cl S (0) 2 C (0) NHCH2-2-Py Me S (0) 2 C (0) NHCH2-2-Py Cl S (= 0) C (0) NHCH2CF3 Me S (= 0) C (0) NHCH2CF3 Cl S (0) 2 C (0) NHCH 2 CF 3 Me S (0) 2 C (0) NHCH 2 CF 3 Cl S (= 0) C (O) HEt Me S (= 0) C (0) NHEt Cl S (0) 2 C (0) NHEt Me S (0) 2 C (0) NHEt CN S (= 0) 1H-1, 2, 4- N02 S (= 0) 1 H-1, 2,4-triazol-triazol-1-yl 1-yl CN S (0) 2 1H-1,2, 4- N02 S (0) 2 1H-1, 2,4-triazol-triazol-1-yl 1-yl CN S (= 0) C (0) NHCH2-2-Py N02 S (= 0) C (0 ) NHCH2-2-Py CN S (0) 2 C (0) NHCH2-2-Py N02 S (0) 2 C (0) NHCH2-2-Py CN S (= 0) C (0) NHCH2CF3 N02 S (= 0) C (0) NHCH2CF3 CN S (0) 2 C (0) NHCH2CF3 N02 S (0) 2 C (0) NHCH2CF3 CN S (= 0) C < 0) NHEt N02 S (= 0) C (O) HEt CN S (0) 2 C (O) NHEt N02 S (0) 2 C (0) NHEt Table 11 H Cl C (O) NHEt H Me C (O) NHEt H Cl C (0) NHCH2CF3 H Me C (0) NHCH2CF3 H Cl C (0) NHCH2-2-Py H Me C (0) NHCH2-2-Py H Cl lH-1,2,4- H Me 1 H-1,2,4-triazol-triazol-l-yl 1-yl Me CN C (O) NHEt Me N02 C (O) NHEt e CN C (0) NHCH2CF3 Me N02 C (0) NHCH2CF3 Me CN C (0) NHCH2-2-Py Me N02 C (0) NHCH2-2-Py Me CN 1H-1,2,4- Me N02 lH-1,2, 4-triazol-triazol-l-yl 1-yl H CN C (O) NHEt H N02 C (O) NHEt H CN C (0) NHCH2CF3 H N02 C (0) NHCH2CF3 H CN C (0) NHCH2-2-Py H N02 C (0) NHCH2-2-Py H CN 1H-1,2,4- H N02 1H-1, 2,4-triazol-triazol-l-yl 1-yl Table 12 Table 13 Table 14 where m is 1, 2, 3, 4 or 5. -Cl 4-C1 triazol-l-yl -C1, CH N Me C (0) HCH2CF3 3-C1, CH N Me 2H-1,2, 4-Cl 4-C1 triazol-l-yl -C1, NN Me C (0) HCH2CF3 3-C1, NN Me iff-1,2,4-C1 5-C1 triazol-1-yl -C1, N CH Me C (0) HCH2CF3 3-C1, N CH Me 2H-1,2,4-Cl 5-C1 triazol-1-yl -C1, CH N e C (0) HCH2CF3 3-C1, CH N Me IH-1,2,4-C1 5-C1 triazol-l-yl -C1, NN CF3 C (0) HCH2CF3 3-C1, NN CF3 1H-1,2,4-Cl 4-C1 triazole-l -ilo -C1, N CH CF3 C <; 0) NHCH2CF3 3-C1, N CH CF3 1H-1, 2, 4-C1-4-C1 triazol-1-yl -C1, CH N CF3 C (0) NHCH2CF3 3-C1, CH N CF3 ?? - 1,2,4-Cl 4-C1-triazol-1-yl -C1, NN CF3 C (0) NHCH2CF3 3-C1, NN CF3 lff-1,2,4-Cl 5-C1 triazol-1-yl -C1, N CH CF3 C (0) NHCH2CF3 3-C1, N CH CF3 1H-1,2,4-C1 5-C1 triazol-1-yl -C1, CH N CF3 C (0) HCH2CF3 3-C1 , CH N CF3 IH-1,2,4 - C1 5-C1 triazol-1-yl Table 15 Me N CH Me C (O) NHEt Me CH N CF3 C (0) HEt Me N CH Me C (0) NHCH2CF3 Me CH N CF3 C (0) NHCH2CF3 Me N CH Me C (0) NHCH2CF3 Me CH N CF3 C (0) NHCH2CF3 Me N CH Me C (0) NHCH2-2-Py Me CH N CF3 C (0) NHCH2-2-Py Me N CH Me C (0) NHCH2-2-Py Me CH N CF3 C (0) HCH2-2-Py Me N CH Me 1H-1,2,4-Me CH N CF 3 1 H-1,2,4-triazol-1-yltriazol-1-yl Me N CH Me 1H-1,2,4- Me CH N CF3 JH-1,2,4-triazol-1-yltriazol-1-yl H N N Me C (O) NHEt H N CH CF3 C (O) HEt H N N Me C (0) HEt H N CH 'CF3 C (O) HEt H N N Me C (0) HCH2CF3 H N CH CF3 C (0) NHCH2CF3 H N N Me C (0) NHCH2CF3 H N CH CF3 C (0) NHCH2CF3 H N N Me C (0) NHCH2-2-Py H N CH CF3 C (0) HCH2-2-Py H N N Me C (0) NHCH2-2-Py H N CH CF3 C (0) HCH2-2-Py H N N Me 1 H -1,2,4-H N CH CF 3 1 H -1,2,4-triazol-1-yltriazol-1-yl H N N Me 1H-1,2,4-H N CH CF 3 JH-1,2,4-triazol-l-yl triazol-1-yl Me N N Me C (0) HEt Me N CH CF3 C (O) NHEt Me N N Me C (O) NHEt Me N CH 'CF3 C (O) NHEt Me N N Me C (0) HCH2CF3 Me N CH CF3 C (0) HCH2CF3 Me N N Me C (0) NHCH2CF3 'Me N CH CF3 C (0) NHCH2CF3 Me N N Me C (0) NHCH2-2-Py Me N CH CF3 C (0) NHCH2-2-Py Me N N Me C (0) NHCH2-2-Py Me N CH CF3 C (0) NHCH2-2-Py Me N N Me lff-1,2,4- Me N CH CF 3 lfl-1,2,4-triazol-l-yl triazol-l-yl Me N N Me 1H-1,2,4-Me N CH CF 3 lff-1,2,4-triazol-l-yl triazol-1-yl H CH N H C (O) HEt H N N CF3 C < 0) NHEt H CH N H C (0) HEt H N N CF3 C (0) HEt H CH N H C (0) NHCH 2 CF 3 H N N CF 3 C (0) NHCH 2 CF 3, H CH N H C (0) NHCH 2 CF 3 H N N CF 3 C (0) HCH 2 CF 3 H CH N H C (0) HCH2-2-Py H N N CF3 C (0) HCH2-2-Py H CH N H C (0) NHCH2-2-Py H N N CF3: C (0) HCH2-2-Py H CH N H IH-1,2,4- H N N CF3 lff-1,2,4-triazol-l-yl triazol-l-yl H CH N H IH-1,2,4-H N N CF 3 1 H-1,2,4-triazol-1-yltriazol-1-yl I CH N H C (O) HEt Me N N CF3 C (O) HEt I CH N H C (O) NHEt Me N N CF3 C (O) NHEt e CH N H C (0) NHCH2CF3 Me N N CF3 C (0) HCH2CF3 I CH N H C (0) NHCH2CF3 Me N N CF3 C (0) NHCH2CF3 I CH N H C (0) HCH2-2-Py Me N N CF3 C (0) HCH2-2-Py I CH NHC (0) HCH2-2-Py Me NN CF3 C (0) HCH2-2-Py e CH NH Itf-1,2,4- Me NN CF3 1H-1,2,4-triazol-1-yl triazol-l-ilo Me CH N H lff-1,2,4-Me N N CF3! H-1,2,4-triazol-l-yl triazol-l-yl Formulation / Utility The compounds of this invention can generally be used as an active ingredient for the elimination of invertebrate pests in a composition, ie formulation with a suitable carrier for agronomic or nonagronomic uses comprising at least one of a diluent liquid, a solid diluent or a surfactant. The ingredients of the formulation or composition are selected to match the physical properties of the active ingredient, mode of application and environmental factors such as soil type, humidity and temperature.
Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and / or suspoemulsions) and the like which optionally can be thickened to gels. The general types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspension, concentrate emulsion, microemulsion and suspo-emulsion. The general types of non-aqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion. General types of solid compositions are fine powders, powders, granules, pellets, lumps, pellets, tablets, filled films (including seed coatings) and the like which may be water dispersible ("wettable") or water soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for the treatment of seeds. The active ingredient can be (micro) encapsulated and can be further shaped into a suspension or solid formulation; alternatively, the entire formulation of the ingredient active can be encapsulated (or "overcoat"). The encapsulation can be of controlled or delayed release of the active ingredient. An emulsifiable granule combines the advantages of an emulsifiable concentrate formulation and a dry granular formulation. High strength compositions are used primarily as intermediates for additional formulations. The sprayable formulations typically are spread in a suitable medium before spraying. These liquid and solid formulations are made to be easily diluted in the spray medium, usually water. The spray volumes may vary from about one to several thousand liters per hectare, but more typically they are in the range of about ten to several hundred liters per hectare. The sprayable formulations can be mixed in a tank with water or other suitable medium for foliar treatment by aerial or terrestrial application or for application to the growth medium of the plant. The liquid and dry formulations can be dosed directly in drip irrigation systems or can be dosed in the irrigation during the seeding. Liquid and solid formulations can be applied to seeds or crops or other desirable vegetation as seed treatments before planting to protect developing roots and other parts of underground plants and / or foliage from systemic uptake. The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which will add 100 percent by weight. Percent by weight Ingredient Thinner Active surfactant Granules, tablets and 0.001-90 0-99.999 0-15 water dispersible and water soluble powders Oil dispersions, 1-50 40-99 0.50 suspensions, emulsions, solutions (including emulsifiable concentrates) Fine powders 1-25 70-99 0-5 Granules and pellets 0.001-99 5-99.999 0-15 Compositions high 90-99 0-10 0.2 resistance Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (for example lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate and sodium sulfate.
Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd edition., Dorland Books, Caldwell, New Jersey. Liquid diluents include, for example, water, N, N-dimethylalkanamides (for example N, N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (for example N-methylpyrrolidinone), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (eg white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerin, glycerol triacetate, sorbitol, triacetin, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and sodium acetate. isobornyl, other esters such as alkylated lactate esters, dibasic esters and? -butyrolactone and alcohols, which can be linear, branched, saturated or unsaturated such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzyl alcohol. Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically from 6 to 22 carbon atoms) such as seed oils from plants and fruits (for example, olive, castor, linseed, sesame, corn, peanut, sunflower, grapefruit, saffron, cotton, soybean, rapeseed, coconut and palm kernel), fats from animal sources (eg beef tallow, pork fat, lard, oil of cod liver, fish oil) and mixtures thereof. Liquid diluents also include alkylated fatty acids (eg methylated, ethylated, butylated), wherein the fatty acids can be obtained by hydrolysis of the glycerol esters from vegetable and animal sources, and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd addendum. Interscience, New York, 1950. McCutcheon's Detergent and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, with lists of surfactants and recommended uses. The solid and liquid compositions of the present invention often include one or more surfactants. When added to a liquid, surfactants (also known as "active agents on their surface") generally modify, and more often reduce the surface tension of the liquid. Based on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, the surfactants may be useful as wetting agents, dispersants, emulsifiers or defoaming agents. Surfactants can be classified as non-ionic, anionic or cationic. Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and are prepared from alcohols and oxide of ethylene, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor oil and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonylphenol ethoxylates and dodecylphenol ethoxylates (prepared from the phenols and oxides of ethylene, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers wherein the terminal blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; tristyrylphenol ethoxylates (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd resins (polyethylene glycol) graft or comb polymers and star polymers; polyethylene glycols (peg); fatty acid esters of polyethylene glycol; silicone based surfactants; and sugar derivatives such as sucrose esters, alkyl polyglucosides and alkyl polysaccharides. Useful anionic surfactants include, but are not limited to: alkylarylsulfonic acids and their salts; ethoxylates of carboxylated alcohol or alkylphenol; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styrylphenol ethoxylates; protein-based surfactants; sarcosine derivatives; sterylphenol ether sulfate; sulfates and sulfonates of fatty acid oils; sulphates and sulphonates of alkylphenol ethoxylates; alcohol sulfates; sulfates of ethoxylated alcohols; amine sulphonates and amides such as N, N-alkyl taurates; sulfonates of benzene, eumeno, toluene, xylene and dodecyl and tridecylbenzenes; condensed naphthalene sulphonates; Naphthalene sulfonates and alkylnaphthalene; fractionated petroleum sulfonates; sulfosuccinamates; and sulfosuccinates and their derivatives such as dialkyl sulfosuccinate salts. Useful cationic surfactants include, but are not limited to: ethoxylated amides and amides; amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetrotetramines and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis- (2-hydroxyethyl) -alkylamine oxides. Also useful for the present compositions are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. The non-ionic, anionic and cationic surfactants and their recommended uses are described in a variety of published references including McCutcheon's Emulsifier and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publis ing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co. , Inc., New York, 1964; and AS Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987. The compositions of this invention may also contain formulation aids and additives, known to those skilled in the art as formulation aids ( some of which can be considered to also function as solid diluents, liquid diluents or surfactants). Said auxiliaries and formulation additives can control: the pH (buffers), the foaming during the processing (antifoams such as polyorganosiloxanes), the sedimentation of active ingredients (suspending agents), the viscosity (thixotropic thickeners), the microbial growth in the container (antimicrobial), product freezing (antifreeze), color (dyes / pigment dispersions), flushing (film formers or adherents), evaporation (evaporation retardants) and other formulation attributes. Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of formulation aids and additives include those included in McCutcheon's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division. The Manufacturing Confectioner Publishing Co.; and the publication WO 03/024222. The compound of formula 1 and any other active ingredient is typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding it in a liquid or dry diluent. Solutions can be prepared, including emulsifiable concentrates by simply mixing the ingredients. If the solvent of a liquid composition designed for use as an emulsifiable concentrate is immiscible with water, an emulsifier is typically added to emulsify the solvent containing the active ingredient by dilution with water. Suspensions of active ingredient with particle diameters up to 2,000 μp? can be wet milled using media mills to obtain particles with average diameters less than 3 μ ?? Aqueous suspensions can be made into finished suspension concentrates (see, for example, US Pat. No. 3,060,084) or can be further processed by spray drying to form water dispersible granules. Dry formulations usually require dry milling processes, which process average particle diameters in the range of 2 to 10 μp ?. The fine powders and powders can be prepared by combination and usually by grinding (for example with a hammer mill or a fluid energy mill). The granules and the pellets can be prepared by spraying the active material on the preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, p. 147-148, Perry's Chemical Engineer's Handbook, fourth edition, McGraw-Hill, New York, 1963, pages 8-57, and following, and WO 91/13546. Pellets can be prepared as described in the document of E.U.A. 4,172,714. The water-dispersible and water-soluble granules can be prepared as described in the document E.U.A. 4,144,050, 3,920,442 and DE 3,246,496. Tablets can be prepared as described in the document of E.U.A. No. 5,180,587; 5,232,701 and 5,208,030. Films can be prepared as described in GB 2,095,558 and the document E.U.A. 3, 299, 566. For additional information regarding the formulation technique see T.S. Woods, "The Formulator's Toolbox-Products Forms for Modern Agriculture" in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds. , Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, p. 120-133. See also document E.U.A. 3,235,361, Col. 6, line 16 to col. 7, line 19 and examples 10-41; document of E.U.A. 3,309,192, col. 5, line 43 to col. 7, line 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; document E.U.A. 2,891,855, col. 3, lines 66 to col. 5, line 17 and examples 1-4; Klingman, Veed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Development in Formulation Technology, PJB Publications, Richmond, UK, 2000. In the following examples all percentages are by weight and all formulations are prepared in a conventional manner. The numbers of compounds refer to compounds in tables of index A-D. Without further elaboration, it is considered that a person skilled in the art using the preceding description can use the present invention in its maximum scope. Therefore, the following examples will be constructed as merely illustrative and not limiting of the description in any way. The percentages are by weight unless otherwise indicated.
Example A High power concentrate Compound 2 98.5% silica airgel 0.5% synthetic amorphous fine silica 1.0% Example b Wettable powder Compound 12 65.0% dodecylphenol polyethylene glycol ether 2-0% sodium lignin sulfonate 4.0% sodium silicoaluminate 6.0 montmorillonite (calcined) 23.0% Example C Granule Compound 16 10.0% granules of atapulguite (material 90.0% low volatile, 0.71 / 0.30 mm); sieves U.S.S. No. 25-50).
EXAMPLE D Extruded pellets Compound 18 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium / magnesium bentonite 59.0% Example E Emulsifiable Concentrate Compound 19 10.0% polyoxyethylene sorbitol hexoleate 20.0% fatty acid methyl ester from 6 to 10 70.0% carbon atoms Example F Microemulsion Compound 2 5.0% copolymer of polyvinylpyrrolidone- 30.0% vinyl acetate alguilpolyglycoside 30.0% glycerol monooleate 15.0% water 20.0% Example G Seed treatment Compound 18 20.00% polyvinylpyrrolidone-5.00% vinyl acetate copolymer monomer acid wax 5.00% calcium ligninsulfonate 1.00% polyoxyethylene / 1.00% polyoxypropylene block copolymer stearyl alcohol (POE 20) 2.00% polyorganosiloxane 0.20% dye of red dye 0.05% water 65.75% Example H Composite Fertilizer Bar 19 2.5% pyrrolidone-styrene copolymer 3.8% tristyrylphenyl 2,3-ethoxylate talcum 0.8% corn starch 5.0% slow release fertilizer 36.0% NitrophoskaMR Permanent 15-9-15 BASF kaolin 38.0% water 10.6% The compounds of this invention show activity against a broad spectrum of invertebrate pests. These pests include invertebrates that inhabit a variety of environments such as, for example, the foliage of plants, roots, soil, harvested crops or other food products, building structures or integuments in animals. These pests include, for example, invertebrates that feed on foliage (which include leaves, stems, flowers and fruits), seeds, wool, textile fibers or animal tissue and therefore cause prejudice or damage, for example to agronomic crops in growth or stored, forests, greenhouse crops, ornamental plants, nursery crops, stored food products or fiber products or houses or other structures and their contents or are harmful to the health of animals or to public health. Those skilled in the art will appreciate that not all compounds are equally effective against all stages of growth of all pests. The present compounds and compositions are therefore useful agronomically to protect field crops of phytophagous invertebrate pests and also non-agronomically to protect other horticultural crops and plant pests of phytophagous invertebrates. This utility includes protecting crops and other plants (both agronomic and non-agronomic) that contain genetic material introduced by genetic engineering (ie, transgenic) or modified by mutagenesis to provide advantageous traits. Examples of such traits include tolerance to herbicides, resistance to phytophagous pests (eg, insects, mites, aphids, spiders, nematodes, snails, fungi pathogenic to plants, bacteria and viruses), improved plant growth, increased tolerance to adverse growth conditions such as high or low temperatures, little or high humidity in the soil and high salinity, increased fluoridation or fruit production, higher crop yields, faster ripening, higher quality and / or nutritional value of harvested product or improved storage or processing properties of harvested products. Transgenic plants can be modified to express multiple traits. Examples of plants containing traits provided by genetic engineering or mutagenesis include varieties of corn, cotton, soybean and potato expressing a Bacillus thuringiensis insecticidal toxin such as YIELD GARDMR, KNOCKOUTMR, STARLINKMR, BOLLGARDMR, NuCOTNMR and NEWLEAFMR, and varieties tolerant to corn, cotton, soybean and rape herbicide such as ROUNDUP READYMR, LIBERTY LINKMR, I IMR, STSMR and CLEARFIELDMR, as well as crops expressing N-acetyltransferase < GAT) to provide resistance to glyphosate herbicide or crops that contain the HRA gene that provides resistance to herbicides that inhibit acetolactates synthase (ALS). The present compounds and compositions can interact in a synergistic manner with traits introduced by genetic engineering or modified by mutagenesis whereby the phenotypic expression or efficacy of the traits is increased or the efficacy of the invertebrate pest control or the compounds and compositions is increased. present In particular, the present compounds and compositions may interact in a synergistic manner with the phenotypic expression of proteins or other natural products toxic to invertebrate pests to provide a greater than additive removal of these pests. The compositions of the invention optionally may also comprise plant nutrients, for example a fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium, magnesium, iron, copper, boron, manganese, zinc and molybdenum Of note are compositions comprising at least one fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium and magnesium. The compositions of the present invention further comprise at least one plant nutrient may be in the form of liquids or solids. It should be noted that they are solid formulations in the form of granules, small bars or tablets. Solid formulations comprising a fertilizer composition can be prepared by mixing the compound or composition of the present invention with the fertilizer composition together with formulation ingredients and then preparing the formulation by methods such as granulation or extrusion. Alternatively, the solid formulations can be prepared by spraying a solution to suspension of a compound or composition of the present invention in the volatile solvent over a previously prepared fertilizer composition in the form of dimensionally stable mixtures, for example granules, small bars or tablets and then evaporate the solvent. Non-agronomic uses refer to the elimination of invertebrate pests in areas other than the fields of crop plants. Non-agronomic uses of the present compounds and compositions include the removal of invertebrate pests in stored grains, seeds and other food products and in textiles such as clothing and carpets. Non-agronomic uses of the present compounds and compositions also include elimination of invertebrate pests in ornamental plants, forests, on land, along the sides of the road and in the rights-of-way of railroads and in lawns such as prada, golf areas and pasture places. Non-agronomic uses of the present compounds and compositions also include the elimination of invertebrate pests in houses and other buildings which can be occupied by humans and / or pets, farm animals, ranches, zoos or other animals. Non-agronomic uses of the present compounds and compositions also include elimination of pests such as termites that can damage wood or other structural materials used in buildings. Non-agronomic uses of the present compounds and compositions also include protecting the health of humans and animals by controlling pests of invertebrates that are parasitic or that transmit infectious diseases. The elimination of animal parasites includes controlling external parasites that are parasites on the body surface of the host animal (for example in the shoulders, armpits, abdomen, inner part of the legs) and internal parasites that are parasites inside the body of the animal. host (for example stomach, intestine, lung, veins, under the skin, lymphatic tissue). External parasitic pests or diseases that transmit diseases include, for example, red larvae, ticks, lice, mosquitoes, flies, mites and fleas. Internal parasites include worms, hookworms and food. The compounds and compositions of the present invention are suitable for the systemic and / or non-systemic elimination of infestation or infection by parasites in animals. The compounds and compositions of the present invention are particularly suitable for controlling pests of external parasites or transmitters of diseases.
The compounds and compositions of the present invention are suitable for combating parasites that infect agricultural labor animals such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese and bees; pets and domestic animals such as dogs, cats, pet birds and aquarium fish; as well as the so-called experimental animals such as hamsters, guinea pigs, rats and mice. By combating these parasites the deaths are reduced and there is a reduction in performance (in terms of meat, milk, wool, skin, eggs, honey, etc.), so that by applying a composition comprising a compound of the present invention allows a more economical and simple handling of animals. Examples of pests of agronomic and non-agronomic invertebrates include eggs, adult larvae of the order Lepidoptera such as false measuring worms, nocturnal caterpillars, measuring caterpillars and fruit worms of the Noctuidae family (for example purple sugar cane borer) (pink stem borer, Sesamia inferens Walker), corn borer (Sesamia nonagrioides Lefebvre), southern armyworm (Spodoptera eridania Cramer), corn moth (fall armyworm, Spodoptera fugiperda JE Smith), gardama (beet) armyworm, Spodoptera exigua Hübner), black donut (cotton leafworm, Spodoptera littoralis Boisduval), pirero worm (yellowstriped armyworm, Spodoptera ornithogalli Guenée), greasy cutworm (Agrotis ipsilon Hufnagel), caterpillar of the legumes (velvetbean caterpillar, Anticarsia Hübner gemmatalis), fruit worm (Lithophane antennata Walker), plague of cabbage ( cabbage armyworm, Barathra brassicae Linnaeus), soy defoliating caterpillar (soybean looper, Pseudoplusia includens Walker), false lobster (cabbage looper, Trichoplusia ni Hübner), tobacco budworm (Tobáceo budworm, Heliothis virescens Fabricius), barrenillos, borers , weaver caterpillar, fruit borers, cabbage worms and skeleton worm of the family Pyralidae (for example, corn borer, Ostrinia n bilalis Hübner), orange worm (navel orangeworm, Amyelois transitella Walker), caterpillar weaver corn (corn root webworm, Cra bus caliginosellus Clemens), Piralidae: adult lawn tissue moth (sod webworms, Crambinae) such as lawn worm (sod worm, Herpetogramma licarsisalis Walker), stem drill of sugar cane (surgarcane) stem borer, Chilo infuscatellus Snellen), tomato fruit borer (small borer tornato, Neoleucinodes elegantalis Guenée), green leafworm (green leafroller, Cnaphalocerus medinalis), vine leaf doubler (Grape leaffolder, Desmia funeralis Hübne), melon borer (melon orm, Diaphania nitidalis Stoll), cabbage center worm (Helluala hydralis Guenée), yellow stem borer (Scirpophaga incertulas Walker), early shoot borer (Scirpophaga infuscatellus Snellen), white stem borer (Scirpophaga innotata Walker), upper shoot borer, top shoot borer (Scripophaga nivella Fabricius), dark-headed rice borer (Chilo polychrysus Meyrick), caterpillar of the cabbage cluster (Caterpillar cabbage cluster, Crocidolomia binotalis English)); moths, lepidoptera, seed worms and fruit worms of the Tortricidae family (for example, moth of the green apple (codling moth, Cydia pomonalla Linnaeus), grapevine moth (grape berry moth, Endopiza viteana Clemens), oriental moth of the fruit (oriental fruit moth, Grapholita molesta Busck), moth of the fake citrus green apple - (citrus false codling moth, Cryptophlebia leucotreta Meyrick), citrus borer (citrus borer, Ecdytolopha aurantiana Lima), moth of the red band (redbanded leafroller, Argyrotaenia velutinana Walker), moth of the oblique bands (obliquebanded leafroller, Choristoneura rosaceana Harris), light brown apple moth (Epiphyas postvittana Walker), European moth of the vine (European grape berry moth, Eupoecilia ambiguella Hübner), moth of the apple buds (apple bud moth, Pandemis pyrusana Kearfott), omnivore moth (omnivorous leafroller, Platinota stultana Walsingham), tortricid striped fruit trees (barred fruit- tree tortrix, Pandemis cerasana Hübner), tortured apple coffee (apple brown tortrix, Pandemis heparana Denis &; Schiffermüller)); and many other economically important lepidoptera (eg, diamondback moth, Plutella xylostella Linnaeus), pink bollworm, Pectinophora gossypiella Saunders, gypsy moths (gipsy moth, Lymantria dispar Linnaeus), peach perforator (peach) fruit borer, Carposina niponensis Walsingham), peach twig borer, Anarsia lineatella Zeller, potato tuberworm, Phthorimaea operculella Zeller, spotted teniform leafminer, Lithocolletis blancardella Fabricius )), Asian apple leaf miner (Asiatic apple leafminer, Lithocolletis ringoniella Matsumura), rice leafroller (rice leaffolder, Lerodea eufala Edwards), apple leafminer (apple leafminer, Leucoptera scitella Zeller); eggs, nymphs and adults of the order Blattodea that include cockroaches of the families Blattellidae and Blattidae (for example, oriental cockroach (Oriental cockroach, Blatta orientalis Linnaeus), Asian cockroach (Asian cockroach, Blatella asahinai Mizukubo), German cockroach (German cockroach, Blatella Germanic Linnaeus), brown-banded cockroach (Brown-banded cockroach, Supelotilla longipalpa Fabricius), American cockroach (American cockroach, American Periplaneta Linnaeus), brown cockroach (Brown cockroach, Periplaneta brunnea Burmeister), Madeira cockroach (Madeira cockroach, Leucophaea maderae Fabricius) ), dark brown cockroach (Periplaneta fuliginosa Service), Australian cockroach (Australian Cockroach, Periplaneta australasiae Fabr.), lobster cockroach (lobster cocroach, Nauphoeta cinérea Olivier), and smooth cockroach (Symplece pallens Stephens)); Eggs, leaf-feeding larvae, fruit-feeding larvae, root-feeding and seed-feeding larvae, and vesicular-feeding larvae and adults of the Coleoptera order including weevils of the families Anthribidae, Bruchidae and Curculionidae (e.g. cotton weevil, Anthonomus granáis Boheman), water weevil (Lysorhoptrus oryzophilus Kuschel), bark weevil (Granary weevil, Sitophilus granarius Linnaeus), rice weevil (Rice weevil, Sitophilus oryzae Linnaeus) , spikelet weevil (annual bluegrass weevil, Listronotus maculicollis Dietz), grass beetle. { bluegrass billbug, Sphenophorus parvulus Gyllenhal), scarab hunter (hunting billbug, Sphenophorus venatus vestitus), Denver beetle (Denver billbug, Sphenophorus cicatristriatus Fahraeus)); fly beetles, cucumber beetles, root worms, leaf beetles, potato beetles and pitchers of the family Chrysomelidae (eg, Colorado potato beetle, Leptinotarsa decemlineata Say), woodworm western root (western corn rootworm Diabrotica virgifera virgifera LeConte), bumblebees and other beetles of the family Scarabaeidae (for example, Japanese beetle (Japanese beetle, Popillia japonica Newman), Anómala orientalis Waterhouse, eastern beetle (Oriental beetle, Exórnala orientalis (Waterhouse) Baraud) ), boreal masked cetonia (northern masked chafer, Cyclocephala borealis Arrow)), southern masked chafer (Cyclocephala i maculata Olivier or C. lurida Bland), genus Aphodius (dung beetle) and white grub), beetle Black Weed (Black Turfgrass Ataenius, Ataenius Spretulus Halderman), June Green Beetle (Green June Beetle, Cotinis Sharp Linnaeus), Asian Garden Beetle (Asiatic Garden Beetle, Marbled Arrow Beetle), Phyllophaga Genus (May / June Beetles) { ay / Jun beetles) and European cetonia (European chafer, Rhizotrogus majalis Razoumowsky), carpet beetles of the Dermestidae family; larvae of beetles of the family Elateridae; beetles of the bark of the family Scolytidae and beetles of the flour of the family Tenebrionidae. In addition, agronomic and non-agronomic pests include: eggs, adults and larvae of the order Dermaptera that include earwigs of the Forficulidae family (for example, European earwig (European earwig, Forfícula auricularia Linnaeus), black tiger (Black earwig, Chelisoches morio Fabricius) eggs, immature larvae, adults and nymphs of the order Hemiptera and Homoptera such as parasites of plants of the family Miridae, cicadas of the family Cicadidae, saltoillas (for example the genus Empoasca) of the family Cicadellidae, mites of the bed (for example Cimex lectularius Linnaeus) - of the family Cimicidae, grasshoppers of the families Fulgoroidae and Delphacidae, tree jumpers of the family Membracidae, psilids of the family Psyllidae, white flies of the family Aleyrodidae, aphids of the family Aphididae, phylloxera of the family Phylloxeridae , pillbugs of the family Pseudococcidae, coconuts of the families Coccidae, Diaspididae and Margarodidae, bed bugs milia Tingidae, bedbugs of the family Pentatomidae, bed bugs. { for example, hairy stink bug (hairy chinch bug, Blissus leucopterus hirtus Montandon), southern bug (Blissus insularis Barber) and other seed bugs of the family Lygaeidae, afroforas of the family Cercopidae, insects of the pumpkins of the family Coreidae and red bugs and cotton stainers of the family Pyrrhocoridae. Also included are eggs, larvae, nymphs and adults of the Acari orders (mites) such as spider mites and red mites of the family Tetranychidae (for example, European red mite (Panonychus ulmi Koch), two-spotted spider mite (two spotted spider mite, Tetranychus urticae Koch), McDaniel mite (McDaniel mite, Tetranychus mcdanieli McGregor)); flat mites of the Tenuipalpidae family (for example, citrus flat mite (citrus fíat mite, Brevipalpus lewisi McGregor)); rust and citrus mites in the family Eriophyidae and other leaf-feeding mites and mites important for the health of humans and animals, that is, dust mites of the family Epidermoptidae, mites of the follicles of the family Demodicidae , mites of the grains of the family Glycyphagidae, ticks of the family Ixodidae, commonly known as ixodids (for example, deer tick (deer tick, Ixodes scapularis Say)), Australian paralysis tick (Australian paralysis tick, Ixodes holocyclus Neumann), American dog tick (Dermacentor variabilis Say), solitary star tick (Lone star tick, Amblyomma americanum Linnaeus), and ticks of the family Argasidae, commonly known as argasides (for example, relapsing fever tick, Ornithodoros turicata), common fowl tick, Argas radiatus); mites of scabies and pruritus of the families Psoroptidae, Pyemotidae and Sarcoptidae; eggs, adults and immature forms of the order Orthoptera that include grasshoppers, locusts and crickets (for example, migratory grasshopper (Migratory grasshopperes, Melanoplus sanguinipes Fabricius, M. differentialis Thomas), American salmon (for example, Schistocerca americana Drury), desert locust (Schistocerca gregaria Forskal), migratory locust (Locusta migratoria Linnaeus), shrimp lobster (genus Zonocerus), house cricket (Acheta domesticus Linnaeus), mole crickets (for example, mole cricket mole (tawny mole cricket, Scapteriscus vicinus Scudder ) and southern mole cricket (Southern mole cricket, Scapteriscus borellii Giglio-Tos); eggs, adults and immature forms of the order Diptera that include leaf miners (for example, Liriomyza genus such as serpentine vegetable haulm miner (serpentine vegetable leafminer, Liriomyza sativae Blanchard)), gnats, fruit flies (Tephritidae), fruit flies (eg Oscin she frit Linnaeus), ground crests, houseflies. { for example Musca domestica Linnaeus), smaller house flies (for example Fannia canicularis Linnaeus, F. femoralis Stein), stable flies (for example Stomoxys calcitrans Linnaeus), face flies, horn flies, wind flies. { for example genus Chryso ya, genus Phormia), and other pests of muscoid flies, horse flies (for example the genus Tabanus), bot flies (for example the genus Gastrophilus, the genus Oestrus), larvae of cattle (for example genus Hypoderma), deer flies (for example the genus Chrysops), parasitic fly of the sheep (for example Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (for example the genera Aedes, Anopheles, Culex), black flies (for example genus Prosimulium, Simulium), gnats that bite, sand flies, sciarids and other Nematocera; eggs, adults and immature forms of the order Thysanoptera that include Thysanoptera of the onion (Thrips tabaci Lindeman), Thysanoptera of the flowers (Frankliniella genus) and other Thysanoptera of foliar feeding; insect pests of the order Hymenoptera that include ants of the family Formicidae that include floristic carpenter ant (Florida carpenter ant, Camponotus floridanus Buckley), red carpenter ant (red carpenter ant, Camponotus ferrugineus Fabricius), black carpenter ant (black carpenter ant, Camponotus pennsylvanicus De Geer), white-footed ant (white-footed ant, Technomyrmex albipes fr. smith), large-headed ants (genus Pheidoles), phantom ant (ghost ant, Tapinoma melanocephalum Fabricius); paraoh ant (Pharaoh ant Monomorium pharaonis Linnaeus), small mincer ant (Little fire ant, Wasmannia auropunctata Roger), mincer ant (fire ant, Solenopsis geminata Fabricius), imported red mincer ant (Red imported fire ant, Solenopsis invicta Burén), Argentine ant ( Argentine ant, Iridomyrmex humilis ayr), crazy ant (crazy ant, Paratrechina longicornis Latreille), pavement ant (Pavement ant, Tetramorium caespitum Linnaeus), corn field ant (cornfield ant, Lasius alienus Fórster) and fragrant house ant (Odorous house ant, Tapinoma sessile Say). Other Hymenoptera including bees (including carpenter bees), hornets, yellow jacket wasps, bumblebees and saw flies (genus Neodiprion, genus Cephus); insect pests of the Isoptera order that include termites of Termitidae (for example the genus Macrotermes, Odontotermes obesus Rambur), Kalotermitidae (for example the genus Cryptotermes) and Rhinotermitidae (for example the genera Reticulitermes, Coptotermes, Heterotermes tenuis Hagen) genus families of eastern subterranean termite (eastern subterranean termite, Reticulitermes flavipes Colrar) western subterranean termite (Reticterns hesperus Banks), Formosan subterranean termite (Formosan subterranean termite, Coptotermes formosanus Shiraki), western dryland termite (West Indian drywood termite, Incisi termes immigrans Snyder), termite sawdust posts (powder post termite, Cryptotermes brevis Walker), dry wood termite (drywood termite, Incisitermes snyderi Light), subterranean subterranean termite (southeastern subterranean termite, Reticulitermes virginicus Banks) Western termite of the m dry adera (western drywood termite, Incisitermes minor Hagen), arboreal termites such as the genus Nasutitermes and other termites of economic importance; insect pests of the order Thysanura such as silverfish (silverfish, Lepisma saccharina Linnaeus) and fire or copperfish insect (firebrat, Thermobia domestica Packard); insect pests of the order Mallophaga including head louse (Pediculus humanus capitis De Geer), body louse (body louse, Pediculus humanus Linnaeus), body louse of chickens (chicken body louse, Menacanthus stramineus) Nitszch), biting louse of dogs (dog biting louse, Trichodectes canis De Geer), lice of the fluff (fluff louse, Goniocotes gallinae De Geer), louse of the body of the sheep (sheep body louse, Bovicola ovis Schrank), louse of short-nosed cattle (short-nosed cattle louse, Haematopinus eurysternus Nitzsen) and long-nosed cattle louse (Linognathus vituli Linnaeus) and other sucking and chewing lice | parasites attacking · - the -man animals; insect pests of the Siphonoptera order which includes the Eastern rat flea (oriental rat flea, Xenopsylla cheopis Rothschild), cat flea (Cetnocephalides felis Bouche), dog flea (Coutnocephalides canis Curtis), flea chickens (hen flea, Ceratophyllus gallinae Schrank), flea from poultry houses (sticktight flea, Echidnophaga gallinaceous Westwood), flea from humans (human flea, Pulex irritans Linnaeus) and other fleas that affect mammals and birds. Additional arthropod pests covered include: Araneae spiders such as brown recluse spider (Loxosceles reclusa Gertsch &Mulaik) and black widow spider (Lactrodectus actans Fabricius) and centipedes of the order Scutigeromorpha such as home centipedes (house centipede, Scutigera coleoptrata Linnaeus). The compounds of the present invention also have activity on members of the Nematoda classes, Cestoda, Trematoda and Acanthocephala that include economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida and Enoplida such as, but not limited to economically important agricultural pests. { for example nematodes of root knots in the genus Meloidogyne, nematodes of lesion of the genus Pratylenchus, nematodes of the bulbous root in the genus Trichodorus, etc.) and pests for the health of animals and humans (ie, all trematodes) , tapeworms and economically important earthworms such as Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus en- borregos, Dirofilaría immitis Leidy in dogs, Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.). The compounds of the invention show particularly high activity against pests of the order Lepidoptera (for example, cotton leaf worm, Alabama argillacea Hübner), fruit tree leaf roller, Archips argyrospila Walker), European leaf roller (A. rosana Linnaeus) and other Archips species, rice stem borer (Chilo suppressalis Walker), rice leaf roller (Cnaphalocrosis medinalis) Guenée), caterpillar of corn root (Corn root webworm, Crambus caliginosellus Clemens), grass-weaver caterpillar (bluegrass webworm, Crambus teterrellus Zincken), green apple moth (codling moth, Cydia pomonella Linnaeus), spiny moth larva (spiny bollworm, Barias insulana Boisduval), spotted moth larvae (spotted bollworm, Earias vittella Fabricius), American moth larvae (American bollworm, Helicoverpa armígera Hübner), corn worms (Corn earworm, Helicoverpa zea Boddie), tobacco worm (Tobáceo budworm, Heliothis virescens Fabricius), grass worm (sod webworm, Herpelogramma licarsisalis Walker), grape fruit moth (grape) berry moth, Lobesia botrana Denis &; Schiffermüller), pink bollworm (Pectinophora gossypiella Saunders), citrus leafminer (citrus leafminer, Phyllocnistis citrella Stainton), large white butterfly (Pieris brassicae Linnaeus), white butterfly (small white butterfly, Pieris rapae Linnaeus), diamondback moth (Diamondback moth, Plutella xylostella Linnaeus), false measuring worm (bect armyworm, Spodoptera exigua Hübner), tobacco worm or measured caterpillar of the groups (tobáceo cutworm, cluster caterpillar, Spodoptera litura Fabricius) , ototño measuring worm (fall armyworm, Spodoptera frugiperda JE Smith), caterpillar measuring caterpillar (cabbage looper, Trichoplusia ni Hübner) and tomato leafminer (tomato leafminer, Tuta absoluta Meyrick)). The compounds of the invention also have Homoptera which include: pea aphid (pea aphid, Acyrthosiphon pisum Harris), cowpea aphid (cowpea aphid, Aphis craccivora Koch), black bean aphid (Aphis fabae Scopoli), aphid of the cotton or aphid of the melon (cotton aphid, melon aphid, Aphis gossypii Glover), aphid of the apple (apple aphid, Aphis pomi De Geer), aphid of espirea (spirea aphid, Aphis spiraecola Patch), aphid of digitalera (foxglove aphid , Aulacorthum solani Kaltenbach), strawberry aphid (strawberry aphid, Chaetosiphon fragaefolii Cockerell), Russian wheat aphid (Russian aphid, Diuraphis noxia Kurd umov / Mordvilko), apple aphid "rosy" (rosy apple aphid, Dysaphis plantaginea) Paaserini), woody apple aphid (Eriosoma lanigerum Hausmann), prune mealy aphid (mealy plum aphid, Hyalopterus pruni Geoffroy), aphid turnip (turnip aphid, Lipaphis erysimi Kaltenbach) , aphid of cereals (cereal aphid, Metopolophium dirrhodum Walker), aphid of potato (potato aphid, Macrosiphum euphorbiae Thomas), aphid of peach and potato or aphid of green peach (peach-potato aphid, green peach aphid, Myzus persicae Sulzer), lettuce aphid, Nasonovia ribisnigri Mosley, aphids of the roots and aphids of the gills (root aphids and gall aphids, genus Pemphigus), aphid of the leaves of corn (corn leaf aphid, Rhopalosiphum maidis Fitch), aphid of birds and cherry-oats (bird cherry-oat aphid, Rhopalosiphum padi Linnaeus), green insect (greenbug, Schizaphis graminum Rondani), English grain aphid (English grain aphid, Si obion avenae Fabricius), aphid speckled alfalfa (spotted alfalfa aphid, Therioaphis aculata Buckton), black citrus aphid (black citrus aphid, Toxoptera aurantii Boyer de Fonscolombe), brown citrus aphid (brown citrus aphid, and Toxoptera citricida Kirkaldy); genus Adelges (adelgids, adelgids); louse of the nut (pecan phylloxera, Phylloxera devastatrix Pergande); white tobacco fly, sweetpotato whitefly (whitefly turtle, sweetpotato whitefly, Bemisia tabaci Gennadius), silverleaf whitefly (Silverleaf whitefly, Bemisia argentifolii Bellows &Perríng), citrus whitefly (citrus whitefly, Dialeurodes citri Ashmead) and greenhouse whitefly (greenhouse whitefiy, Trialeurodes vaporariorum Westwood); potato leafhopper (potato leafhopper, Empoasca fabae Harris), small brownhopper (Laodelphax striatellus Fallen), leafhopper aster (leafhopper aster, Macrolestes quadrilineatus Forbes), green leafhopper, Nephotettix cinticeps Uhler, leafhopper rice (rice leafhopper, Nephotettix nigropictus Stál), brown lobster (brown planthopper, Nilaparvata lugens Stál), corn locust (corn planthopper, Peregrinus maidis Ashmead), white locust (White-backed planthopper, Sogatella furcifera Horvath), rice (rice delphacid, Sogatodes orizicola Muir), white apple leafhopper (white apple leafhopper, Typhlocyba pomaria McAtee, genus Erythroneoura. (grape leafhopper, grape leafhoppers); cicada periodic (newspaper cicada, Magicidada septendecim Linnaeus); cottony cushion scale (Icerya purchasi Maskell), San Jose scale (San José scale, Quadraspidiotus perniciosus Comstock); citrus insect (citrus mealybug, Planococcus citri Risso); genus Pseudococcus (other complex insects; pear fly (Psyllium pear, Cacopsylla pyricola Foerster), carnation rust (persimmon psylla, Trioza diospyri Ashmead) The compounds of this invention also have activity on members of the order Hemiptera which include: stink insect green (green stink bug, Acrosternum hilare Say), pumpkin bug (squash bug, Anasa tristis De Geer), bed bugs (chinch bug, Blissus leucopterus leucopterus Say), bed bugs (bed bug, Cimex lectularius Linnaeus), bed bugs cotton tie (Corythuca gossypii Fabricius), tomato bug (Cyrtopeltis modesta Distant), cotton stainer, cotton stainer, Dysdercus suturellus Herrich-Scháffer, brown spot bug (Brown stink bug Euchistus servus Say) ), insect spotter with a spot { one-spotted stink bug, Euchistus variolarius Palisot de Beauvois), genus Graptosthetus (insects complex of seeds), insect of pine seeds with legs such as leaves (leaf-footed pine seed bug, Leptoglossus corculus Say), insect of bleached plants (tarnished plant bug, Lygus lineolaris Palisot de Beauvois), southern green stink bug, southern green stink bug, Nezara Linnaeus viridula), stink bug (Rice stink bug, Oebalus pugnax Fabricius), large milkweed bug (Oncopeltus fasciatus Dallas), cotton fleahopper flea (Pseudatomoscelis seriatus Reuter). Other orders of insects killed by the compounds of the present invention include Thysanoptera (e.g., western flower thrips (Frankliniella occidentalis Pergande), citrus piojillo (citrus thrips, Scirthothrips citri Moulton), soybean piojiloo (soybean thrips, Sericothrips variabilis Beach), and onion thrips, Thrips tabaci Lindeman, and the order Coleoptera (eg, Colorado potato beetle, Leptinotarsa decemlineata Say), bean beetle Mexican bean (Mexican bean beetle, Epilachna varivestis Mulsant) and catenary worms of the genus Agriotes, Athous or Limonius.) Note that some contemporary classification systems place Homoptera as a suborder of the Hemiptera order.The use of compounds of this invention is noteworthy for control diamond backbone moth (Plutella xylostella) It is worth noting the use of the compounds of this invention. ion to control armyworm or corn moth. { Spodoptera frugiperda). Of note is the use of the compounds of this invention to control cotton and melon aphid (Aphis gossypii). The compounds of this invention can also be mixed with one or more additional biologically active compounds or agents including insecticides, bactericidal nematicidal fungicides, acaricides, herbicides, growth regulators such as root generation stimulants, chemosterilants, semiochemicals, repellents, attractants. , pheromones, food stimulants, other biologically active compounds or entomopathogenic bacteria, viruses or fungi to form a multi-component pesticide that provides an even broader spectrum of agronomic and non-agronomic utility. Thus, the present invention also relates to a composition comprising a biologically effective amount of a compound of formula 1, an N-oxide or a salt thereof and an effective amount of at least one additional biologically active compound or an agent and may further comprise at least one of the surfactants, solid diluents or liquid diluents. To the mixtures of the present invention, other biologically active compounds or agents can be formulated together with the present compounds, which include the compounds of formula 1, to form a premix or other biologically active compounds or agents can be formulated separately from the present compounds, which includes compounds of formula 1 and the two formulations are combined together before their application (for example in a spray tank) or alternatively applied in succession. Other biologically active compounds or agents utilizing the compositions of the present invention may be selected from agents for the removal of invertebrate pests having different modes of action or a different chemical class including macrocyclic lactones, neonicotinoids, octopamine receptor ligands. , ryanodine receptor ligands, ecdysone agonists, sodium channel modulators, chitin synthesis inhibitors, nereisotoxin analogs, mitochondrial electron transport inhibitors, cholinesterase inhibitors, cyclodiene insecticides, shedding inhibitors, channel blockers chlorine regulated by GABA (α-aminobutyric acid), juvenile hormone mimics, lipid biosynthesis inhibitors and biological agents including nucleopolyhedron virus (NPV), members of Bacillus thuringiensis, encapsulated delta endotoxins of Bacillus thuringiensis and other insecticidal viruses as found d e natural way or genetically modified. Of note are the additional biologically active compounds or agents that are selected from insecticides from the group consisting of pyrethroids, carbamates, neonicotinoids, neuronal sodium channel blockers, macrocyclic insecticide lactones, α-aminobutyric acid antagonists, insecticidal urea and imitators. juvenile hormones, members of Bacillus thuringiensis, a delta endotoxin of Bacillus thuringiensis and a viral insecticide as found naturally or genetically modified. Examples of said biologically active compounds or agents with which the compounds of this invention can be formulated are: insecticides such as abamectin, acephate, acetamiprid, acetoprol, amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, bistrifluron, buprofezin, carbofuran, cartap, chlorfenapyr, chlorfluazuron, chlorantraniliprol (DPX-E2Y45), chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, ciflumetofen, cyfluthrin, ß-cyfluthrin, cyhalothrin,? -cyhalothrin,? -cyhalothrin, cypermethrin , cyromazine, deltamethrin, diafentiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diofenolane, emamectin, endosulfan, esfenvalerate, etiprole, phenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamide, flubendiamide, flucitrinate, tau-fluvatinate, flufenerim (UR-50701), flufenoxuron, fonophos, halofenozide, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, isofenfos, lu fenuron, malathion, metaflumizone, metaldehyde, metamididophos, metidation, methomyl, methoprene, methoxychlor, metoflutrin, monocrotophos, methoxyfenozide, monocrotophos, nitenpyram, nitiazine, novaluron, noviflumuron (XDE-007), oxamyl, parathion, parathion-methyl, permethrin, phorate , phosalone, fosmet, phosphamidon, pirimicarb, profenofos, proflutrin, protrifenbuto, pymetrozine, pyfluprol, pyrethrin, pyridalyl, pirifluquinazona, piriprol, piriproxifen, rotenone, ryanodine, espinetarama, espinosad, espirodiclofeno, espiromesifeno (BSN 2060), spirotetrama, sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinfos, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpirad, tralometrine, triazamate, trichlorfon and triflumuron; fungicides such as acibenzolar, aldimorf, amisulbrom, azaconazole, azoxystrobin, benalaxyl, benomyl, benthiavalicarb, bentiavalicarb-isopropyl, binomial, biphenyl, bitertanol, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), boscalide / nicobifen, bromuconazole, bupirimate , butyrobate, carboxy, carpropamide, captafol, captan, carbendazim, chloroneb, chlorothalonil, clozolinate, clotrimazole, copper oxychloride, copper salts such as copper sulfate and copper hydroxide, cysoxamide, cyflunamide, cymoxanil, cyproconazole, cyprodinil, diclofluanid, diclocimet, diclomezine, dichloram, dietofencarb, difenoconazole, dimetomorph, dimoxiestrobin, diniconazole, diniconazole-M, dinocap, disctrobin, ditianon, dodemorf, dodin, econazole, etaconazole, edifenfos, epoxiconazole, etaboxam, etirimol, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fencaramide, fenfuram, fenhexamide, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate , fentanyl hydroxide, ferbam, ferfurazoate, ferimzone, fluazinam, fludioxonil, flumetover, fluopicolide, fluoxastrobin, fluquinconazole, fluquinconazole, flusilazole, flusulfanamide, flutolanil, flutriafol, folpet, fosetyl-aluminum, fuberidazole, furalaxyl, furametapir, hexaconazole, himexazole, guazatine , imazalil, imiibenconazole, iminoctadine, iodicarb, ipconazole, iprobenfos, iprodione, iprovalicarb, isoconazole, isoprothiolane, kasugamycin, kresoxim-methyl, mancozeb, mandipropamide, maneb, mapanipyrine, mefenoxam, mepronil, metalaxil, metconazole, metasulfocarb, metiram, metominostrobina-fenominostrobina , mepanipirim, metrafenone, miconazole, myclobutanil, neo-asozine (ferric methanocarsonate), nuarimol, octilinone, ofurace, orisastrobin, oxadixyl, oxolinic acid, oxpoconazole, oxycarboxine, paclobutrazol, penconazole, pencycuron, pentiopyrad, perfurazoate, phosphonic acid, phthalide, picobenzamide , picoxystrobin, polyoxin, probenazole, prochloraz, procymidone, propamoc arb, propamocarb hydrochloride, propiconazole, propineb, proquinazide, protioconazole, pyrazotroph, priazophos, pirifenox, pyrimethanil, pirifenox, piroinitrin, pyroquilon, quinconazole, quinoxifene, quintozene, silthiopham, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, teczane, tecloftalam, tecnazeno, tetraconazole, thiabendazole, thifluzamide, thiophanate, thiophanate, thiophanate-methyl, thiram, thiadinyl, tolclofos-methyl, tolifluanide, triadimefon, triadimenol, triarimol, triazoxide, tridemorph, trimopramide tricyclazole, trifloxystrobin, triforine, triticonazole, uniconazole, validamycin, vinclozoline, zineb , ziram, and zoxamide; nematocides such as aldicarb, imiciaphos, oxamyl and fenamiphos; bactericides such as esptreptomycin; acaricides such as amitraz, cinometionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, ethoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexitiazox, propargite, pyridaben and tebufenpyrad; and biological agents including entomopathogenic bacteria such as Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, the encapsulated d endotoxins of Bacillus thuringiensis (eg Celicap, PV, NPVII); entomopathogenic fungi such as green muscardin fungi and entomopathogenic viruses including baculovirus, nucleopolyhedron virus (NPV) such as Helicoverpa zea nucleopolyhedrovirus (HzNPV), Anagraphafalcifera nucleopolyhedrovirus (Af PV); and granulosis virus (GV) such as Cidiaomonella granulosis virus (CpGV). The compounds of this invention and the compositions thereof can be applied to plants genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis endotoxins d). The effect of the compounds for the elimination of exogenously applied invertebrate pests of this invention can be synergistic with the toxin proteins expressed. The general references for these agricultural protectors (ie, insecticides, fungicides, nematocides, acaricides, herbicides and biological agents) include The Pesticide Manual, 13 th Edition, CDS Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, United Kingdom, 2003 and The BioPesticide Manual, 2nd Edition, LG Copping, Ed., British Crop Protection Council, Farnham, Surrey, United Kingdom 2001. A composition of the present invention is noted wherein at least one additional biologically active compound or agent is selected from the group consisting of Abamectin. , acephate, acetamiprid, acetoprol, aldicarb, amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, bistrifluron, buprofezin, carbofuran, cartap, cinometionat, chlorfenapyr, chlorfluazuron, chlorantraniliprole, chlorpyrifos, chlorpyrifosmethyl, chlorobenzilate, chromafenozide, clothianidin , ciflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyharthrine, lambda-cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, diafentiuron, diazinon, dicofol, dieldrin, dienochlor, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, etiprole, ethoxazole, fenamiphos, fenazaquine, fenbutatin oxide, phenothiocarb, fenoxicarb, fenpropatrine, fenpyroximate, fenvalerate, fipronil, flonicamid, flubendiamide, flucitrinate, - tau-fluvalinate, flufenerim, flufenoxuron, fonofos, halofenozide, hexaflumuron, hexitiazox, hydramethylnon, imiciaphos, imidacloprid, indoxacarb, isofenfos, lufenuron, malathion, metaflumizone, metaldehyde, methamidophos, metidation, methomyl, methoprene , methoxychlor, methoxyfenozide, metoflutrin, monocrotopos, nitempiram, nitiazine, novaluron, noviflumuron, oxamyl, parathion, parathion-methyl, permethrin, phorate, fosalone, fosmet, phosphamidon, pirimicarb, profenofos, proflutrin, propargite, protrifenbut, pymetrozine, pyrafluprol, pyrethrin , pyridaben, piridalil, pirifluquinazona, piriprol, piriproxifeno, rotenona, ryanodina, espinet arama, espinosad, espirodiclofeno, espiromesifeno, espirotetramat, sulprofos, tebufenozida, tefufenpirad, teflubenzuron, tefluthrin, terbufos, tetraclorvinfos, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpirad, tralometrina, triazamate, triclorfon, triflumuron; Bacillus thuringiensis subsp. Aizawai, Bacillus thuringiensis subsp. Kurstaki, nucleopolyhedrovirus and delta encapsulated endotoxins of Bacillus thuringiensis, baculovirus, entomopathogenic bacteria, entomopathogenic and entomopathogenic fungi. Particularly noted is a composition of the present invention wherein at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acephate, acetamiprid, acetoprol, amidoflumet < S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, bistrifluron, buprofezin, carbofuran, cartap, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyfluthrin, beta-cyfluthrin, cyhalothrin,? -cialotrina ,? -cialothrin, cypermethrin, cyromazine, deltamethrin, diafentiuron, diazinon, dieldrin, diflubenzuron, dimethoate, dinotefuran, diofenolane, emamectin, endosulfan, esfenvalerate, etiprole, phenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flunicamide, flubendiamide, flucitrinate, tau -fluvalinato, flufenerim (UR-50701), flufenoxuron, halofenozide, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, metaflumizone, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, methoxyfenozide, metofluthrin, monocrotophos, methoxyfenozide, nitenpyram, nitiazine, novaluron, noviflumuron (XDE-007), oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, fos meth, phosphamidon, pirimicarb, profenofos, profluthrin, protrifenbuto, pymetrozine, pyrethrin, pyridalyl, piriproxifen, rotenone, ryanodine, S1812 (Valent), spinosad, spiririclofen, spiromesifen (BSN 2060), sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorinated , thiaclopride, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpirad, tralometrine, triazamate, trichlorfon, triflumuron, aldicarb, fenamiphos, amitraz, quinomethionate, chlorobenzilate, cyhexatin, dicofol, dienochlor, ethoxazole, fenazaquine, fenbutatin oxide, fenpyroximate, hexythiazox, propargite , pyridaben, tebufenpyrad, Bacillus thuringiensis aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, entomopathogenic and entomopathogenic fungi. Also noteworthy is a composition of the present invention wherein at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acetamiprid, amitraz, avermectin, azadirachtin, bifenthrin, buprofezin, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos , clothianidin, cyfluthrin, ß-cyfluthrin, cyhalothrin, γ-cyclinthrin, cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolane, emamectin, endosulfan, esfenvalerate, etiprole, phenothiocarb, fenoxycarb, fenvalerate, fipronil, flunicamide, flubendiamide, flufenoxuron, hexaflumuron , hydramethylnon, imidacloprid, indcxacarb, lufenuron, metaflumizone, methomyl, methoprene, methoxyfenozide, nitenpyram, nitiazine, novaluron, oxamyl, pymetrozine, pyrethrin, pyridaben, pyridalyl, piroproxyfen, ryanodine, espirnetoram, spinosad, spiridiclofen, spiromesifen tebufenozide, thiaclopride, thiamethoxam, thiodicarb, thiosultap-sodium, tralometrine, triazamate, triflumuron, Bacillus thuringiensis subsp. Aizawai, Bacillus thuringiensis subsp. Kurstaki, nucleopolyhedrovirus and encapsulated delta endotoxin from Bacillus thuringiensis. A composition of the present invention is noted wherein at least one additional biologically active compound or agent is selected from the group consisting of cypermethrin, cyhalothrin, cyfluthrin and β-cyfluthrin, esfenvalerate, fenvalerate, tralometrine, phenothiocarb, methomyl, oxamyl, thiodicarb, acetamiprid, clothianidin, imidacloprid, thiamethoxam, thiacloprid, indoxacarb, spinosad, abamectin, avermectin, emamectin, endosulfan, etioprol, fipronil, flufenoxuron, triflumuron, diofenolane, priproxifene, pymetrozine, amitraz, Bacillus thuringiensis aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis delta endotoxin and entomophagous fungi. For embodiments wherein one or more of these various mixing partners are used, the weight ratio of these various mixing partners (in total) to the compound of formula 1 is typically between about 1: 3000 and about 3000: 1. It is noted that the weight ratios between about 1: 300 and about 300: 1 (e.g., ratios between about 1:30 and about 30: 1). A person skilled in the art can easily determine by simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity. It will be apparent that the inclusion of these additional components can expand the spectrum of invertebrate pests eliminated beyond the spectrum removed by the compound of formula 1 alone. In certain cases, combinations of a compound of this invention with other biologically active compounds or agents (ie, active ingredients) (particularly for the removal of invertebrate pests) may result in a greater effect on the additive (ie, synergistic) .
It is always desirable to reduce the amount of active ingredients released into the environment while ensuring effective pest control. When the synergism of the active ingredients for the elimination of invertebrate pests occurs at application rates that provide agronomically satisfactory concentrations of invertebrate pest elimination, such combinations can be advantageous to reduce the costs of crop production and decrease the environmental burden. Of note is a combination of a compound of formula 1 with at least one other active ingredient for the elimination of invertebrate pests. Particularly noted is a combination wherein the other active ingredient for the elimination of invertebrate pests has an action site different from the compound of formula 1. In some cases, a combination with at least one other active ingredient for the elimination of invertebrate pests. having a similar control spectrum but a different site of action will be particularly advantageous for administration to avoid resistance. In this manner, a composition of the present invention may additionally comprise a biologically effective amount of at least one additional active ingredient for the removal of invertebrate pests having a similar control spectrum but a different site of action. By contacting a genetically modified plant to express an invertebrate pest compound (for example protein) or the plant site with a biologically effective amount of a compound of this invention can also provide a spectrum of plant protection. wider and may be advantageous for the administration of resistance. Table A includes a list of specific combinations of a compound of formula 1 with other agents illustrating the mixtures, compositions and methods of the present invention for the elimination of invertebrate pests. The first column of Table A shows the specific agents for the elimination of invertebrate pests (for example, "Abamectin" in the first line). The second column d-Table A shows the mode of action (if known) of the chemical class of the agents for the elimination of invertebrate pests. The third column of table A shows one or several modalities of the proportions by weight ratios for the rates at which the agent for the elimination of invertebrate pests can be applied in relation to a compound of formula 1, an N-oxide or a salt thereof (eg, "50: 1 to 1:50" of abamectin in relation to the compound of formula 1, by weight). Thus, for example, the first line of Table A specifically describes the combination of a compound of formula 1 with abamectin which can be applied in a weight ratio between 50: 1 and 1:50. The remaining lines in Table A are constructed in a similar way. It is further noted that Table A includes specific combinations of a compound of formula 1 with other agents for the removal of invertebrate pests illustrative of the mixtures, compositions and methods of the present invention and includes additional embodiments of the weight ratio ranges. for application rates.
Table A Agent for the Mode of action or chemical class Relationship in pest elimination typical invertebrate weight Abamectin macrocyclic lactones 50: 1 to 1: 50 Acetamiprid neonicotinoides 150: 1 to 1: 200 Amitraz Octopamine receptor ligands 200: 1 to 1: 100 Avermectin macrocyclic lactones 50: 1 to 1: 50 Azadirachtin ecdysone agonists 100: 1 to 1: 120 Beta-cyfluthrin sodium channel modulators 150: 1 to 1: 200 Bifenthrin sodium channel modulators 100: 1 to 1: 10 Buprofezin chitin synthesis inhibitors 500: 1 to 1: 50 Cartare analogs of nereistoxin 100: 1 to 1: 200 Chlorantraniliprol ryanodine receptor ligands 100: 1 to 1: 120 Chlorfenapyr transport inhibitors from 300: 1 to 1: 200 mitochondrial electrons Clopiriphos cholinesterase inhibitors 500: 1 to 1: 200 Clotianidin neonicotinoides 100: 1 to 1: 400 Ciflutrin sodium channel modulators 150: 1 to 1: 200 Cihalotrin sodium channel modulators 150: 1 to 1: 200 Cypermethrin sodium channel modulators 150: 1 to 1: 200 Ciromazin inhibitors of chitin synthesis 400: 1 to 1: 50 Deltametrin sodium channel modulators 50: 1 to 1: 400 Dieldrin cyclodiene insecticides 200: 1 to 1: 100 Dinotefuran neonicotinoids 150: 1 to 1: 200 Diofenolan moulting inhibitor 150: 1 to 1: 200 Emamectin macrocyclic lactones 50: 1 to 1: 10 Cyclodiene insecticide endosulfan 200: 1 to 1: 100 Esfenvalerate sodium channel modulators 100: 1 to 1: 400 Etiprol chloride channel blockers 200: 1 to 1: 100 regulated by GABA Fenotiocarb 150: 1 to 1: 200 Fenoxicarb juvenile hormone mimics 500: 1 to 1: 100 Fenvalerate sodium channel modulators 50: 1 to 1: 200 Fipronil chloride channel blockers 150: 1 to 1: 100 regulated by -GABA Flonicamid 200: 1 to 1: 100 Flubendiamide ryanodine receptor ligands 100: 1 to 1: 120 Flufenoxuron chitin synthesis inhibitors 200: 1 to 1: 100 Hexaflumuron inhibitors of chitin synthesis 300: 1 to 1: 50 Hydramethylnon transport inhibitors from 150: 1 to 1: 250 mitochondrial electrons Imidacloprid neonicotinoid 1000: 1 to 1: 1000 Indoxacarb sodium channel modulators 200: 1 to 1: 50 Lambda-Cihalotrin sodium channel modulators 50: 1 to 1: 250 Lufenuron chitin synthesis inhibitors 500: 1 to 1: 250 Metaflumizon 200: 1 to 1: 200 ethomyl cholinesterase inhibitors 500: 1 to 1: 100 Metoprene imitate juvenile homons 500: 1 to 1: 100 Methoxyphenozide ecdysone agonists 50: 1 to 1: 50 Nitenpyram neonicotinoids 150: 1 to 1: 200 Nitiazine neonicotinoides 50: 1 to 1: 200 Novaluron chitin synthesis inhibitors 500: 1 to 1: 150 Oxamyl Cholinesterase Inhibitors 200: 1 to 1: 200 Pymetrozine 200: 1 to 1: 100 Piretrin sodium channel modulators 100: 1 to 1: 10 Pyridabeno transport inhibitors from 200: 1 to 1: 100 mitochondrial electrons Pyridalyl 2? 0: 1 to 1: 100 Juvenile Hormone Pyriproxyfen 500: 1 to 1: 100 Rianodine ryanodine receptor ligands 100: 1 to 1: 120 Spinetoram macrocyclic lactones 150: 1 to 1: 100 Spinosad macrocyclic lactones 500: 1 to 1: 10 Spirodiclofen inhibitors of lipid biosynthesis 200: 1 to 1: 200 Espiromesifeno inhibitors of lipid biosynthesis 200: 1 to 1: 200 Tephfenozide ecdysone 500 agonists: 1 to 1: 250 Thiacloprid neonicotinoides 100: 1 to 1: 200 Tiametroxam neonicotinoides 1250: 1 to 1: 1000 Thiodicarb cholinesterase inhibitors 500: 1 to 1: 400 Tiosultap-sodium 150: 1 to 1: 100 Tralometrine sodium channel modulators 150: 1 to 1: 200 Triazamate cholinesterase inhibitors 250: 1 to 1: 100 Triflumuron chitin synthesis inhibitors 200: 1 to 1: 100 Bacillus thuringiensis biological agents 50: 1 to 1: 10 Bacillus thuringiensis biological agents 50: 1 to 1: 10 delta-endotoxin NPV (for example biological agents 50: 1 to 1: 10 Gemstar) A modality of agents for the elimination of invertebrate pests < for example insecticides and acaricides) for mixing with compounds of this invention includes sodium channel modulators such as bifenthrin, cypermethrin, cyhalothrin, β-cytothrin, cyfluthrin, β-cyfluthrin, deltamethrin, dimefluthrin, esfenvalerate, fenvalerate, indoxacarb, metofluthrin, profluthrin. , pyrethrin and tralometrine; cholinesterase inhibitors such as clopyriphos, methomyl, oxamyl, thiodicarb and triazamate; neonicotinoids such as acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nitiazine, thiacloprid and thiamethoxam; macrocyclic insecticidal lactones such as spinetoram, spinosad, abamectin, avermectin and emamectin; chloride channel blockers regulated by GABA (α-aminobutyric acid) such as endosulfan, etiprole and fipronil; inhibitors of chitin synthesis such as buprofezin, cyromazine, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron and triflumuron; imitators of juvenile hormones such as diofenolane, phenoxycarb, methoprene and pyriproxyfen; octopamine receptor ligands, such as amitraz; ecdysone agonist such as azadirachtin, methoxyfenozide and tebufenozide; ryanodine receptor ligands such as ryanodine, anthranilic diamides such as chlorantraniliprole (see U.S. Patent 6,747,047, PCT publications WO 2003/015518 and WO 2004/067528) and flubendiamide (see U.S. Patent 6,603,044); Nereistoxin analogues such as cartap; inhibitors of mitochondrial electron transport such as chlorfenapyr, hydramethylnon and pyridaben; inhibitors of lipid biosynthesis such as spirodiclofen and spiromesifen; cyclodiene insecticides such as dieldrin; ciflumetofen; phenothiocarb; flonicamide; metaflumizone; pirafluprol; pyridalloyl; pyriprole; pymetrozine; spirotetramat; and thiosultap-sodium. One embodiment of biological agents for mixing with compounds of this invention include polyhedrovirus nuclei such as HzNPV and AfNPV; Bacillus thuringiensis and encapsulated d endotoxins of Bacillus thuringiensis such as Cellcap, MPV and MPVII; as well as viral insecticides as they occur naturally or genetically modified, including members of the Baculoviridae family as well as entomophagous fungi. The composition of the present invention is noted wherein at least one additional biologically active compound or agent is selected from the invertebrate pest elimination agents that is included in Table A above. The proportions by weight of a compound, which includes a compound of formula 1, an N-oxide or a salt thereof with respect to the additional agent for the elimination of invertebrate pests are typically between 1000: 1 and 1: 1000, with a constituted between 500: 1 and 1: 500, another modality is between 250: 1 and 1: 200 and another modality is between 100: 1 and 1:50. Table B, which is presented in the following, shows modalities of the specific compositions comprising a compound of formula 1 (the number of compounds refers to the compounds of indices A-C) and an additional agent for the elimination of invertebrate pests.
Table B Comp. and Mix Comp. and No. No. No. No. A-l 2 and Abamectin B-12 and Abamectin A-2 2 and Acetamiprid B-2 12 and Acetamiprid A-3 2 and Amitraz B-3 12 and Amitraz A-4 2 and Avermectin B-4 12 and Avermectin A-5 2 and Azadirachtin B-5 12 and Azadirachtin A-6 2 and β-cyfluthrin B-6 12 and β-cyfluthrin A-7 2 and Bifenthrin B-7 12 and Bifenthrin A-8 2 and Buprofezin B-8 12 and Buprofezin A-9 2 and Cartap B-9 12 and Cartap A-10 2 and · Chlorantraniliprol B-10 12 and Chlorantraniliprole A-l l 2 and Clorfenapir B-l l 12 and Clorfenapir A-12 2 and · Chlorpyrifos B-12 12 and Chlorpyrifos A-13 2 and Clotianidin B-13 12 and Clotianidin A-14 2 and Ciflutrin B-14 12 and Ciflutrin A-15 2 and Cialothrin B-15 12 and Cialothrin A-16 2 and Cypermethrin B-16 12 and Cypermethrin A-17 2 and Ciromazine B-17 12 and Ciromazine A-l 8 2 and Deltamethrin B-18 12 and Deltamethrin A-19 2 and Dieldrin B-19 12 and Dieldrin A-20 2 and Dinotefuran B-20 12 and Dinotefuran A-21 2 and Diofenolane B-21 12 and Diofenolane A-22 2 and Emamectin B-22 12 and Emamectin A-23 2 and Endosulfan B-23 12 and Endosulfan A-24 2 and Esfenvalerate B-24 12 and Esfenvalerate A-25 2 and Etiprol B-25 12 V Etioprol A-26 2 and Fenotiocarb B-26 12 and Fenotiocarb A-27 2 and Fenoxicarb B-27 12 and Fenoxicarb A-28 2 and Fenvalerate B-28 12 and Fenvalerate A-29 2 and Fipronil B-29 12 and Fipronil A-30 2 and Flonicamid B-30 12 and Flonicamid A-31 2 and Flubendiamide B-31 12 and Flubendiamide A-32 2 and Flufenoxuron B-32 12 and Flufenoxuron A-33 2 and Hexaflumuron B-33 12 and: Hexaflumuron A-34 2 and Hydramethylnon B-34 12 and Hydramethylnon A-35 2 and Imidacloprid B-35 12 and Imidacloprid A-36 2 and Indoxacarb B-36 12 and Indoxacarb A-37 2 and? -cialotrin B-37 12 and? -cialotrine A-38 2 and Lufenuron B-38 12 and Lufenuron A-39 2 and Metaflumizona B-39 12 and Metaflumizona A-40 2 and Methomil B-40 12 and Methomil A-41 2 and Metoprene B-41 12 V Metoprene A-42 2 and Methoxyfenozide B-42 12 and Methoxyfenozide A-43 2 and Nitenpyram B-43 12 and Nitenpyram A-44 2 and Nitiazine B-44 12 and Nitiazine A-45 2 and Novaluron B-45 12 and Novaluron A-46 2 and Oxamil B-46 12 and Oxamil A-47 2 and Pymetrozine B-47 12 and Pymetrozine A-48 2 and Pyrethrin B-48 12 and Pyrethrins A-49 2 and Pyridaben B-49 12 and Pyridaben A-50 2 and Piridalilo B-50 12 and Piridalilo A-51 2 and Pyriproxyfen B-51 12 and Pyriproxyfen A-52 2 and Rianodyne B-52 12 and Rianodyne A-53 2 and Espinetoram B-53 12 and Espinetoram A-54 2 and Espinosad B-54 '2 and Espinosad A-55 2 and Espirodiclofeno B-55 12 and Espirodiclofeno A-56 2 and Spiroesifen B-56 12 y. Spiroesifen A-57 2 and Tebufenozide B-57 12 and Tebufenozide A-58 2 and Thiacloprid B-58 12 and Thiacloprid A-59 2 and Thiamethoxam B-59 12 and Thiamethoxam A-60 2 and Thiodicarb B-60 12 and Thiodicarb A-61 2 and Tiosultapo of B-61 12 and Sodium sodium toxicity A-62. 2 and Tralometrin B-62 12 and Tralometrine A-63 2 and Triazamate B-63 12 and Triazamate A-64 2 and Trifiumuron B-64 12 and Trifiumuron - - A-65 2 and Bacillus B-65 12 and Bacillus thuringiensis thuringiensis A-66 2 and Bacillus B-66 12 and Bacillus thuringiensis thuringiensis d-endotoxin d-endotoxin A-67 9 and NPV (for B-67 12 and NPV (for example Gemstar) Gemstar) C-l 18 and Abamectin D-l 19 and Abamectin C-2 18 and Acetamiprid D-2 19 and Acetamiprid C-3 18 and Amitraz D-3 19 and Amitraz C-4 18 and Avermectin D-4 19 and Avermectin C-5 18 and Azadirachtin D-5 19 y. Azadirachtin C-6 18 and ß-cyfluthrin D-6 19 and ß-cyfluthrin C-7 18 and Bifenthrin D-7 19 and Bifenthrin C-8 18 and Buprofezin D-8 19 and Buprofezin C-9 18 and · Cartap D-9 19 and Cartap C-10 18 and Clorantraniliprol D-10 19 and Chlorantraniliprole C-l 18 and Clorfenapyr D-1 19 and Chlorfenapyr C-12 18 and Chlorpyrifos D-12 19 and Chlorpyrifos C-13 18 and Clotianidin D-l 3 19 and Clotianidin C-14 18 and Ciflutrin D-14 19 and Ciflutrin C-15 18 and Cialotrina D-l 5 19 and Cialotrina C-16 18 and Cipermetrina D-16 19 and Cipermetrina C-17 18 and Ciromazine D-17 19 and Ciromazine C-18 18 and Deltamethrin D-18 19 and Deltamethrin C-19 18 and Dieldrin D-19 19 and | Dieldrina C-20 18 and Dinotefurano D-20 19 and Dinotefuran C-21 18 and Diofenolane D-21 19 and Diofenolane C-22 18 and Emamectin D-22 19 and Emamectin C-23 18 and Endosulfan D-23 19 and Endosulfan C-24 18 and Esfenvalerate D-24 19 and Esfenvalerate C-25 18 and Etiprol D-25 19 and Etioprol C-26 18 and Phenothiocarb D-26 19 and Phenothiocarb C-27 18 and Fenoxicarb D-27 19 and Fenoxicarb C-28 18 and Fenvalerate D-28 19 and Fenvalerate C-29 18 and Fipronil D-29 19 and Fipronil C-30 18 and Flonicamid D-30 19 and Flonicamid C-31 18 and Flubendiamide D-31 19 and Flubendiamide C-32 18 and Flufenoxuron D-32 19 and Flufenoxuron C-33 18 and Hexaflumuron D-33 19 and Hexaflumuron C-34 18 and Hydramethylnon D-34 19 and Hydramethylnon C-35 18 and Imidaeloprid D-35 19 and Imidaeloprid C-36 18 and Indoxacarb D-36 19 and Indoxacarb C-37 18 and? -cialothrin D-37 19 and? -cialotrine C-38 18 and Lufenuron D-38 19 and Lufenuron C-39 18 and Metaflumizona D-39 19 and Metaflumizona C-40 18 and Metomil D-40 19 and Methomil C-41 18 and Metoprene D-41 19 and Metoprene C-42 18 and Methoxyfenozide D-42 19 and Methoxyfenozide C-43 18 and Nitenpyram D-43 19 and Nitenpyram C-44 18 and Nitiazine D-44 19 and Nitiazine C-45 18 and Novaluron D-45 19 and Novaluron C-46 18 and Oxamil D-46 19 and Oxamil C-47 18 and Pymetrozine D-47 19 and Pymetrozine C-48 18 and Pyrethrin D-48 19 and Pyrethrins C-49 18 and Pyridaben D-49 19 and Pyridaben C-50 18 and Pyridalyl D-50 19 and Pyridalyl C-51 18 and Pyriproxyfen D-51 19 and Pyriproxyfen C-52 18 and Rianodyne D-52 19 and Rianodyne C-53 18 and Espinetoram D-53 19 and Espinetoram C-54 18 and Espinosad D-54 19 and Espinosad C-55 18 and Spirodiclofeno D-55 19 and Espirodiclofeno C-56 18 and Spiroesifen D-56 19 and Spiroesifeno C-57 18 and Tebufenozide D-57 19 and Tebufenozide C-58 18 and Thiacloprid D-58 19 and Thiacloprid C-59 18 and Thiamethoxam D-59 19 and Thiamethoxam C-60 18 and Thiodicarb D-60 19 and Thiodicarb C-61 18 and Tiosultapo of D-61 19 and Tiosultapo-sodium sodium C-62 18 and Tralometrina D-62 19 and Tralometrina C-63 18 and Triazamate D-63 19 and Triazamate C-64 18 and Triflumuron D-64 19 and Triflumuron C-65 18 and Bacillus D-65 19 and Bacillus th ringiensis thuringiensis C-66 18 and Bacillus D-66 19 and Bacillus thuringiensis thuringiensis d-endotoxin d-endotoxin C-67 18 and NPV (for D-67 19 and NPV (for example Gemstar) Gemstar) The specific mixtures that are included in the table B typically combine a compound of formula 1 with another additional agent for the elimination of invertebrate pests in the proportions specified in table A. Invertebrate pests are eliminated in agronomic and non-agronomic applications by applying one or more compounds of this invention, typically in the form of a composition, in a biologically effective amount to the environment of the pests, which include the place of agronomic and / or non-agronomic infestation, to the area to be protected or directly to the pests to be eliminated.
Thus, the present invention comprises a method for controlling an invertebrate pest in agronomic and / or non-agronomic applications comprising contacting the invertebrate pest or its environment with a biologically effective amount of one or more of the invertebrate compounds. The invention or a composition comprising at least one of said compounds or a composition comprising at least one of said compounds and a biologically effective amount of at least one additional biologically active compound or agent. Examples of suitable compositions comprising a compound of the invention and a biologically effective amount of at least one additional biologically active compound or agent include granular compositions wherein the additional active compound is present in the same granule as the compound of the invention or in granules separated from those of the compound of the invention. For contact with a compound or composition of the invention to be carried out to protect a harvest field from invertebrate pests, the compound or composition is typically applied to the seed of the crop before planting it, to the foliage (eg leaves). , stems, flowers, fruits) of the harvest plants or to the soil or other growth medium before or after the crop is sown.
One mode of a contact method is by spray. Alternatively, a granular composition comprising a compound of the invention can be applied to the foliage of a plant or to the soil. The compounds of this invention can also be effectively delivered by uptake by the plant by contacting the plant with a composition comprising a compound of this invention applied as a soil drained of a liquid formulation, a granular formulation to the soil. , the treatment of a greenhouse box or by immersion of transplants. It is noted that the composition of the present invention in the form of a liquid drainage formulation for the soil. Also noted is a method for removing an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of the present invention or a composition comprising a biologically effective amount of a Composite of the present invention. It is further noted that this method where the environment is soil and the composition is applied to the soil as a drainage formulation for the soil. It is further noted that the compounds of this invention are also effective by localized application to the site of infestation. Other contact methods include application of a compound or a composition of the invention by the direct and residual application of sprays, aerial sprays, gels, seed coatings, microencapsulations, systemic uptake, baits, ear tags, bolus, nebulizers, fumigants , aerosols, powders and many others. One embodiment of a contact method is a dimensionally stable fertilizer granule, bar or tablet comprising a compound or composition of the invention. The compounds of this invention can also be impregnated into materials for making invertebrate control devices (eg insect nets). The compounds of this invention are also useful in the treatment of seeds to protect the seeds of invertebrate pests. In the context of the present description and claims, treat a seed medium by contacting the seed with a biologically effective amount of a compound of this invention, which is typically formulated as a composition of the invention. This treatment of the seed protects the seed of the invertebrate soil pests and generally also protects the roots and other parts of the plants in contact with the soil from the development of seedlings from the seed in germination. The treatment of the seeds also provides foliage protection by displacement of the compound of this invention or a second active ingredient within the developing plant. Seed treatments can be applied to all types of seeds that include those from which genetically transformed plants will germinate to express specialized traits. Representative examples include those that express proteins toxic to invertebrate pests such as Bacillus thuringiensis toxin or those that express resistance to herbicides such as glyphosate acetyltransferase, which provides resistance to glyphosate. A method of treating seeds is by sprinkling or spraying the seed with a compound of the invention (ie, as a formulated composition) before sowing the seeds. Compositions formulated for seed treatment generally comprise a film former or an adhesive agent. Therefore, typically, a seed coat composition of the present invention comprises a biologically effective amount of a compound of formula 1, an N-oxide or a salt thereof and a film-forming or adhesive agent. The seed can be spray-coated from a flowable suspension concentrate directly into a coating bed by drumming seeds and then drying the seeds. Alternatively, other types of formulations such as moistened powders, solutions, suspoemulsions, emulsifiable concentrates and emulsions in water can be sprinkled on the seeds. This procedure is particularly useful for applying film coatings on the seeds. Various machines and coating processes are available to those skilled in the art. Suitable procedures include those indicated in P. Kosters et al., Seed Treatment: Progress and Prospect, 1994 BCPC Mongraph No. 57 and the references included in that document. The treated seed typically comprises a compound of the present invention in an amount of about 0.1 g to 1 kg per 100 kg of seed (ie, from about 0.0001 to 1% by weight of the seed, before treatment). A flowable suspension formulated by seed treatment typically comprises from about 0.5 to about 70% of the active ingredient, from about 0.5 to about 30% of a film-forming adhesive, from about 0.5 to about 20% of a dispersing agent, from 0 to about 5% of a thickener, from 0 to about 5% of a pigment and dye, from 0 to about 2% of an antifoam agent, from 0 to about 1% of a preservative and from 0 to about 75% of a liquid diluent volatile. The compounds of this invention can be incorporated into a bait composition that is consumed by an invertebrate pest or used within a device such as a trap, a bait station and the like. Said bait composition may be in the form of granules which comprise: (a) active ingredients, specifically a biologically effective amount of a compound of formula 1, an N-oxide or a salt thereof; (b) one or more food materials; optionally (c) an attractant and optionally (d) one or more humectants. It is noted the granules or bait compositions which comprise between about 0.001-5% of active ingredients, about 40-99% of food material and / or attractant; and optionally about 0.05-10 of humectants, which are effective in controlling invertebrate pests in the soil at very low application rates, particularly at doses of active ingredient that are fatal by ingestion rather than by direct contact. Some food materials can function as a source of food and as an attractant. Food materials include carbohydrates, proteins and lipids. Examples of food materials are vegetable flour, sugar, starches, animal fat, vegetable oil, yeast extracts and milk solids. Examples of attractants are odorants and flavorings, such as fruit or plant extracts, perfume or other animal or vegetable components, pheromones or other agents that are known to attract an objective invertebrate pest. Examples of humectants, ie, moisture retaining agents are glycols of other polyols, glycerin and sorbitol. A bait composition (and a method using said bait composition) used to control at least the vertebrate pest that is selected from the group consisting of ants, termites and cockroaches is noted. A device for controlling the invertebrate pest may comprise the present bait composition and a housing adapted to receive the bait composition, wherein the housing has at least one opening that is sized to allow the invertebrate pest to pass through. of the opening so that the invertebrate pest has access to the bait composition from a location outside the housing, and wherein the housing is further adapted to be positioned or near the site of potential or known activity for the invertebrate pest. The compounds of this invention can be applied without other adjuvants but very often the application will be of a formulation comprising one or more active ingredients with suitable carriers, diluents and surfactants and possibly in combination with a food, depending on the end use contemplated. An application method involves spraying a water dispersion or refined oil solution of a compound of the present invention. Combinations with spray oil, spray oil concentrations, spray tackifiers, adjuvants, other solvents and synergists such as piperonyl butoxide often increase the effectiveness of the compound. For non-agronomic uses such sprays can be applied from spray cans such as a can, bottle or other container, either by means of a pump or by releasing it from the precipitated container, for example, a pressurized aerosol spray can. Said spray compositions can take various forms, for example sprays, mists, foams, fumes or mists. Said spray compositions therefore may further comprise propellants, foaming agents, etc. according to the case. A spray composition comprising a biologically effective amount of a compound or a composition of the present invention and a carrier is noted. One embodiment of said spray composition comprises a biologically effective amount of a compound or a composition of the present invention and a propellant. Representative propellants include, but are not limited to methane, ethane, propane, butane, isobutane, butene, pentane, isopentane, neopentane, pentene, hydrofluorocarbons, chlorofluorocarbons, dimethyl ether and mixtures thereof. A sprinkling composition is noted. { and a method using said spray composition supplied from a spray vessel) which is used to control at least one invertebrate pest that is selected from the group consisting of mosquitoes, black flies, barn flies, deer flies, horse flies, wasps, yellow jacket wasps, hornets, ticks, spiders, ants, mosquitoes and the like, which include individually or in combinations. Non-agronomic applications include protecting an animal, particularly a vertebrate, more particularly a homeothermic vertebrate (e.g., a mammal or bird) and more particularly a mammal from an invertebrate parasitic pest by administering an effective parasiticidal amount (i.e. biologically effective) of a compound of the invention, typically in the form of a composition formulated for veterinary use to the animal to be protected. Therefore, a method for protecting an animal comprising administering to the animal an effective parasiticidal amount of a compound of the invention is noted. With reference to the current description and claims, the term "parasiticide" and "parasiticidally" refers to the observable effects on an invertebrate parasite pest to provide protection to an animal from the pest. The parasiticide effects are typically related to decreased presentation or activity of the target parasitic and vertebrate pest. Such effects on the pest that include necrosis, death, retarded growth, diminished mobility or diminished capacity to remain on or within the host animal, reduce its feeding and inhibition of reproduction. These effects on pests of invertebrate parasites provide control (including prevention, reduction or control) of parasitic infestation or infection of the animal. Examples of pests of controlled invertebrate parasites administering a parasitically effective amount of a compound of the invention to an animal to be protected include hectoparasites (atropods, mites, etc.) and endoparasites (helminths, eg, nematodes, trematodes, cestodos, acanthos, etc.). In particular, the compounds of the invention are effective against ectoparasites including: flies such as Haematobia (Lyperosia) irritans (horn flies), Stomoxys calcitrans (stable flies), genus Simulium (black aphid), genus Glossina (tsetse flies), Hydrotaea irritans (head flies), Musca autumnalis (face flies), Musca domestica (house flies), Morellia simplex (sweet flies), genus Tabanus (horse flies), Hypoderma bovis, Hypoderma lineatum, Lucila sericata, Lucila cuprina (greenbottle), genus Calliphora (botfly), genus Protophormia, Oestrus ovis (nasal botfly), genus Culicoides, mosquitoes), Hippobosca equine, Gastrophilus intestinalis, Gastrophilus haemorrhoidalis and Gastrophilus naslis, lice such as Bovicola (Damalinia) bovis , Bovicola equi, Haematopinus asini, Felicola subrostratus, Heterodoxus spiniger, Lignonathus setosus and Trichodectes canis; keds such as Melophagus ovinus mites such as genus Psoroptes, Sarcoptes scabei, Chorioptes bovis, Demodex egui, genus Cheyletiella, Notoedres cati, genus Trombicula and Otodectes cyanotis (mites of the ear); ticks such as genus Ixodes, genus Boophilus, genus Rhipicephalus, genus Amblyomma, genus Dermacentor, genus Hyalonuna and genus Haemaphysalis and fleas such as Ctenocephalides felis (cat flea) and Ctenocephalides -can.is (dog flea). Non-agronomic applications in the veterinary sector are by conventional means such as enteral administration in the form, for example, of tablets, capsules, beverages, drainage preparations, granules, pastes, bolus, through-feed methods or suppositories; or by parenteral administration, for example, by injection (including intramuscular, subcutaneous, intravenous, intraperitoneal), implants; by nasal administration; by topical administration, for example in the form of dipping or dripping, spraying, washing, powder coating or application to a small area of the animal and through articles such as collars on the neck, ear tags, tail bands, bands in the limbs or fasteners comprising compounds or compositions of the present invention. Typically, a parasiticidal composition according to the present invention comprises a mixture of a compound of formula 1, an N-oxide or a salt thereof with one or more pharmaceutically or veterinarily acceptable carriers comprising auxiliary excipients which are selected with respect to the proposed route of administration (eg, oral, topical or parenteral administration, for example as an injection) and in accordance with standard practice. In addition, a suitable carrier is selected based on compatibility with one or more active ingredients in the composition that include considerations such as stability in relation to pH and moisture content. Therefore, a composition for protecting an animal from an invertebrate parasitic pest comprising an effective parasiticidal amount of a compound of the invention and at least one carrier is noted. For parenteral administration including intravenous, intramuscular and subcutaneous injection a compound of the present invention may be formulated in suspension, solution or emulsion in oily or aqueous vehicles and may contain adjuvants such as suspension improving agents, stabilizers and / or dispersants. Pharmaceutical compositions for injection include aqueous solutions or water-soluble forms of active ingredients. { for example a salt of an active compound), preferably in physiologically compatible buffers that contain other excipients or auxiliaries as are known in the pharmaceutical formulating art. For oral administration including solutions (which are more readily available for absorption), emulsions, suspensions, pastes, gels, capsules, tablets, boluses, powders, granules, rumen retention and feed / water / lick blocks, a compound of the present invention can be formulated with binders / filling materials known in the art as suitable for oral administration compositions such as sugars (for example lactose, sucrose, mannitol, sorbitol), starch (for example corn starch, wheat starch) , rice starch, potato starch), cellulose and derivatives (for example methylcellulose, carboxymethylcellulose, ethylhydroxycellulose), protein derivatives (for example zein, gelatin) and synthetic polymers (for example polyvinyl alcohol, polypyrrolidone). If desired, lubricants (for example magnesium stearate), disintegrating agents (for example crosslinked polyvinylpyrrolidone, agar, alginic acid) and dyes or pigments can be added. Pastes and gels often also contain adhesives (eg acacia gum, alginic acid, bentonite, cellulose, xanthan gum, magnesium and aluminum colloidal silicate) to help keep the composition in contact with the oral cavity and so that it does not be expelled easily.
If the parasitic compositions are in the form of feed concentrates, the carrier is typically selected from high performance feed, feed cereals or protein concentrates. Said compositions containing food concentrate can, in addition to the active ingredients parasiticides comprise additives that promote the health and growth of the animal, which improve the quality of the meat of the animals for slaughter or useful in some other way for the children of the animals. animals. These additives include, for example, vitamins, antibiotics, chemotherapeutic, bacteriostatic, fungistatic, coccidiostatic and hormone substances. It has been found that the compounds of the present invention have favorable pharmacokinetic and pharmacodynamic properties that provide systemic availability from oral administration and ingestion. Therefore, after ingestion by the animal to be protected, the parasiticidally effective concentrations of the compounds of the invention in the bloodstream protect the treated animal from insect pests that suck blood such as fleas, ticks and lice. . Therefore, a composition is noted to protect an animal from a plague of invertebrate parasites in a form for oral administration (ie, comprising, in addition to the parasiticidal effective amount of a compound of the invention, one or more carriers that they are selected from binders and fillers suitable for oral administration and carriers with food concentrate). Formulations for topical administration are typically in the form of powder, cream, suspension, spray, emulsion, foam, paste, spray, ointment, ointment or gel. More typically, a topical formulation is a water-soluble solution which may be in the form of a concentrate that is diluted before use. Parasiticidal compositions suitable for topical administration typically comprise a compound of the present invention and one or more topically suitable carriers. In applications of a parasiticide composition topically to the outside of an animal such as a line or a point (ie "staying" treatment), the active ingredient is expected to travel over the surface of the animal to cover most or all of its external surface area. As a result, the treated animal is particularly protected from invertebrate pests that feed on the animal's epidermis such as ticks, fleas and lice. Therefore, formulations for topical localized administration often comprise at least one organic solvent to facilitate the transport of the active ingredient on the skin and / or penetration into the animal's epidermis. Solvents commonly used as carriers in such formulations include propylene glycol, paraffins, aromatics, esters such as isopropyl myristate, glycol ethers and alcohols such as ethanol and n-propanol. The application rate required for effective control (ie, the "biologically effective amount") will depend on factors such as the species of invertebrates to be controlled, the life cycle of the pest, the life stage, its size, location, time of year, harvest or host animal, feeding behavior, mating behavior, environmental humidity, temperature and the like. Under normal circumstances, application rates of approximately 0.01 to 2 kg of active ingredients per hectare are sufficient to control pests in agronomic ecosystems, but an amount as small as 0.0001 kg / hectare may suffice or such an amount may be required. Big as 8 kg / hectare. For non-agronomic applications, effective usage rates vary from approximately 1.0 to 50 mg / square meter, but an amount as small as 0.1 mg / square meter may be required, or an amount as large as 150 mg / may be required. square meter. A person skilled in the art can readily determine the biologically effective amount necessary for the desired level of invertebrate pest control. In general, for veterinary use, a compound of formula 1, an N-oxide or a salt thereof is administered in an effective amount parasiticide to an animal to be protected from pests of invertebrate parasites. An effective parasiticidal amount is the amount of active ingredient that is needed to obtain an observable effect that decreases the presentation or activity of the target invertebrate parasite pest. A person skilled in the art will appreciate that the parasiticidal effective dose may vary for the various compounds and compositions of the present invention. The desired parasiticidal effect and duration, the target invertebrate pest species, the animal to be protected, the mode of application and the like, as well as the amount that is needed to obtain a particular result can be determined by simple experimentation. For oral administration to homeothermic animals, the daily dosage of a compound of the present invention typically ranges from about 0.01 mg / kg to about 100 mg / kg, more typically from about 0.5 mg / kg to about 100 mg / kg of the body weight of the animal. For topical (e.g. dermal) administration, dips and sprays typically contain from about 0.5 ppm to about 5000 ppm, more typically from about 1 ppm to about 3000 ppm of a compound of the present invention. The following abbreviations are used in the following A-D Index Tables: CF3 means trifluoromethyl, -CN is cyano, and -N02 is nitro. The abbreviation "Ex." indicates "Examples" and is followed by a number indicating in which example the compound is prepared. In index tables A, B and C, (2) m refers to the combination of (R2) n as shown with instance of Z which is CR2, as specified for formula 1.
INDEX TABLE A Compound (') m U R R Q P-f. (° C) 1 (ex.l) 3-C1, 5-CI C (= 0) CH3 HC (= 0) NHCH2CF3 ** 2 (ex.2) 3-CI, 5-C1 Q = 0) CH3 HC (= 0) NHCH2-2-pyridinyl ** 3 (ex.4) HC (= 0) H -CN -N02 ** 4 (ex.3) 3-C1, 5-C1 S (= 0) CH3 HC (= 0) NHCH2 -2-pyrydinyl ** 5 3-FC (= 0) CH3 H iH-l, 2,4-triazol-l-yl * 6 3-C1, 5-C1 C (= 0) CH3 H lH-l , 2,4-triazol-l-yl * 7 3-FC (= 0) CH3 HC (= 0) NHCH2-2-pyridinyl * 8 3-C !, 5-C1 C (= 0) Cl H 4-morpholinyl * 9 3-CI, 5-C1 C (= 0) HH -CN * 10 3-C1, 4-C1 C (= Q) CH3 H lH-1, 2,4-triazole -] - ilo * 11 3- C1 C (= 0) CH3 H lH-1,2,4-triazol-l-yl 12 3-C1, 4-C1 C (= 0) CH3 HC (= 0) NHCH2-2-pyridinyl * 13 3-C1 C (= 0) CH3 H C (= 0) NHCH2-2-pyridinyl * 14 3-C1, 5-C1 S (= 0) CH3 H lH-l, 2,4-triazol-l-yl * 15 3-C1, 5-C1 S (= 0) 2 CH3 H 1 H-1, 2,4-triazol-1-yl * 16 3-C1, 5-C1 C (= 0) -CN H lH-1, 2,4-triazol-1-yl * 17 3-C1, 5-C1 C (= 0) CH3 H Br * 18 3-C1, 5-C1 S (= 0) 2 CH3 H C (= 0) NHCH2-2-pyridinyl * 19 3-C1, 5-C1 c (= o) CH3 H C (= 0) NHCH (CH3) -2-pyridinyl * See index table C for H-NMR data * See synthesis example for NMR data INDEX TABLE B See index table C for H-NMR data INDEX C-TABLE See synthesis example for NMR data TABLE INDEX D Compound 1H NMR data (solution CDC13, unless otherwise indicated) 3 5 d 8.25 (s, 1H), 8.12 (s, 1H), 7.58 d wide ,. 2H), 7.53-7.47 < m, 4H), 7.39-7.33 (m, 6H), 7.21 (dt, 2H), 7.68 (d, 1H), 4.68 (d, 1H), · 4.36 (d, 1H), 2.27 (s, 3H). 6 d 8.26 < s, 1H), 8.12 (s, 1H), 7.57-7.50 (m, 5H), 7.36 (d, 1H), 4.68 (d, 1H), 4.35 (d, 2H), 2.27 < s, 3H). 7 6 7.80-7.20 (m, 11H), 4.74 (d, 2H), 4.65 (d, 1H), 4.34 (d, 1H), 2.50 (s, 3H) 8 d 7.56-7.35 (m, 5H), 7.06 (d, 1H), 4.57 (d, 1H), 4.24 (d, 1H), 3.87 (m, 4H), 3.03 (m, 4H). 5 9 d 7.73-7.68 (m, 4H), 7.51 (s, 1H), 7.48 (s, 2H), 4.64 (d, 1H), 4.30 (d, 1H). 10 d 8.60 (s, 1H), 8.09 (s, 1H), 7.91 (d, 1H), 7.81 (d, 1H), 7.75-7.69 (m, 3H), 7.47 (d, 1H), 5.05 (d, 1H), 4.84 (d, 1H), 2.26 (s, 3H). 11 d 8.60 (s, 1H), 8.09 (s, 1H), 7.76-7.60 (m, 6H), 7.47 < d, 1H), 5.05 < d, 1H), 4.82 (d, 1H), 2.26 (s, 3H). 12 d 8.50 (d, 1H), 8.02 (t, 1H), 7.88 < d, 1H), 15 7.78-7.61 (m, 6H), 7.41 (d, 1H), 7.21 (dd, 1H), 4.98 (d, 1H), 4.77 (d, 1H), 4.65 td, | 2H), 2.45 (s, 3H) ). 13 d 8.48 < d, 1H), 8.04 (t, 1H), 7.74-7.52 (m, 20 8H), 7.41 (d, 1H), 7.21 (dd, 1H), 4.98 (d, 1H), 4.75 (d, 1H), 4.65 (d, 2H), 2.45 (s, 3H). 14 (1: 1 mixture of diastereomers) d 8.25 (s, 0.5?), 8.22 (s, 0.5H), 8.13 (s, 0.5H), 8.12. (s, 0.5H), 7.50 < m, 3H), 7.34 < t, 1H), 7.12- 7.04 (m, 2H), 4.75 (d, 0.5H), 4.58 (d, 0.5H), 4.42 (d, 0.5H), 4.22 (d, 0.5H), 2.25 (s) , 1.5H), 2.23 (s, 1.5H). 5 15 d 8.27 (s, 1H), 8.13 (s, 1H), 7.54 (t, 1H), 7.49. { s broad, 2H), 7.40 (d, 1H), 7.33 (broad d, 1H), 7.28 (dd, 1H), 4.68 (d, 1H), 4.33 (d, 1H), 2.27 (s, 3H). 16 d 8.76 (s, 1H), 8.18 (s, 1H), 8.02 < m, 2H), 10 7.84 (d, 1H), 7.52 (m, 3H), 4.70 (d, 1H), 4.38 < d, 1H). 17 d 7.54 < d, 1H), 7.50-7.48 (m, 3H), 7.41 (d, 1H), 7.22 (dd, 1H), 4.58 (d, 1H), 4.24 (d, | 1H). 15-18 d 8.51 (d, 1H), 8.03 (broad t, 1H), 7.79-7.75 (m, 4H), 7.62 < d, 1H), 7.46 < d, 1H), 7.34 < m, 2H), 7.25. { dd, 1H), 5.14 (d, 1H), 4.92 (d, 1H), 4.68 (d, 2H), 2.47 (s, 3H). 19 d 8.51 (d, 1H), 7.70 (dt, 1H), 7.49 (s) 20 broad, 4H), 7.41 < -dd, 1H), 7.35-7.29 (m, | 3H), 7.21 (dd, 1H), 5.31 (quintet, 1H), 4.62. { d, 1H), 4.28 (d, 1H), 2.49 (s, 3H), 1.58 (d, 3H)) 25 101 d 8.32 (d, 1?), 7.81 (d, 1H), 7.73 (broad d, 1H), 7.65 (m, 2H), 7.53 (t, 1H), 7.50 (m, 2H), 7.31 (d , 1H), 4.63 (d, 1H), 4.29 (d, 1H). 102 d 8.47 (d, 1H), 8.39 (m, 1H), 7.73 < m, 1H),. 7.64 (m, 2H), 7.57 < m, 3H), 7.51 (broad s, .3H), 7.31 < dd, 2H), 7.18 (t, 1H), 4.77 (d, 2H), 4.58 (d, 1H), 4.28 < d, 1H). 103 d 8.40 (broad t, 1H), 8.34 (m, 1H), 7.95 (m, 1H), 7.79-7.66 (m, 8H), 4.97 (d, 1H), 4.86 (d, 1H), 4.40 (m , 2H). a XH NMR data are in downfield ppm for tetramethylsilane. The couplings are designated as s) singlet, < d) doublet, (t) triplet, (m) multiplet, (s broad) wide singlet, (d a) wide doublet, (t a) wide triplet, (dd) doublet of doublet and (dt) doublet of triplet.
BIOLOGICAL EXAMPLES OF THE INVENTION The following tests demonstrate the control efficacy of the compounds of this invention on specific pests. The "control efficacy" represents inhibition of development of invertebrate pests (including mortality) that causes significantly reduced feeding. The pest control protection provided by the compounds, however, is not limited to these species. See tables of index A-D for description of compounds.
TEST A To evaluate the control of the diamond lead moth (Plutella xylostella), the test unit consists of a small open container with a 2-14-day-old radish plant inside. Pre-infest with 10-15 neonatal larvae on a piece of insect diet by using a core sampler to control a plug of a leaf of the hardened insect diet that has many larvae growing on it and the plug is transferred which contains the larvae and diet to the test unit. The larvae move on the test plant as the diet plug dries. The test compounds are formulated using a solution containing 10% acetone, 90% water and 300 ppm nonionic surfactant X-77MR Spreader Lo-Foam Formula containing alkylaryl polyoxyethylene, free fatty acids, glycols and isopropanol (Loveland Industries, Inc. Greeley, Colorado, USA). The formulated compounds are applied in 1 ml of liquid through an SUJ2 atomizer nozzle with a 1/8 JJ adapted body (Spraying Systems Co. Wheaton, Illinois, USA) placed 1.27 cm (0.5 inches) above the top of each test unit. All the experimental compounds in these tests were sprayed at 50 ppm and were made in duplicate, three times. After spraying the formulated test compound, each test unit is allowed to dry for 1 hour and then a black screw cap is placed on top. The test units are maintained for 6 days in a growth chamber at 252C and 70% relative humidity. The control efficacy level of the test compound is then determined usually based on foliage feed damage and larval mortality of each test unit. Of the compounds of formula 1 tested the following provided very good to excellent levels of protection of the plant (20% less feeding damage or 80% or more mortality): 1, 2, 6, 10, 12, 13, 15 , 16, 18, 19 and 102.
TEST B To evaluate the control of the autumn worm (Spodoptera frugiperda), the test unit consists of a small open container with a 4-5-day-old corn plant inside. This is pre-infested (using core sampler) with 10-15 1-day-old larvae on a piece of insect diet.
The test compounds are formulated and sprayed at 250 ppm as described for test A and are duplicated three times. After spraying, the test units are maintained in a growth chamber and then visually classified as described for test A. Of the compounds of formula 1 tested, the following provide very good to excellent levels of plant protection (20% or less of feeding damage or 80% or more of mortality): 1, 2, 16, 18 and 19.
TEST C To evaluate the control of western flowering tisanóptaro (Frankliniella occidentalis) through contact and / or systemic medium, the test unit consisted of a small open container with a 5-7-day-old Longio Bean plant in its inside. The test compounds are formulated and sprayed at 250 ppm and duplicated three times as described for test A. After spraying, the test units are allowed to dry for 1 h and then 22-27 adult Thysanoptera are added to each unit and a black bolted lid is placed on top. The test units are maintained for 7 days at 25 eC and relative humidity 45-55%. A mortality classification is determined for each test unit.
Of the compounds tested, the following provided very good to excellent levels of protection to the plant (20% or less of damage by feeding or 80% or more of mortality): 2, 12, 18 and 19.
TEST D To evaluate the control of potato hopper (Empoasca fabae Harris) through a contact and / or systemic medium, the test unit consists of a small open container with a Soleil bean plant for 5-6 days of age (with primary germinated leaves) inside. White sand is added to the top of the soil and one of the primary leaves is cut before application. The test compounds are formulated and sprayed at 250 ppm and the test is doubled three times as described for test A. After spraying, the test units are allowed to dry 1 hour before they are postinfestated with five skips. of potatoes (adults 18 to 21 days old). A black bolted cover is placed on top of the cylinder. The test units are maintained for 6 days in a growth chamber at 19-21 aC and a relative humidity of 50-70%. The control efficiency of each test unit is then determined visually by the mortality of the insects. Of the compounds of formula 1 tested, the following provided very good to excellent levels of control efficacy (70% or more of mortality): 2, 12, 16, 18, 19 and 103.
TEST E To evaluate the control of the green peach aphid (Myzus persicae) through contact and / or systemic medium, the test unit consists of a small open container with a 12-15-day-old radish plant in its inside. This is pre-infested by placing 30-40 aphids on a sheet of the test plant on a piece of cut plant from a crop plant (cut-leaf method). The larvae move to the test plant as the piece of leaf dries. After the preinf station, the floor of the test unit is covered with a layer of sand. All test compounds are formulated and sprayed at 250 ppm as described for test A and duplicated three times. After spraying the formulated test compound, each test unit is allowed to dry for 1 hour and then a black threaded cap is placed on top. The test units are maintained for 6 days in a growth chamber at 19-21 SC and relative humidity 50-70%. Each test unit is then visually determined to determine insect mortality. Of the compounds of formula 1 tested, the following resulted in 50% or more mortality: 2, 18 and 19.
TEST F To evaluate the control of the cotton melon aphid (Aphis gossypii) through the contact and / or systemic medium, the test unit consists of a small open container with a cotton plant 6-7 days old in its interior. This is preinfesta with 30-40 insects on a piece of sheet, according to the method of cutting-sheet described by test C and the floor of the test unit is covered with a layer of sand. The test compounds are formulated and sprayed at 250 ppm, as described for test A. The applications are duplicated three times. After spraying the formulated test compound, each test unit is allowed to dry for 1 hour and then a black screwed layer is placed on top. The test units are kept for 6 days in a growth chamber at 19-21 eC and relative humidity 50-70%. Each test unit is then visually determined to determine insect mortality. Of the compounds of formula 1 tested, the following result in 50% or more of mortality: 16, 18 and 19.
TEST G To evaluate the control of the cat flea (Ctenocephalides felis Bouche), a CD-1MR mouse (male, approximately 30 g obtained from Charles River Laboratories, Wilmington, A) is orally dosed with the compound test at 30 ppm solubilized in propylene glycol / glycerol formal (60:40). Two hours after oral administration of the test compound, approximately 8 to 16 adult fleas were placed in each mouse. Fleas were then evaluated for mortality 48 hours after the application of the fleas in mice. Of the tested compounds, the following compounds caused a mortality of 50% or greater: 1, 2, 12, 13, 16, 18, 19 and 102. It is noted that in relation to this date, the best method known by the applicant to carry the practice said invention is that which is clear from the present description of the invention.

Claims (27)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. A compound of formula 1, an N-oxide or a salt thereof, 1 characterized in that G is O or NR3; U is C { = 0), S (= O), C (= S) or S (0) 2; Z is N or CR2; A1 is CR4 OR N; A2 is CR5 O N; A3 is CR6 OR N; A4 is CR7 OR N; Q is a saturated or unsaturated 5- or 6-membered heterocycle optionally substituted with one or more substituents that are independently selected from halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 10 atoms of carbon, halohalocycloalkyl of 3 to 1 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, haloalkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, haloalkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 carbon atoms, haloalkylsulfonyl of 1 to 6 carbon atoms, alkylamino of 1 to 6 carbon atoms, dialkylamino of 2 to 8 carbon atoms carbon, cyano, nitro, C (= 0) NR8R9, C (= 0) OR10, phenyl and pyridinyl, each phenyl or pyridinyl is optionally substituted with one or more substituents that are independently selected from R11; or Q is C (0) NR12R13, C (S) NR12R13, S (0) 2NR1R15 or R16; R1 is cyano, alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms or cycloalkylalkyl from 4 to 7 carbon atoms, each optionally substituted with one or more substituents that are independently selected from R17; each R2 is independently H, halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, haloalkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, haloalkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 carbon atoms, haloalkylsulfonyl of 1 to 6 carbon atoms alkylamino of 1 to 6 carbon atoms, dialkylamino of 2 to 8 carbon atoms, alkoxycarbonyl of 2 to 4 carbon atoms, alkylaminocarbonyl of 2 to 4 carbon atoms, dialkylaminocarbonyl of 3 to 9 carbon atoms, cyano or nitro; R3 is H, cyano or -CHO; or alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms, cycloalkylalkyl of 4 to 7 carbon atoms, phenyl, alkylcarbonyl of 1 to 6 carbon atoms, alkoxycarbonyl of 1 to 6 carbon atoms, alkylaminocarbonyl of 2 to 6 carbon atoms or dialkylaminocarbonyl of 3 to 9 carbon atoms, each optionally substituted with one or more substituents that are independently selected from R18; R4, R5, R6 and R7 are independently selected from H, halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, halocycloalkyl of 3 to 6 carbon atoms alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, haloalkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, haloalkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 carbon atoms, haloalkylsulfonyl of 1 to 6 carbon atoms, alkylamino of 1 to 6 carbon atoms, dialkylamino of 2 to 8 carbon atoms, cyano and nitro; or R6 and R7 are taken together to form a fused aromatic ring, the fused aromatic ring contains as ring member, in addition to the bridgehead atoms A3 and A4, 3 atoms selected from 1 to 2 carbon atoms, 0 to 2 nitrogen atoms, 0 to 1 oxygen atom and 0 to the sulfur atom, or 4 atoms that are selected from 2 to 4 carbon atoms and 0 to 2 nitrogen atoms; each R8, R12 and R14 is independently H, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms, cycloalkylalkyl of 4 to 7 carbon atoms, alkylcarbonyl of 2 to 7 carbon atoms, alkoxyalkyl of 2 to 6 carbon atoms or alkoxycarbonyl of 2 to 7 carbon atoms; each R9, R10, R13 and R15 is independently H; or alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms or cycloalkylalkyl of 4 to 7 carbon atoms, each optionally substituted with one or more substituents that are independently selected from R19; each R11, R23 and R24 is independently halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, haloalkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, haloalkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 carbon atoms, haloalkylsulfonyl of 1 to 6 carbon atoms, alkylaminosulfonyl of 1 to 6 carbon atoms, alkylamino of 1 to 8 carbon atoms, dialkylamino of 2 to 8 carbon atoms, alkoxycarbonyl of 2 to 4 carbon atoms, cyano or nitro; R16 is halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, halocycloalkyl of 3 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy from 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, haloalkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, haloalkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 carbon atoms, haloalkylsulfonyl of 1 to 6 carbon atoms, alkylamino of 1 to 6 carbon atoms, dialkylamino of 2 to 8 carbon atoms, cyano or nitro; each R17 and R18 is independently halogen, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 atoms of carbon, cyano or nitrecada R19 is independently halogen, alkyl
1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 carbon atoms, alkylcarbonyl of 2 to 6 carbon atoms carbon, alkoxycarbonyl
2 to 6 carbon atoms, trimethylsilyl, cyano, nitro or Q1, - each Q1 is independently a phenyl or a saturated or unsaturated heterocycle of 5 or 6 members, each optionally substituted with one or more substituents that are independently selected from halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, halocycloalkyl of 3 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, haloalkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, haloalkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl of 1 to 6 carbon atoms, haloalkylsulfonyl from 1 to 6 carbon atoms, alkylamino of 1 to 6 carbon atoms, dialkylamino of 2 to 8 carbon atoms, cyano, nitro, C (O) NR20R21, C (0) OR22, phenyl or pyridinyl, each phenyl or pyridinyl is optionally substituted with one or more substituents that are independently selected from R23; each R20 is independently H, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms , alkylcycloalkyl of 4 to 7 carbon atoms, cycloalkylalkyl of 4 to 7 carbon atoms, alkylcarbonyl of 2 to 7 carbon atoms? alkoxycarbonyl of 2 to 7 carbon atoms; each R21 and R22 is independently H; or alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms, cycloalkylalkyl of 4 to 7 carbon atoms, phenyl or pyridinyl; each phenyl or pyridinyl is optionally substituted with one or more substituents that are independently selected from R24; and n is 1, 2, 3 or 4; and with the proviso that R16 is different from methoxy. 2. The compound according to claim 1, characterized in that: Q is a pyridinyl ring, a pyrimidinyl ring, a triazinyl ring, a pyrazolyl ring, a triazolyl ring, an imidazolyl ring, an oxazolyl ring, an isoxazolyl ring, a thiazolyl ring or an isothiazolyl ring, each ring optionally being substituted with one or more substituents which are independently selected from halogen, alkyl of 1 to 6 carbon atoms, haloaicyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, halocycloalkyl of 3 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, haloalkylthio of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 6 carbon atoms, haloalkylsulfinyl of 1 to 6 carbon atoms, alkylsulfonyl from 1 to 6 carbon atoms, haloalkylsulfonyl of 1 to 6 carbon atoms, alkylamino of 1 to 6 carbon atoms, dialkylamino of 2 to 8 carbon atoms, cyano, nitro, C (0) NR8R9, C (0) OR10 , phenyl and pyridi nyl, each phenyl and pyridinyl, is optionally substituted with one or more substituents that are independently selected from R 11; or Q is C (0) NR12R13, S (0) 2NR1R15 or R16; Z is CR2; R1 is alkyl of 1 to 3 carbon atoms optionally substituted with one or more substituents that are independently selected from R17; each R2 is independently selected from H, halogen or haloalkyl of 1 to 2 carbon atoms; R3 is H or cyano; or alkyl of 1 to 4 carbon atoms optionally substituted with one or more substituents that are selected from halogen; R4 and R5 are independently selected from halogen, alkyl of 1 to 3 carbon atoms, haloalkyl of 1 to 3 carbon atoms, cyano and nitro; R6 and R7 are independently selected from halogen, alkyl of 1 to 3 carbon atoms, haloalkyl of 1 to 3 carbon atoms, cyano and nitro; or R6 and R7 are taken together to form a fused aromatic ring, the fused aromatic ring contains as ring members, in addition to the bridgehead atoms A3 and A4, four atoms which are selected from 3 to 4 carbon atoms and to 1 nitrogen atom; each R8 is independently H, alkyl of 1 to 6 carbon atoms, alkylcarbonyl of 2 to 7 carbon atoms or alkoxycarbonyl of 2 to 7 carbon atoms; each R9 and R10 is independently H; or alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, alkynyl of 2 to 4 carbon atoms, cycloalkyl of 3 to 4 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms or cycloalkylalkyl of 4 to 7 carbon atoms, each optionally substituted with one or more substituents that are selected from R19; R12 and R14 are independently H, alkyl of 1 to 6 carbon atoms, alkylcarbonyl of 2 to 7 carbon atoms or alkoxycarbonyl of 2 to 7 carbon atoms; R13 and R15 are independently H; or alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, alkynyl of 2 to 4 carbon atoms, cycloalkyl of 3 to 4 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms or cycloalkylalkyl of 4 to 7 carbon atoms, each optionally substituted with one or more substituents that are selected from R19; R16 is halogen, haloalkyl of 1 to 3 carbon atoms, dialkylamino of 2 to 4 carbon atoms, cyano or nitro; each R19 is independently selected from halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, cyano, nitro and -Q1; each Q1 is independently selected from phenyl, pyridinyl and thiazolyl, each optionally substituted with one or more substituents that are independently selected from halogen, alkyl of 1 to 3 carbon atoms, haloalkyl of 1 to 3 carbon atoms, cyano, phenyl and pyridinyl; and n is 1 or 2; with the proviso that at most one of A1, A2, A3 and A4 is N.
3. The compound according to claim 2, characterized in that: R 1 is alkyl of 1 to 3 carbon atoms substituted with halogen; and U is C (= 0). The compound according to claim 3, characterized in that: Q is a pyrazolyl ring, a triazolyl ring or an imidazolyl ring, each ring is linked through nitrogen and is optionally substituted with one or more substituents that are independently selected from halogen, alkyl of 1 to 4 carbon atoms, haloalkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, haloalkoxy of 1 to 4 carbon atoms, cyano, nitro, C (0) NR8R9, C ( 0) 0R10; Or Q is C (O) NR12R13; R1 is CF3; R6 and R7 are independently selected from H, halogen, alkyl of 1 to 3 carbon atoms, haloalkyl of 1 to 3 carbon atoms, cyano and nitro; or R6 and R7 are taken together to form a fused aromatic ring, the fused aromatic ring contains 4 carbon atoms as ring members in addition to the bridgehead atoms A3 and A4; each R8 is H; each R9 and R10 is independently alkyl of 1 to 4 carbon atoms optionally substituted with a Q1 and optionally substituted with one or more substituents that are selected from halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms , alkylthio of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms and cyano; R12 is H; R13 is H; or alkyl of 1 to 4 carbon atoms optionally substituted with one or more substituents that are selected from R19; and each R19 is independently selected from halogen and Q1. 5. The compound according to claim 4, characterized in that: each R2 is independently H, halogen or CF3; and R3 is CH3, CH2CH3 or CH2CF3. 6. The compound according to claim 5, characterized in that: G is O; and [El] with the proviso that A1, A2, A3 and A4 are each different from N. 7. The compound according to claim 1, characterized in that it is selected from the group consisting of: 4- [5- ( 3, 5-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide; 4- [5- (3,5-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2-methyl-N- (2,2,2-trifluoroethyl) benzamide; 4- [5- (3,5-dichlorophenyl) -2-oxide-5- (trifluoromethyl) -1,2, 3-oxathiazolidin-3-yl] -2-methyl-N- (2-pyridinylmethyl) -benzamide; 2-Nitro-5- [2-oxo-5-phenyl-5- (trifluoromethyl) -3-oxazolidinyl] benzonitrile; 4- [4- (3,5-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide; 4- [4- (3, -dichlorophenyl) 3-methyl-2-oxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide; 4- [5- (3,4-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide; 5- [5- (3,5-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2- (1 H -1,2,4-triazol-1-yl) -benzonitrile; 4- [5- (3,5-dichlorophenyl) -2,2-dioxido-5- (trifluoromethyl) -1,2,3-oxathiazolidin-3-yl] -2-methyl-N- (2-pyridinylmethyl) benzamide; and 4- [5- (3,5-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2-methyl-N- [1- (2-pyridinyl) ethyl] benzamide. 8. A composition characterized in that it comprises a compound according to claim 1 and at least one additional component that is selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, the composition optionally further comprising at least an additional biologically active compound or agent. 9. A composition for controlling an invertebrate pest characterized in that it comprises a biologically effective amount of a compound according to claim 1 and at least one additional component that is selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, the composition optionally further comprises a biologically effective amount of at least one additional biologically active compound or agent. The composition according to claim 9, characterized in that at least one additional biologically active compound or agent - is selected from insecticides of the group consisting of macrocyclic lactones, neonicotinoids, octopamine receptor ligands, ryanodine receptor ligands, ecdysone agonists, sodium channel modulators, chitin synthesis inhibitors, nereisotoxin analogues, mitochondrial electron transport inhibitors, cholinesterase inhibitors, cyclodiene insecticides, shedding inhibitors, chloride channel blockers regulated by? -aminobutyric acid , juvenile hormone mimics, lipid biosynthesis inhibitors and biological agents influencing nucleopolyhedrovirus, members of Bacillus thuringiensis, encapsulated d-endotoxins of Bacillus thuringiensis and other insecticidal viruses as found naturally or genetically modified. 11. The composition according to claim 9, characterized in that at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acephate, acetamiprid, acetoprol, aldicarb, amidoflumet, amitraz, avermectin, azadirachtin, azinphosphine, methyl, bifenthrin, bifenazate, bistrifluron, buprofezin, carbofuran, cartap, quinometionat, chlorfenapyr, chlorfluazuron, chlorantraniliprole, chlorpyrifos, clopyriphos-methyl, chlorobenzilate, chromafenozide, clothianidin, ciflumetofen, cyfluthrin, ß-cyfluthrin, cialothrin,? -cialothrin,? - cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, diafentiuron, diazinon, dicofol, dieldrin, dienochlor, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diofenolane, emamectin, endosulfan, esfenvalerate, etiprole, ethoxazole, fenamiphos, fenazaquin, fenbutatin oxide, phenothiocarb, phenoxycarb, fenpropatrine, fenpyroximate, fenvalerate, fipronil, flunicamide, flubendiamide, flucitr inato, tau-fluvalinate, flufenerim, flufenoxuron, fonofos, halofenozida, hexaflumuron, hexitiazox, hydrametilnon, imiciafos, imidaclopride, indoxacarb, isofenfos, lufenuron, malathion, metaflumizone, metaldehyde, methamidophos, metidation, methomil, methoprene, methoxychlor, methoxyfenozide, metofluthrin, monocrotophos, nitenpyram, nitiazine, novaluron, noviflumuron, oxamyl, parathion, parathion-ethyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pyrimicarb, profenofos, profluthrin, propargite, protrifenbuto, pymetrozine, pyrafluprol, pyrethrin, pyridaben, pyridalyl, pirofluguinazone, piriprole, piroproxifen, rotenone, ryanodine, espinetoram, spinosad, spiririclofen, spiromomesifen (BSN 2060), Spirotetramat, sulprofos, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, thiacloprid, thiamethoxam, tiodicar-b, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate, trichlorfon, triflumuron, Bacillus thuringiensis subsp aizawai, Bacillus thuringiensis subsp kurstaki, nucleopolyhedrovirus , encapsulated delta endotoxin from Bacillus thuringiensis, baculovirus, entomopathogenic bacteria, entomopathogenic and entomopathogenic fungi. The composition according to claim 11, characterized in that at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acetamiprid, amitraz, avermectin, azadirachtin, bifenthrin, buprofezin, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyfluthrin, beta-cyfluthrin, cyhalothrin, β-cyclinomer, cypermethrin, cipromazine, deltamethrin, dieldrin, dinotefuran, diofenolane, emamectin, endosulfan, esfenvalerate, ethiprole, phenothiocarb, fenoxycarb, fenvalerate, fipronil, flunicamide, flubendiamide, flufenoxuron, hexaflumuron, hydramethylnon, imidaclopride, indoxacarb, lufenuron, metaflumizone, methomyl, methoprene, methoxyfenozide, nitenpyram, nitiazine, novaluron, oxamyl, pymetrozine, pyrethrin, pyridaben, pyridyl, pyroproxyphene, ryanodine, espirnetoram, spinosad, spiryriclofen, spiromomesifen, tebufenozide, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralometrine, triazam ato, triflumuron, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, nucleopolyhedrovirus and delta endotoxin, encapsulated from Bacillus thuringiensis. The composition according to claim 9, characterized in that it is in the form of a liquid drainage formulation for the soil. 1
4. A spraying composition for controlling an invertebrate pest, characterized in that it comprises: (a) a biologically effective amount of the compound according to claim 1 or the composition according to claim 9; and (b) a propellant. 1
5. A bait composition for controlling an invertebrate pest, characterized in that it comprises: (a) a biologically effective amount of the compound according to claim 1 or the composition according to claim 9; (b) one or more food materials; (c) optionally an attractant; and (d) optionally a humectant. 1
6. A trap device for controlling an invertebrate pest, characterized in that it comprises: (a) the bait composition according to claim 15; and (b) a housing adapted to receive the bait composition, wherein the housing has at least one opening that is sized to allow the invertebrate pest to pass through the opening so that the invertebrate pest has access to the bait composition from a location outside the housing, and wherein the housing is further adapted to be placed at or near a site of potential or known activity for the invertebrate pest. 1
7. A method for controlling an invertebrate pest characterized in that it comprises contacting the invertebrate pest or its environment with a biologically effective amount of a compound according to claim 1. 1
8. A method for controlling an invertebrate pest, characterized because it comprises contacting the invertebrate pest or its environment with a composition according to claim
9. 19. The method according to claim 18, characterized in that the environment is soil and the composition is applied in soil as a formulation of drained to the ground. 20. A method for controlling cockroaches, ants or termites, characterized in that it comprises contacting the cockroach, ant or termite with the ebo composition in a trap device in accordance with claim 16. 21. A method for controlling mosquitoes, black flies, barn flies, deer flies, horse fly, hornet, yellow jacket wasps, bumblebees, ticks, spiders, ants or mosquitoes, characterized in that it involves contacting the mosquito, the black fly, the barn fly, the deer fly, the horse fly, the hornet, the yellow jacket wasp or the bumblebee, the tick, the spider, the ant or the mosquito with the spray composition according to claim 14 supplied from a spray vessel. 22. A method for protecting a seed of an invertebrate pest characterized in that it comprises contacting the seed with a biologically effective amount of a compound according to claim 1. 23. The method according to claim 22, characterized in that the The seed is coated with the compound according to claim 1 formulated as a composition comprising a film former or an adhesive agent. 24. A treated seed, characterized in that it comprises a compound according to claim 1 in an amount from about 0.0001 to 1% by weight of the seed before treatment. 25. A composition for protecting an animal from an invertebrate parasitic pest characterized in that it comprises an effective parasiticidal amount of a compound according to claim 1 and at least one carrier. 26. The composition according to claim 25, characterized in that it is in a form for oral administration. 27. A method for protecting an animal from an invertebrate parasitic pest characterized in that it comprises administering to the animal an effective parasiticidal amount of a compound according to claim 1. SUMMARY OF THE INVENTION A compound of formula (1) is described which includes all geometric isomers and stereoisomers, N-oxides and salts thereof wherein G is O or NR3; U is C (= 0), C (= S) or S (0) 2; Z is N or CR2; R1 is cyano or alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms or cycloalkylalkyl from 4 to 7 carbon atoms, each optionally substituted with one or more substituents that are independently selected from R17; R3 is H, cyano or -CHO; or alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, alkylcycloalkyl of 4 to 7 carbon atoms, cycloalkylalkyl of 4 to 7 carbon atoms, phenyl, alkylcarbonyl of 2 to 6 carbon atoms, alkoxycarbonyl of 2 to 6 carbon atoms, alkylaminocarbonyl of 2 to 6 carbon atoms, dialkylaminocarbonyl of 3 to 9 carbon atoms, each optionally substituted with one or more substituents that are independently selected from R18; Q is an optionally substituted 5 to 6 membered saturated or unsaturated heterocycle; or Q is C (0) NR12R13, C (S) NR12R13, S (O) 2NR1R15 or R16; and R2, R12, R13, R14, R15, R16, R17, R18, A1, A2, A3, A4 and n are as defined in the description. Also described are compositions containing the compounds of formula 1 and methods for controlling invertebrate pests comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound or composition of the invention.
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