BRPI0710380A2 - compound, composition, pest control composition, invertebrate, spray, bait, trap device, control methods, protection methods, treated seed and protection composition - Google Patents

Abstract

COMPOUND, COMPOSITION, COMPOSITION OF INVERTEBRATED PEST CONTROL, SPRAYING, BAIT, TRAP DEVICE, CONTROL METHODS, PROTECTION METHODS, TREATED SEED AND PROTECTION COMPOSITION. Compounds of Formula (1) are described, including all their geometric isomers and stereoisomers, N-oxides and salts, where G is O or NR ^ 3 ^; U is 0 (= O), S (= O), 0 (= S) or S (O) ~ 2 ~; Z is N or CR ^ 2 ^; R ^ 1 ^ is cyan; or C ~ 1 ~ -C ~ 6 ~ alkyl, C ~ 2 ~ -C ~ 6 ~ alkenyl, C ~ 2 ~ -C ~ 6 ~ alkynyl, C ~ 3 ~ -C ~ 6 ~ cycloalkyl, C ~ 4 ~ alkylcycloalkyl -C ~ 7 ~ or C ~ 4 ~ -C ~ 7 ~ cycloalkylalkyl, each optionally substituted with one or more substituents selected independently from R ^ 17 ^ ^; R ^ 3 ^ is H, damage or -CHO; or C ~ 1 ~ -C ~ 6 ~ alkyl, C ~ 2 ~ -C ~ 6 ~ alkenyl, C ~ 2 ~ -C ~ 6 ~ alkynyl, C ~ 3 ~ -C ~ 6 ~ cycloalkyl, C ~ 4 ~ alkylcycloalkyl -C ~ 7 ~, C ~ 4 ~ cycloalkylalkyl, -C ~ 7 ~, phenyl, C ~ 2 ~ -C ~ 6 ~ alkyl, C ~ 2 ~ -C ~ 6 ~ alkoxycarbonyl, C ~ 2 ~ -C ~ 6 alkylaminocarbonyl ~, C ~ 3 ~ -C ~ 9 ~ dialkylaminocarbophyl, each optionally substituted with one or more substituents selected independently from R ~ 18 ~; it is an optionally substituted five or six membered saturated or unsaturated heterocycle; or Q is C (O) NR ^ 12 ^ R ^ 13 ^, C (S) NR ^ 12 ^ R ^ 13 ^, S (O) ~ 2 ~ NR ^ 14 ^ R ^ 15 ^ or R ^ 16 ^; and R ^ 2 ^, R ^ 12 ^, R ^ 13 ^, R ^ 14 ^, R ^ 15 ^, R ^ 16 ^, R ^ 17 ^, R ^ 18 ^, A ^ 1 ^, A ^ 2 ^ , A ^ 3 ^, A ^ 4 ^ en are as defined in the specification. Also described are compositions containing the compounds of Formula 1 and invertebrate pest control methods that comprise contacting the invertebrate pest or its environment with a biologically effective amount of compound or composition according to the present invention.

Description

"COMPOSITION, COMPOSITION, CONTROL COMPOSITION OF INVERTED, SPRAYING, Bait, PESTING DEVICE, CONTROL METHODS, PROTECTIVE METHODS, TREATED SEED AND PROTECTIVE COMPOSITION"

Field of the Invention

The present invention relates to certain five membered heterocyclic derivatives, their N-oxides, salts and compositions suitable for agronomic and non-agronomic uses, including the uses listed below, and methods of their use for the control of invertebrate pests such as arthropods in agronomic environments. not agronomic.

Background of the Invention

Invertebrate pest control is extremely important to achieve high production efficiency. Damage by invertebrate pests to crop and stored crops may cause a significant reduction in yield and thus result in increased costs for the consumer. Control of invertebrate pests in forest products, greenhouse crops, ornamental plants, seedling crops, stored food and fiber products, livestock, domestic animals, lawns, wood products, and animal and public health is also important. Many products are commercially available for these purposes, but there remains a need for new compounds that are more effective, cost-effective, less toxic, environmentally safer, or have different modes of action.

PCT Patent No. WO 93/22298 describes deoxazolidine derivatives and their pharmaceutically acceptable salts as antihyperlipidemic.

Japanese Patent No. 03176476 describes imidazolidinones as chiral auxiliaries useful for the production of penem or carbapenem antibiotics.

U.S. Patent No. 4,186,129 describes oxazolidinonasubutives as neuroleptics and phosphodiesterase inhibitors.

Brief Description of the Invention The present invention relates to compounds of Formula 1, including all geometric isomers and stereoisomers thereof, as well as agricultural compositions containing them and their use for invertebrate pest control:

<formula> formula see original document page 3 </formula>

on what:

G is O or NR3;

U is C (= 0), S (= 0), C (= S) or S (O) 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 five or six membered saturated or unsaturated heterocycle optionally substituted with one or more substituents independently selected from halogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C6 alkoxy C1-C61haloalkoxy C61 C1-C61 haloalkylthio C1-C61 alquilsulfinila C1-C6 haloalquilsulfinila C1-C6 alquilsulfonila C1-C6 haloalquilsulfonila C1C61alquilamino C1-C6 dialkylamino, C2 C8l cyano, nitro, C (O) NR8R91 C (O) OR101fenila and pyridinyl wherein each phenyl or pyridinyl is optionally substituted with one or more substituents independently selected from R 11, or

-Q is C (O) NR12R131 C (S) NR12R131S (O) 2NR14R15 or R16;

-R 1 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;

each R2 is independently H1 halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6-alkylthio, C1-C61-alkylsulfinyl C1-C61-haloalkylsulfonyl-C1-C61-alkylsulfonyl-C1-6 alkylsulfonyl C61 -C2 dialkylamino, C2 -C4 alkoxycarbonyl, C2 -C4 alkylaminocarbonyl, C2 -C4 dialkylaminocarbonyl or nitro;

-R3 is cyano H1 or -CHO; or C1-C61 alkyl C2-C61 alkenyl C2-C61 alkynyl C3-C6 cycloalkyl C4-C7 alkylcycloalkyl, C4-C7 cycloalkylalkyl, phenyl, C1-C61 alkylcarbonyl C1-C61 alkylamino carbonyl or optionally substituted C3-C6 alkylamino or more substituents independently selected from R18;

-R41 R51 R6 and R7 are independently selected from H1 halogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C6 halocycloalkyl, C1-C6 haloalkoxy, C1-C6 alkylthio, haloalkyl C 1 -C 6, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkylamino, C 2 -C 6 dialkylamino cyano; or

- R 6 and R 7 are taken together to form a fused aromatic ring, wherein the fused aromatic ring contains, as the forward members, in addition to the bridgehead atoms A3 and A4, three atoms selected from one to two carbon atoms, zero to one. two nitrogen atoms, zero to one oxygen atom and zero to one sulfur atom, or four atoms selected from two to four carbon atoms and zero to two nitrogen atoms;

each R 8, R 12 and R 14 are independently H 1 C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 4 -C 7 cycloalkyl, C 4 -C 7 cycloalkyl, C 2 -C 7 alkylcarbonyl, C 2 -C 6 alkoxyalkyl or C 2 -C 7 alkoxycarbonyl;

each R 9, R 10, R 13 and R 15 are independently H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 4 -C 7 alkylcycloalkyl or C 4 -C 7 cycloalkylalkyl each which is optionally substituted with one or more substituents independently selected from R 19;

each R 11, R 23 and R 24 are independently halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkyl, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkylaminosulfonyl C 1 -C 8 alkylamino, C 2 -C 8 dialkylamino, C 2 -C 4 alkoxycarbonyl, cyano or nitro;

R16 is halogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 haloalkyl, C1-C6 alkylsulfinyl C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-6 haloalkylsulfonyl, C1-C6 alkylamino, C2-C8 dialkylamino, cyano or nitro;

each R 17 and R 18 are independently halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 alkylsulfonyl, cyanoor nitro;

- each R 19 is independently halogen, C 1 -C 6 alkyl,

C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, trimethylsilyl, cyano, nitro or Q1;

each Q 1 is independently a phenyl or a 5- or 6-membered heterocyclesaturated or unsaturated, each optionally substituted with one or more substituents independently selected from halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 halocycloalkyl -C6, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C61 haloalkylsulfinyl C1-C61 haloalkylsulfonyl C1-C6 alkylamino C1-C61 dialkylamino nitro, C (O) NR 20 R 21 C (O) OR 221 phenyl or pyridinyl, wherein each phenyl or pyridinyl is optionally substituted with one or more substituents independently selected from R 23;

- each R20 is independently H1 C1 -C61 alkyl halo C1 -C61 alkyl C2 -C6 alkenyl, C2 -C6 alkynyl, C3 -C6 cycloalkyl C4 -C7 alkylcycloalkyl C2 -C7 cycloalkyl C2 -C7 alkylcarbonyl;

each R 21 and R 22 is independently H 1 C 1 -C 6 alkyl, C 1 -C 6 haloalkyl C 2 -C 6 alkenyl C 2 -C 6 alkynyl C 3 -C 6 cycloalkyl C 4 -C 7 cycloalkyl C 4 -C 7 cycloalkyl alkyl phenyl or pyridinyl; wherein each phenyl or pyridinyl is optionally substituted by one or more substituents independently selected from R 24; and

n is 1,2, 3 or 4;

provided that R16 is other than methoxy.

The present invention also provides an invertebrate pest control composition comprising a biologically effective amount of a compound of Formula 1, its N-oxide or salt and at least one additional component selected from the group consisting of a surfactant, solid diluent and liquid diluent, wherein said composition optionally further comprises a biologically effective amount of at least one additional biologically active agent or compound.

The present invention also provides an invertebrate pest control spray composition which comprises a biologically effective amount of a compound of Formula 1, one of its salts or Î ± -oxides or of the composition described above and a propellant. The present invention also provides a bait composition for controlling invertebrate pests comprising a biologically effective amount of a compound of Formula 1, its A / oxide or salt, or of the composition described above, one or more food materials, optionally an attractive and optionally a humectant.

The present invention further provides an invertebrate pest control trap device comprising said bait composition and a shelter adapted to receive said bait composition, wherein the shelter contains at least one dimensioned opening to allow the invertebrate pest to pass through the aperture. so that the invertebrate pest can gain access to said bait composition from a location outside the shelter and where the shelter is further adapted for placement in a known activity site or potential for or near invertebrate pests.

The present invention also provides an invertebrate pest control method comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula 1, its N-oxide or salt (such as a composition described herein). The present invention also relates to a method wherein the pragainvertebrate or its environment is contacted with a composition comprising a biologically effective amount of a compound of Formula 1, its N-oxide or salt and at least one additional component selected from the group. consisting of a surfactant, a solid diluent and a liquid diluent, wherein said composition further optionally comprises a biologically effective amount of at least one additional biologically active compound or compound. The present invention also provides a method of protecting against invertebrate pests which comprises contact the seed with a biologically effective amount of a compound of Formula 1, its N-oxide or salt (such as a composition described herein). The present invention also relates to the treated seed. The present invention further provides a method of protecting animals against parasitic invertebrate pests comprising administering to the animal a parasiticidal effective amount of a compound of Formula 1, its A-oxide or salt (such as a composition described herein).

Detailed Description of the Invention

As used herein, the terms "comprises", "comprising", "includes", "including", "has", "has", "contains", "contains" or any of its variations are intended to cover non-exclusive inclusion. A composition, mixture, process, method, article or apparatus comprising a list of elements, for example, is not necessarily limited to those elements only, but may include other elements not expressly related to or inherent in that composition, mixture, process, method, article or apparatus. . In addition, unless expressly stated otherwise, "or" indicates inclusive and not exclusive. A condition A or B is met, for example, by any of the following: True air (or present) and B is false (or absent), A is false (or absent) and true B (or present) or both AeB are true (or present).

In addition, the undefined "one" and "one" articles preceding an element or component according to the present invention are intended to be non-restrictive with respect to the number of cases (ie occurrences) of the element or component. "One" or "one", therefore, should be read as including one or at least one, and the form of the element's singular word or component also includes the plural, unless the number is obviously intended to be singular.

As indicated herein, the term "invertebrate pest" includes arthropods, gastropods, and nematodes of economic importance as pests. The term "arthropod" includes insects, mites, spain, scorpions, centipedes, myriads, mealybugs and aphids. The term "gastropod" includes colens, ises, and other stylomatophores. The term "helminths" includes phylum worms of the nemaltelminths, platyelminths, and acanthocephalus such as roundworms, cardiac parasites, and phytophagous (nematode), fasciole (trematoid), cestode (cestode), and ctenophorous nematodes.

In the context of this descriptive report, "control of invertebrate pests" indicates inhibition of the development of invertebrate pests (including mortality, reduced feeding and / or disruption of maturation) and relative expressions are defined analogously.

The term "agronomic" indicates the production of field crops, such as for food and fiber, and includes the growth of corn, soybean and other vegetables, rice, cereals (such as wheat, oats, barley, rye, white corn rice). , leafy vegetables (such as lettuce, cabbage and other decouve crops), fruit vegetables (such as tomatoes, pepper, eggplant, cruciferous and pumpkins), potatoes, sweet potatoes, grapes, cotton, fruit trees (such as pomegranate, drupe and citrus fruits ), small fruits (berries, cherries) and other specialized harvests (such as canola, sunflower, olives). The term "nonagronomic" indicates applications in other horticultural crops (such as greenhouse plants, seedlings or ornamentals not cultivated in a field), residential and commercial structures in urban and industrial environments, lawns (such as grass plantations, pastures, golf courses, lawns residences, recreational sports fields, etc.), wood products, stored products, vegetation and agroforestry management, public (human) health and animal health (such as domesticated animals such as domesticated animals, farmed animals and birds, undomesticated animals such as wild animals). ).

In the above descriptions, the term "alkyl", used alone or in compound words such as "alkylthio" or "haloalkyl", includes straight or branched middle alkyl such as methyl, ethyl, n-propyl, i-propyl or the different butyl isomers. , pentyl or hexyl. "Alkenyl" includes straight or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl and the different isomers of butenyl, pentenyl and hexenyl. "Alkenyl" also includes polyols such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight or branched chain alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different isomers of butynyl, pentinyl and hexinyl. "Alkynyl" may also include portions composed of several multiple triple unions, such as 2,5-hexadiinyl.

"Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy the different isomers of butoxy, pentoxy and hexyloxy. "Alkylthio" includes straight or branched chain alkylthio moieties such as methylthio, ethylthio and the different isomers of propylthio, butylthio, pentylthio and hexylthio. "Alkylsulfinyl" includes the two enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" include CH3S (O) -, CH3CH2S (O) -, CH3CH2CH2S (O) -, (CH3) 2CHS (O) - and the different isomers of butylsulfinyl, pentylsulfinyl and hexylsulfinyl. Examples of "alkylsulfonyl" include CH3S (O) 2-, CH3CH2S (O) 2-, CH3CH2CH2S (O) 2 -, (CH3) 2CHS (O) 2- and the different isomers of butylsulfonyl, pentylsulfonyl and hexylsulfonyl. "Alkylamino", "dialkylamino" and the like are defined analogously to the above examples. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "alkylcycloalkyl" denotes alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, i-propylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. The term "cycloalkylalkyl" denotes cycloalkyl substitution over a alkyl portion. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl and other cycloalkyl moieties attached to straight chain or branched alkyl groups.

The term "halogen", either alone or in compound words such as "haloalkyl", or when used in descriptions such as "halogen substituted alkyl", includes fluorine, chlorine, bromine or iodine. In addition, when used in compound words such as " "haloalkyl", mentioned alkyl may be partially or fully substituted with halogen atoms which may be identical or different. Examples of "haloalkyl" or "halogen substituted alkyl" include F3C-, CICH2-, CF3CH2- and CF3CCI2-. The terms "halocycloalkyl", "haloalkoxy", "haloalkylthio" and the like are defined analogously to the term "haloalkyl". Examples of "haloalkoxy" include CF3O-, CCl3CH2O-, HCF2CH2CH2O- and CF3CH2O-. Examples of "haloalkylthio" include CCI3S-, CF3S-, CCI3CH2S- and CICH2CH2CH2S-. Examples of "haloalkylsulfinyl" include CF3S (O) -, CCl3S (O) -, CF3CH2S (O) - and CF3CF2S (O) -. Examples of "haloalkylsulfonyl" include CF3S (O) 2-, CCI3S (O) 2-, CF3CH2S (O) 2- and CF3CF2S (O) 2-.

"Alkylcarbonyl" denotes straight chain or branched alkyl moieties attached to a C (= O) moiety. Examples of "alkylcarbonyl" include CH 3 C (= 0) -, CH 3 CH 2 CH 2 C (= 0) - and (CH 3) 2 CHC (= 0) -. Examples of "alkoxycarbonyl" include CH30C (= 0) -, CH3CH20C (= 0) -, CH3CH2CH20C (= 0) -, (CH3) 2CH0C (= 0) - and the different butoxy or pentoxycarbonyl isomers.

The total amount of carbon atoms in the substituent group is indicated by the prefix "C1 -C1", where i and j are integers from 1 to 9. C1 -C4 alkylsulfonyl, for example, means methylsulfonyl to butylsulfonyl: C2 alkoxyalkyl denotes CH3OCH2; C 3 alkoxyalkyl means, for example, CH 3 CH (OCH 3), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2; and C4 alkoxyalkyl denotes the various isomers of an alkyl group substituted with an alkoxy group which contains a total of four carbon atoms, examples of which include CH3CH2CH2OCH2 and CH3CH2OCH2CH2.

When a compound is substituted with a substituent containing a subscript indicating that the number of said substituents may exceed 1, said substituents (when exceeding 1) are independently selected from the group of defined substituents such as (R2) n, η is 1, 2, 3 or 4. When a group contains a substituent which may be hydrogen, such as R2, when that substituent is taken as hydrogen, it is recognized to be equivalent to said unsubstituted group.

The term "heterocycle", "heterocyclic ring" or "heterocyclic ring system" denotes rings or ring systems in which at least one ring atom is not carbon, such as nitrogen, oxygen or sulfur. Typically, a heterocyclic ring contains no more than four nitrogen, no more than two oxygen and no more than two sulfur. The heterocyclic ring may be attached via any available carbon or nitrogen by hydrogen substitution on said carbon or nitrogen. The heterocyclic ring may be a saturated, partially unsaturated or fully unsaturated ring. Where a fully unsaturated heterocyclic ring satisfies the Hückel leid, said ring is also referred to as a "heteroaromatic ring" or "aromatic heterocyclic ring".

The term "aromatic ring" or "aromatic ring system" denotes fully unsaturated carbocycles and heterocycles wherein at least one ring of the polycyclic ring system is aromatic (where aromatic indicates that Hückel's law is satisfied for the ring system). The term "fused bicyclic ring system" indicates that a ring system containing two fused rings in which each ring may be saturated, partially saturated or fully unsaturated. The term "fused heterobicyclic ring system" means a ring system containing two fused rings wherein at least one ring atom is non-carbon and which may be aromatic or nonaromatic as defined above.

The term "optionally substituted" with respect to heterocyclic rings denotes groups that are unsubstituted or contain at least one non-hydrogen substituent that does not eliminate the bio-deficient activity of the unsubstituted analog. As used herein, the following definitions shall apply unless otherwise specified. The term "optionally substituted" is used interchangeably with the expression "substituted or unsubstituted" or the expression "(unsubstituted)". Unless otherwise indicated, an optionally substituted group may contain one substituent at each substitutable position in the group and each substitution is independent of the other.

Where Q or Q1 is a five-membered five-membered nitrogen heterocycle, it may be attached to the remainder of Formula 1 by any available nitrogen or carbon ring atom unless otherwise indicated. Those skilled in the art recognize 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; consequently, "pyridinyl" and "pyridyl" are used herein as synonyms.

As illustrated above, Q1 may be (among others) phenyl optionally substituted with one or more substituents selected from a group of substituents as defined in the Invention's Summary Description. An example of phenyl optionally substituted with one or more substituents is the ring illustrated as U-1 in Illustration 1, wherein Rv is any substituent as defined in the Summary Description of the Invention for Q1 and r is an integer from 0 to 5.

As indicated above, Q or Q1 may be (but are not limited to) five or six membered saturated or unsaturated heterocycles optionally substituted with one or more substituents selected from the substituent group as defined in the Summary Description of the Invention. Examples of five- or six-membered unsaturated aromatic heterocycles optionally substituted with one or more substituents include the rings U-2 through U-61 shown in Illustration 1 wherein Rv is any substituent as defined in the Summary Description of the Invention for Q or Q1 and r is an integer of Note that some U groups can only be replaced with less than four Rv groups (such as U-2 to U-5, U-7 to IM8, and U-52 to U-61).

Although Rv groups are displayed in structures U-1 through U-61, it is noted that they do not need to be present as they are optional substituents. Note that when Rv is H when bonded to an atom, this is identical to if said atom is not substituted. Nitrogen atoms that need replacement to fill their valence are replaced with H or Rv. Note that when the bonding point between (Rv) r and group U is illustrated as floating, (Rv) r can be attached to any available carbon atom or nitrogen atom of group U.

<formula> formula see original document page 14 </formula> <formula> formula see original document page 15 </formula>

Note that when Q or Q1 is a five- or six-membered saturated or unsaturated nonaromatic heterocycle optionally substituted with one or more substituents selected from the substituent group as defined in the Summary Description of the Invention is Q or Q11 one or two ring members. carbon of the heterocycle may optionally be in the oxidized form of a carbonyl moiety. Examples of non-aromatic or saturated five- or six-membered unsaturated heterocycles include rings Q-1 to Q-35, as shown in Illustration 2, where Rv is any substituent as defined in the Invention's Summary Description for Q1. Note that when the bonding point between (Rv) Q or Q1 is shown as floating, (Rv) r can be attached to any available carbon atom or nitrogen atom of group U. Note that when The binding point on the group Q or Q1 is illustrated as floating, the group Q or Q1 may be attached to the remainder of Formula 1 by any available carbon or nitrogen group Q or Q1 by substitution of a hydrogen atom. Optional substituents may be attached to any available carbon or nitrogen by substitution of a hydrogen atom.

Note that when Q or Q1 comprises an anelect from Q-28 through Q-35, Q2 is selected from O, S, or N. Note that when Q2 is Ν, the nitrogen atom can complete the suavalence by substituting with H or the substituents defined in the Summary Description of the Invention for Q or Q1.

Illustration 2

<formula> formula see original document page 16 </formula> <formula> formula see original document page 17 </formula>

The compounds according to the present invention may exist in the form of one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometry isomers. Those skilled in the art will appreciate that one stereoisomer may be more active and / or may exhibit beneficial effects when enriched with respect to other stereoisomer (s) or when separated from other stereoisomer (s). Further, those skilled in the art know how to selectively separate, enrich and / or prepare said stereoisomers.

Accordingly, the present invention comprises compounds selected from Formula 1, their N-oxides and salts suitable for agricultural use. The compounds according to the present invention may be present in the form of a mixture of stereoisomers, individual stereoisomers or in an optically active form.

Those skilled in the art will appreciate that not all nitrogen-containing heterocycles may form N-oxides, as nitrogen requires an available parisolate for oxidation to the oxide; technicians in the art will recognize nitrogen-containing heterocycles that can form N-oxides. Those skilled in the art will also recognize that tertiary amines may form A / oxides. Synthetic methods of preparing tertiary amine A-oxides and oxides are very well known to those skilled in the art, including oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA) 1 hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate and dioxiranes such as dimethoxypyran. These A / oxide preparation methods have been extensively described and analyzed in literature; see, for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, p. 748-750, S. V. Ley (Ed.), Pergamon Press; M. Tisler eB. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, p. 18-20, A.J. Boulton and A. McKiIIop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advanees in Heterocycle Chemistry, vol. 43, p. 149-161, A. R. Katritzky (Ed.), Academic Press; M. Tisler and B. Stanovnik in Advanees in Heterocyclie Chemistry, vol. 9, p. 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advanees in Heterocycle Chemistry, vol. 22, p. 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.

Salts of the compounds according to the present invention include acid addition salts with organic or inorganic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic acid, tartaric, 4-toluenesulfonic or valeric. Salts of the compounds of the present invention also include those formed with organic bases (such as pyridine, ammonia or triethylamine) or inorganic bases (such as sodium, potassium, lithium, calcium, magnesium or barium hydrides, hydroxides or carbonates) when The compound contains an acid moiety, such as when Q1 is phenyl substituted with C (O) OR22 and R22 is Η.

Accordingly, the present invention comprises compounds selected from Formula 1, their N-oxides and salts.

Embodiments of the present invention as detailed in the Summary Description of the Invention include:

Embodiment 1. A compound of Formula 1 wherein G is O.

Embodiment 2. A compound of Formula 1 wherein G is NR3.

Embodiment 3. A compound of Formula 1 wherein R 3 is H or cyano, or C 1 -C 4 alkyl optionally substituted with one or more substituents selected from halogen.

Embodiment 4. A compound of Embodiment 3 wherein R 3 is CH 3, CH 2 CH 3 or CH 2 CF 3.

Embodiment 5. A compound of Formula 1 wherein U is C (= 0).

Embodiment 6. A compound of Formula 1 wherein Z is CR2.

Embodiment 7. A compound of Formula 1 wherein each R2 is independently selected from H1 halogen or C1-C2 haloalkyl.

Embodiment 8. A compound of Embodiment 7 wherein each R2 is independently H, halogen or CF3.

Embodiment 9. A compound of Formula 1 wherein A1 is CR4.

Embodiment 10. A compound of Formula 1 wherein A2 is CR5.

Embodiment 11. A compound of Formula 1 wherein A3 is CR6.

Embodiment 12. A compound of Formula 1 wherein A3 is CR7.

Embodiment 13. A compound of Formula 1 wherein R4 and R5 are independently selected from H1 halogen, C1-C3 alkyl, C1-C3 haloalkyl, cyano and nitro.

Embodiment 14. A compound of Formula 1 wherein R 6 and R 7 are independently selected from H 1 halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyano and nitro; or R 6 and R 7 are taken together to form a fused aromatic ring, wherein the fused aromatic ring contains as ring members, in addition to the bridgehead atoms A3 and A41 four atoms selected from three to four atoms and carbon and zero to one atom of nitrogen.

Embodiment 15. A compound of Embodiment 14 wherein R6 and R7 are independently selected from H, halogen, C1-C3 alkyl, C1-C3 haloalkyl, cyano and nitro.

Embodiment 16. A compound of Embodiment 14 wherein R 6 and R 7 are taken together to form a fused aromatic ring, wherein the fused aromatic ring contains as ring members, in addition to the bridging atoms A3 and A4, four atoms selected from three to four carbon atoms and zero to one nitrogen atom.

Embodiment 17. A compound of Embodiment 14 or 16 wherein the fused annular aromatic contains four carbon atoms as ring members in addition to bridgehead atoms A3 and A4.

Embodiment 18. The compound of Formula 1 wherein Q is a pyridinyl ring, pyrimidinyl ring, triazinyl ring, pyrazolyl ring, triazolyl ring, ringimidazolyl ring, oxazolyl ring, isoxazolyl ring, thiazolyl ring or isothiazolyl ring, wherein each ring is optionally substituted with one or more independently selected from halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 alkoxyalkylC 1 C 6 haloalkoxy, C 1 -C 6 alkylthio C 1 -C 6 haloalkyl C 1 -C 6 alkylsulfinyl C 1 -C 6 alkylsulfinyl -C6, C1-C6 haloalkylsulfonyl, C1-C6 alkylamino, C2-C8 dialkylamino, cyano, nitro, C (O) NR8R9, C (O) OR10, phenyl and pyridinyl, wherein each phenyl and pyridinyl is optionally substituted with one or more substituents independently selected from R 11, or Q is C (= 0) NR 12 R 13, S (O) 2 NR 14 R 15 or R 16.

Embodiment 19. Compound of Embodiment 18 wherein Q is a pyridinyl ring, pyrimidinyl ring, triazinyl ring, pyrazolyl ring, triazolyl ring, ringimidazolyl ring, oxazolyl ring, isoxazolyl ring, thiazolyl ring or isothiazolyl ring, wherein each ring is optionally substituted with one or more independently selected from halogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-C6-alkylthio, C1-C61-haloalkyl-C1-C6-alkylsulfinyl haloalkyl C1-C6, C1-C6 alkylsulfonyl, C1-C61 haloalkylsulfonyl C1-C61 alkylamino C2-C8l dialkylamino cyano, nitro, C (O) NR8R91 C (O) OR101phenyl and pyridinyl, wherein each phenyl and pyridinyl is optionally substituted by one or more substituents independently selected from R11.

Embodiment 20. Compound of Embodiment 19 wherein Q is a ring pyrazolyl, triazolyl ring or imidazolyl ring, wherein each ring is nitrogen-bonded and optionally substituted with one or more substituents independently selected from halogen, C1-C4 alkyl, C1 haloalkyl C 3 -C 6 cycloalkyl C 3 -C 6 halocycloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylamino, C 2 -C 4 dialkylamino, cyano, nitro, C (O) NR 8 R 9, C (O) OR 10, phenyl and pyridinyl, wherein each phenyl and pyridinyl is optionally substituted with one or more substituents independently selected from R 11.

Embodiment 21. Compound of Embodiment 20 wherein Q is a ring pyrazolyl, triazolyl ring or imidazolyl ring, wherein each ring is nitrogen-bonded and optionally substituted with one or more substituents independently selected from halogen, C1-C4 alkyl, C1 haloalkyl -C4, C1 -C4 alkoxy, C1 -C4 haloalkoxy cyano, nitro, C (O) NR8 R9 and C (O) OR10.

Embodiment 22. Compound of Embodiment 21 wherein Q is a ring pyrazolyl, triazolyl ring or imidazolyl ring, wherein each ring is nitrogen-bonded and optionally substituted with one or more substituents independently selected from halogen, C1 -C3 alkyl and C1 -C3 haloalkyl.

Embodiment 23. Compound of Embodiment 22 wherein Q is a triazolyl ring or imidazolyl ring, wherein each ring is nitrogen bonded and optionally substituted with one or more substituents independently selected from halogen, C1-C3 alkyl and C1-C3 haloalkyl.

Embodiment 24. A compound of Formula 1 wherein each R 8 is independently H, C 1 -C 6 alkyl, C 2 -C 7 alkylcarbonyl or C 2 -C 7 alkoxycarbonyl.

Embodiment 25. A compound of Embodiment 24 wherein each R8 is H.

Embodiment 26. A compound of Formula 1 wherein each R 9 is independently H; or C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 4 cycloalkyl, C 4 -C 7 alkylcycloalkyl or C 4 -C 7 cycloalkylalkyl, each optionally substituted with one or more substituents selected from R 19.

Embodiment 27. A compound of Embodiment 26 wherein each R 9 is independently C 1 -C 4 alkyl optionally substituted with one or more substituents selected from R 19.

Embodiment 28. A compound of Embodiment 27 wherein each R 9 is independently C 1 -C 4 alkyl optionally substituted with a Q 1 and optionally substituted with one or more substituents selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfonyl ecian.

Embodiment 29. A compound of Formula 1 wherein each R 10 is independently H; or C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 4 cycloalkyl, C 4 -C 7 alkylcycloalkyl or C 4 -C 7 cycloalkylalkyl each optionally substituted with one or more substituents selected from R 19. wherein each R10 is independently C1-C4 alkyl optionally substituted with one or more substituents selected from R19.

Embodiment 31. A compound of Embodiment 30 wherein each R10 is independently C1-C4 alkyl optionally substituted with a Q1 and optionally substituted with one or more substituents selected from halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-alkylsulfonyl -C4 cyan.

Embodiment 32. A compound of Formula 1 wherein each R19 is independently selected from halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfonyl, cyano, nitro and Q1.

Embodiment 33. A compound of Embodiment 32 wherein each R19 is independently selected from halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfonyl and cyano.

Embodiment 34. A compound of Embodiment 18 wherein Q is C (= 0) NR 12 R 13.

Embodiment 35. A compound of Formula 1 wherein R 12 is H, C 1 -C 6 alkyl C 2 -C 7 alkylcarbonyl or C 2 -C 7 alkoxycarbonyl.

Embodiment 36. A compound of Embodiment 35 wherein R12 is H.

Embodiment 37. A compound of Formula 1 and m wherein R 13 is H; C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 4 cycloalkyl, C 4 -C 7 alkylcycloalkyl or C 4 -C 7 cycloalkylalkyl, each optionally substituted by one or more substituents selected from R 19.

Embodiment 38. A compound of Embodiment 37 wherein R 13 is H; or C1-C4 alkyl optionally substituted with one or more substituents selected from R19.

Embodiment 39. A compound of Embodiment 38 wherein R 13 is H; or C1-C4 alkyl optionally substituted with Q1 and optionally substituted with one or more substituents selected from halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfonyl, C2-C4 alkylcarbonyl) alkoxycarbonyl C2 -C4 and cyano.

Embodiment 40. A compound of Embodiment 39 wherein R 13 is H; or C1-C4 alkyl optionally substituted with one Qi and optionally substituted with one or more fluorine.

Embodiment 41. A compound of Formula 1 wherein each R19 is independently selected from halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfonyl, C1-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl C4, cyano, nitro and Q1.

Embodiment 42. A compound of Embodiment 41 wherein each R19 is independently selected from halogen and Q1.

Embodiment 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 independently selected from halogen, C1-C3 alkyl, C1-C3 haloalkyl, cyano, phenyl and pyridinyl.

Embodiment 44. A compound of Embodiment 43 wherein Q 1 is phenyl, pyridinyl or thiazolyl.

Embodiment 45. A compound of Embodiment 18 wherein Q is R16.

Embodiment 46. A compound of Embodiment 18 wherein Q is S (O) 2 NR 14 R 15.

Embodiment 47. A compound of Formula 1 wherein R 14 is H, C 1 -C 6 alkyl, C 2 -C 7 alkylcarbonyl or C 2 -C 7 alkoxycarbonyl.

Embodiment 48. A compound of Embodiment 47 wherein R14 is H.

Embodiment 49. A compound of Formula 1 wherein R15 is H; C 1 -C 4 alkyl, C 2 -C 4 alkenyl C 2 -C 4 alkynyl C 3 -C 4 cycloalkyl, C 4 -C 7 alkylcycloalkyl or C 4 -C 7 cycloalkylalkyl, each optionally substituted by one or more substituents selected from R 19.

Embodiment 50. A compound of Embodiment 49 wherein R 15 is H; or C1-C4 alkyl optionally substituted with one or more substituents selected from R19.

Embodiment 51. Compound of Embodiment 50 wherein each R 15 is H, or C 1 -C 4 alkyl optionally substituted with one or more substituents selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl C 4 -C 2 alkylcarbonyl, C 2 -C 4 alkoxycarbonyl, cyano and at most one Q 1.

Embodiment 52. A compound of Embodiment 51 wherein each R 15 is H or C 1 -C 4 alkyl optionally substituted with one or more fluorine and, at most, one Q 1.

Embodiment 53. A compound of Formula 1 wherein Q is different from R16.

Embodiment 54. A compound of Formula 1 wherein R 16 is halogen, C 1 -C 3 haloalkyl, C 2 -C 4 dialkylamino, cyano or nitro.

Embodiment 55. A compound of Formula 1 wherein R 1 is C 1 -C 3 alkyl optionally substituted with one or more substituents independently selected from R 17.

Embodiment 56. A compound of Embodiment 55 wherein R 1 is C 1 -C 3 alkyl substituted with one or more halogens.

Embodiment 57. A compound of Embodiment 56 wherein R1 is CF3.

Embodiment 58. A compound of Formula 1 wherein η is 1 or 2.

Embodiment 59. A compound of Formula 1 wherein at most three of A1, A2, A3 and A4 are N.

Embodiment 60. A compound of Embodiment 59 wherein at most A1, A21 A3 and A4 are N.

Achievement 61. A compound of Achievement 60 wherein at most A1, A21 A3 and A4 is N.

Embodiment 62. A compound of Embodiment 61 wherein each of A1, A2, A3 and A4 is different from N.

Embodiment 63. A compound of Formula 1 wherein, when Z is CH and R2 is attached to the phenyl ring at position 4, said R2 is different from C1-C6 alkoxy.

Embodiment 64. A compound of Formula 1 wherein when U is C (= 0) and G is NR31 R3 is different from H.

The embodiments of the present invention, including Embodiments 1a 64 above as well as any other embodiments described herein, may be combined in any way and the descriptions of the embodiments variables relate not only to the compounds of Formula 1 but also starting compounds and compounds. intermediaries. Further, embodiments of the present invention, including Embodiments 1 to 64 above as well as any other embodiments described herein and any combination thereof, relate to the compositions and methods according to the present invention.

Combinations of Achievements 1 through 64 are illustrated by:

Embodiment A. A compound of Formula 1 wherein:

Q is a pyridinyl ring, pyrimidinyl ring, triazinyl ring, ringpyrazolyl ring, triazolyl ring, imidazolyl ring, oxazolyl ring, isoxazolyl ring, ringthiazolyl or isothiazolyl ring, wherein each ring is optionally substituted with one or more substituents independently selected from halogen, C1-alkyl C1-C6 haloalkyl, C1-C6 cycloalkyl, C1-C6 halocycloalkyl, C1-C6 alkoxy C1-C6 haloalkoxy C1-C6 alkylthio C1-C6 alkylsulfinyl C1-C6l haloalkyl C1-C6-alkylsulfonyl halo C6, C1 -C6 alkylamino C2 -C8 dialkylamino, cyano, nitro, C (O) NR8 R9, C (O) OR101 phenyl and pyridinyl, wherein each phenyl or pyridinyl is optionally substituted with one or more substituents independently selected from R11; or Q is C (O) NR 12 R 13, S (O) 2 NR 14 R 15 or R 16;

Z is CR2;

R 1 is C 1 -C 3 alkyl optionally substituted with one or more substituents independently selected from R 17;

each R2 is independently selected from H1halogen or C1-C2 haloalkyl;

R3 is H or cyano; or optionally substituted C1-C4 alkyl with one or more substituents selected from halogen; - R4 and R5 are independently selected from

halogen, C1-C3 alkyl, C1-C3 haloalkyl, cyano and nitro;

R6 and R7 are independently selected from halogen, C1-C3 alkyl, C1-C3 haloalkyl, cyano and nitro; or R 6 and R 7 are taken together to form a fused aromatic ring, wherein the fused aromatic ring contains as ring members, in addition to the bridgehead atoms A3 and A41 four atoms selected from three to four carbon atoms and zero to one atom of nitrogen;

each R 8 is independently H, C 1 -C 6 alkyl, C 2 -C 7 alkylcarbonyl or C 2 -C 7 alkoxycarbonyl; - each R 9 and R 10 is independently H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 4 cycloalkyl, C 4 -C 7 alkylcycloalkyl or C 4 -C 7 cycloalkylalkyl, each optionally substituted with one or more substituents selected from from R19;

R 12 and R 14 are independently H, C 1 -C 6 alkyl, C 2 -C 7 alkylcarbonyl or C 2 -C 7 alkoxycarbonyl;

R13 and R15 are independently H1 C1 -C4 alkyl, C2 -C4 alkenyl, C2 -C4 alkynyl, C3 -C4 cycloalkyl, C4 -C7 alkylcycloalkyl or C4 -C7 cycloalkylalkyl, each optionally substituted with one or more substituents selected from R19;

R16 is halogen, C1 -C6 haloalkyl, C2 -C4 dialkylamino, cyano or nitro;

each R19 is independently selected from halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfonyl, cyano, nitro and Q1;

each Q1 is independently selected from defenyl, pyridinyl and thiazolyl, each optionally substituted with one or more substituents independently selected from halogen, C1-C3 alkyl, C1-C3 haloalkyl, cyano, phenyl and pyridinyl; and

η is 1 or 2;

provided that a maximum of 1 out of A11 A21 A3 and A4 is N.

Achievement B. A compound of Achievement A wherein:

R1 is halogen substituted C1-C3 alkyl; and

- U is C (= 0).

Achievement C. A compound of Achievement B wherein:

Q is a pyrazolyl ring, triazolyl ring or imidazolyl ring, wherein each ring is nitrogen bonded and optionally substituted with one or more substituents independently selected from halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, haloalkoxy C 1 -C 4, cyano, nitro, C (O) NR 8 R 9 and C (O) OR 10; or Q is C (O) NR 12 R 13;

R1 is CF3;

R6 and R7 are independently selected from H1halogen, C1-C3 alkyl, C1-C3l haloalkyl cyano and nitro; or R 6 and R 7 are taken together to form a fused aromatic ring, wherein the fused aromatic ring contains four carbon atoms as ring members in addition to the bridgehead atoms A3 and A4;

each R 8 is H, each R 9 and R 10 is independently C 1 -C 4 alkyl optionally substituted with one Q 1 and optionally substituted with one or more substituents selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 6 alkylsulfonyl C4 and cyano;

R12 is H;

R13 is H or C1 -C4 alkyl optionally substituted with one or more substituents selected from R19; and

Each R19 is independently selected from halogen and Q1.

Embodiment D. A compound of Embodiment C wherein: each R 2 is independently H 1 halogen or CF 3; eR 3 is CH 3, CH 2 CH 3 or CH 2 CF 3.

Embodiment E. A compound of Embodiment D wherein: G is O, provided that A11 A21 A3 and A4 are different from N.

Specific embodiments include compounds of Formula 1 selected from the group consisting of:

4- [5- (3,5-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide;

4- [5- (3,5-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2-methyl-N- (2,2,2-trifluoroethyl) benzamide;

4- [5- (3,5-dichlorophenyl) -2-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-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide;

4- [4- (3,5-dichlorophenyl) -3-methyl-2-oxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide;

4- [5- (3,4-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2-methyl- [2- (2-pyridinylmethyl) benzamide;

5- [5- (3,5-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2- (1H-1,2,4-triazol-1-yl) benzonitrile;

4- [5- (3,5-dichlorophenyl) -2,2-dioxide-5- (trifluoromethyl) -1,2,3-oxathiazolidin-3-yl] -2-methyl-A / - (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 selected from the group immediately above.

Compounds according to the present invention which are characterized by favorable soil metabolic and / or residual patterns and exhibit control activity of a spectrum of agronomic and non-agronomic pests deserve observation.

It deserves specific observation, for reasons of economic importance and spectrum of invertebrate pest control, that the protection of agronomic defects against injury or damage caused by invertebrate pests through invertebrate pest control is an accomplishment of the present invention. The compounds according to the present invention, due to their favorable translocation properties or plant systemicity, also protect leaf or other plant parts that are not directly contacted with a compound of Formula 1 or a composition comprising the compound.

Also noted as embodiments of the present invention are invertebrate pest control compositions comprising a biologically effective amount of a compound according to any of the foregoing embodiments, as well as any other embodiments described herein and any combinations thereof, and at least one additional component selected from the above. a group consisting of a surfactant, solid diluent and liquid diluent, wherein said composition optionally further comprises a biologically effective amount of at least one additional biologically active agent or compound. Embodiments of the present invention further include invertebrate control methods comprising pest contact. invertebrate or its environment with a biologically effective amount of a compound according to any of the foregoing embodiments (such as in the composition described herein).

Embodiments of the present invention also include a composition comprising a compound according to any of the foregoing embodiments, in the form of liquid soil-soaking formulation. Embodiments of the present invention further include invertebrate pest control methods comprising contacting the soil with a soil-soaking liquid composition comprising a biologically effective amount of a compound according to any of the foregoing embodiments.

Embodiments of the present invention also include an invertebrate pest control spray composition comprising a biologically effective amount of a compound according to any of the foregoing embodiments and a propellant. Embodiments of the present invention further include an invertebrate pest control bait composition comprising a biologically effective amount of a compound according to any of the foregoing embodiments, one or more food materials, optionally an attractive and optionally a humectant. Embodiments of the present invention also include an invertebrate pest control device comprising said bait composition and a shelter adapted to receive said bait composition, wherein the shelter has at least one dimensioned opening to allow the invertebrate pest to pass through the aperture. that the invertebrate pest may have access to the said bait composition from a location outside the shelter and where the shelter is further adapted for placement in a known activity site or potential for or near the invertebrate pest.

The compounds of Formula 1 may be prepared by one or more of the following methods and variations as described in Schemes 1 to 14. The definitions of R1, R2, A1, A2, A3, A4, G, U, Q, Z and η The compounds of Formulas 1 to 24 below are as defined above in the Summary Description of the Invention. Formulas 1a and 1b are subsets of Formula 1 and Formula 2a is a subset of Formula 2.

As shown in Scheme 1, a Formula 1 compound can be prepared by treating a Formula 2 amine with an appropriate Formula 3 reagent (where L is an appropriate nucleophilic reaction group such as halogen or imidazole) in the presence of a base (such as triethylamine, N, N-diisopropylethylamine or hydrogen carbonate sodium). They are also useful as polymer-supported acidic extractant bases such as N, N-diisopropylethylamine and 4- (dimethylamino) pyridine polymer-joined equivalents, such as N - [(4-ethenylphenyl] methyl)] -N-methyl-2-polymer. 4-pyridinamine with dietenylbenzene and ethenylbenzene (CAS Registry No. 82942-26-5, hereinafter referred to as "PS-DMAP"). The method of Scheme 1 may be carried out with a wide variety of Formula 3 reagents such as 1,1'-carbonyldiimidazole, phosgene, trichloromethyl chloroformate, triphosgene (ie when U is C (= 0)), thiophosgene, 1,1 ' -thiocarbonyl diimidazole (ie when U is C (= S)), thionyl chloride (ie when U is S (= O)) and sulfuryl chloride (ie when U is S (O) 2).

<formula> formula see original document page 33 </formula>

The reaction may be conducted neat or in a solvent such as dichloromethane, chloroform, tetrahydrofuran, acetonitrile or 1,2-dichloroethane. Temperatures for this reaction may range from 0 to 90 ° C. The method of Scheme 1 is illustrated in Step F of Example 1, Step D of Example 2 and Example 3.

The compounds of Formula 2a (Formula 2 wherein G is O) may be made by ring-ringing an appropriate Formula 4 epoxide by treatment with an Formula 5 amine in a solvent such as methanol, ethanol, chloroform, tetrahydrofuran, acetonitrile or 1,2-dichloroethane at temperatures ranging from 25 to 90 ° C as illustrated in Scheme 2. The method of Scheme 2 is illustrated in Step E of Example 1 and Step C of Example 2.

Scheme 2

<formula> formula see original document page 33 </formula>

The epoxides of Formula 4 may be prepared from Formula 6 ketones by treatment with a sulfonium ylide, which is typically generated in situ by reacting a Formula 7 detrimethylsulfoxon halide with an appropriate base such as sodium hydride, hydride, hydride. potassium or sodium tert-butoxide in a suitable solvent such as dimethyl sulfoxide, N, N-dimethylformamide or tert-butanol as illustrated in Scheme 3. The method of Scheme 3 is illustrated in Step D of Example 1.

Trimethylsulfoxon halides of Formula 7 are commercially available.

Scheme 3

<formula> formula see original document page 34 </formula>

As shown in Scheme 4, ketones of Formula 6 may be obtained by treating compounds of Formula 8 with metallic lithium, an organolithium reagent such as n-butyllithium, sec-butyl lithium or tert-butyl lithium, or an alkylmagnesium halide such as as ethyl or methyl magnesium chloride or bromide at temperatures typically from -78 ° C to 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 residual group such as Cl, Br1OCH3 or OCOCF3 to generate the ketone of Formula 6. The reaction is conducted in an organic solvent, preferably tetrahydrofuran or diethyl ether. The method of Scheme 4 is illustrated in Step C of Example 1. Scheme 4

<formula> formula see original document page 35 </formula>

Alternatively, compounds of Formula 1a (Formula 1 wherein G is O and U is C (= O)) may be prepared from oxazolidinones of Formula 10 by reaction with aromatic halide intermediates of Formula 11 (wherein L2 is a group). such as F or CI) as shown in Scheme 5.

Scheme 5

<formula> formula see original document page 35 </formula>

In this reaction, the oxazolidinone of Formula 10 is contacted with a base, such as sodium hydride or potassium tert-butoxide, and then treated with a compound of Formula 11 typically in a solvent (such as N, N-dimethylformamide or sulfoxide). of dimethyl). The method of Scheme 5 is illustrated in Step B of Example 4. Alternatively, when Formula 11 is an aryl bromide (ie L 2 is BR), the reaction may be conducted with two equivalents of a base such as potassium carbonate in the presence of a copper (I) catalyst such as copper (I) iodide (typically 3 to 5 mol%) and frans-cyclohexanediamine (to solubilize Cul) using the method described in Organic Letters 2003, 5, 963-965.

As shown in Scheme 6, compounds of Formula 1 may 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, biarylbismutane. trialkylstannane or trialkylsiloxane. The reaction may be conducted in a solvent such as dichloromethane, chloroform outetrahydrofuran and in the presence of a copper salt such as copper (II) acetate and a base (such as triethylamine or pyridine) as shown in Scheme 6. For general procedures of this type of reaction, see Ley1 S. V .; Thomas, A.W., Angewandte Chemie, International Edition 2003, 42, 5400-5449.

Scheme 6

<formula> formula see original document page 36 </formula>

Oxazolidinones of Formula 10 may be prepared by daring amino alcohols of Formula 13 with triphosgene or detrifogene substitutes which result in carbonylation (such as diphosgene, phosgene, (bis) trichloromethyl carbonate or 1,1'-carbonyl diimidazole). The reaction is conducted in an appropriate organic solvent such as dichloromethane, 1,2-dichloroethane outetrahydrofuran in the presence of a base such as triethylamine, sodium hydrogen carbonate or sodium carbonate as illustrated in Scheme 7.

Scheme 7

<formula> formula see original document page 36 </formula>

Amino alcohols of Formula 13 may be prepared by reducing the cyanohydrins of Formula 14 with a reducing agent such as lithium tetrahydroaluminate in an appropriate organic solvent such as diethylether or tetrahydrofuran as illustrated in Scheme 8. The methods of Schemes 7 and 8 are illustrated in Step A of Example 4.

Scheme 8

<formula> formula see original document page 37 </formula>

Cyanohydrins of Formula 14 may be prepared from the corresponding ketones (i.e. Formula 6) by one of a number of cyanation methods well known in the art (see, for example, North, M., Science of Synthesis 2004, 19 , 235-284).

The compounds of Formula 1b (i.e. Formula 1 wherein G is NR 3 and U is C (= 0)) may be prepared by reducing the imide of Formula 15 with sodium borohydride in an appropriate solvent such as methanol and then reducing. of the resulting 5-hydroxy intermediate with sodium borohydride and trifluoroacetic acid. Ketone and alcohol reduction methods are well documented in the art. See, for example, Mehrotra, Μ. M. et al., JoumaIofMedicinaI Chemistry2004, 47, 2037-2061 and Johnson, M. R .; Rickborn, B .; Journal of Organic Chemistry1970, 35, 1041-1045. The method of Scheme 9 is illustrated in Example 5, Steps E and F, as well as Example 6, Steps B and C.

Scheme 9

<formula> formula see original document page 37 </formula> As shown in Scheme 10, compounds of Formula 15 may be prepared by cyclizing urea from Formula 16 by treatment with aqueous hydrochloric acid according to the general method described by Cook1. AH; Hunter1 G. D .; Journal of the Chemical Society 1952,3789-3796. For compounds of Formula 15 wherein R3 is other than H, the cyclized intermediate (where R3 is H) is then treated with L3-R3 (where L3 is a residual group) in the presence of of an appropriate base such as sodium hydride to generate compounds of Formula 15. The second step of the method of Scheme 10 is illustrated in Example 6, Step A.

Figure 10

<formula> formula see original document page 38 </formula>

As shown in Scheme 11, compounds of Formula 16 may be obtained by reacting Formula 17 α-aminonitriles with Formula 18 comisocyanates according to the general method of Van Dort1 M. E.; Junt, Y.-W .; Bioorganic & Medicinal Chemistry Letters 2004, 14 (21), 5285-5288.

Scheme 11

<formula> formula see original document page 38 </formula>

The compounds of Formula 17 may be obtained by converting ketones of Formula 6 into the corresponding imines 20, followed by the addition of a cyanide source (such as HCN) to the imine intermediates, followed by the addition of cyanide, which is well documented in the art. (see, for example, Organic Reactions 2002, 59, 1-714 and Koos, M .; Mosher, HS; Tetrahedron 1993, 49, 1541-1546).

The method shown in Scheme 12 is particularly useful for preparing imines 20 when R1 is CF3.

Figure 12

<formula> formula see original document page 39 </formula>

As shown above, a ketone of Formula 6 is first treated with lithium bis (trimethylsilyl) amide, which results in the formation of an imine intermediate 19, which is then solvolized to methanol to give a stable imine 20 according to the method. Gosselin, F. et al., Organic Letters 2005, 7, 355-358.

Alternatively, compounds of Formula 15 may be prepared by heating compounds of Formula 21 with Formula 5 amines (see Scheme 13) in the presence of a catalyst such as 4- (dimethylamino) pyridine or trifluoroacetic acid. The formed hydantoinasciclised can then 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 Scheme 3 is illustrated in Example 5, Step D.

Figure 13

<formula> formula see original document page 39 </formula> As shown in Scheme 14, compounds of Formula 21 can be obtained by reacting Formula 22 α-ketoesters with benzyl carbamate, after dehydration, to form Formula 23 imines. followed by the addition of Grignard intermediates 24, which may be derived from compounds of Formula 8 as described above for the method of Scheme 4. For general reference, see Dessipri, E .; Tirrell, D.A. Macromolecules 1994, 27, 5463-5470. The method of Scheme 14 is illustrated in

Example 5, Steps A-C.

Scheme 14

<formula> formula see original document page 40 </formula>

Those skilled in the art will recognize that compounds of Formula 1 and the intermediates described herein may be subjected to various electrophilic, nucleophilic, radicals, organometallic, oxidation and deduction reactions to add existing substituents or modify substituents. It is also recognized that some reagents and reaction conditions described above for the preparation of compounds of Formula 1 may not be compatible with certain functionalities present in the intermediates. In these cases, the incorporation of protection and deprotection sequences or functional group interconversions in the synthesis will assist in obtaining the desired products. The use and selection of protecting groups will be apparent to those skilled in the art of chemical synthesis (see, for example, Greene1 T.W .; Wuts1 P. G. M., Protective Groups in Organic Synthesis, Second Edition; Wiley: New York, 1991). Those skilled in the art will recognize that, in some cases, upon introduction of a given reagent as illustrated in any individual scheme, it may be necessary to perform additional routine step synthetics not described in detail to complete the synthesis of Formula 1 compounds. It will also be appreciated in the art that a combination of the steps illustrated in the above schemes may be required in a different order from that indicated by the specific sequence presented to prepare the compounds of Formula 1.

Without further elaboration, it is believed that the subject matter, using the above descriptive report, may utilize this invention to the fullest extent possible. The following Examples should therefore be considered merely illustrative and not limiting the descriptive report in any way. 1 H NMR spectra are reported in ppm from tetramethylsilane; 19F NMR spectra are reported in PPM using trichlorofluoromethane as a reference; "s" indicates isolated, "d" indicates double, "t" indicates triple, "m" indicates multiple, "dd" indicates pair of doubles, "dt" indicates pair of trios, "br s" indicates broad isolate and "br t "indicates broad triple.

Example 1

Preparation of 4-5- (3,5-dichloro-phenyl-2-0x0-5- (trifluoromethyl) -3-oxazolidinyl-2-methyl- / V- (2,2,2-trifluoroethyl) benzamide Step A: Preparation of 4- (acetylamino) ) -2-meth- / V- (2,2,2-trifluoroethylbenzamide

To a stirred solution of 4- (acetylamino) -2-methylbenzoic acid (Aldrich, 1.9 g, 9.8 mmol) in tetrahydrofuran (9 ml) at room temperature was added 1,1'-carbonyldiimidazole (1, 65 g, 10.1 mmol). After eighteen hours, 2,2,2-trifluoroethanamine (1.6 g, 16.0 mmol) was added, followed by a catalytic amount of 4- (dimethylamino) pyridine (also known as N1N-dimethyl-4-pyridinamine). After 24 hours, water was added to the reaction mixture and the resulting precipitate was collected by filtration and dried to provide the title compound as white powder (2.1 g).

1 H NMR (DMSO-Cfe): δ 10.01 (s, 1Η), 8.80 (t, 1Η), 7.46 (d, 1Η), 7.45 (s, 1Η), 7.31 ( d, 1H), 4.02 (m, 2H), 2.31 (s, 3H), 2.05 (s, 3H).

Step B: Preparation of 4-Amino-2-Methyl-AM2,2,2-Trifluoroethyl) Benzamide ·

To 4- (acetylamino) -2-methyl-A / - (2,2,2-trifluoroethyl) benzamide (ie, the product of Step A), concentrated hydrochloric acid was added and the reaction mixture was heated to 100 ° C for two hours. The reaction mixture was cooled using an external ice-water bath and aqueous sodium hydroxide (50 wt.%, 20 ml) was added until the reaction mixture was neutralized, causing a solid to precipitate. The solid was filtered, washed with water and dried in a vacuum oven at 60 ° C overnight to provide the title compound as a white powder (0.89g).

1 H NMR (DMSO-cfe) δ 8.42 (t, 1H), 7.18 (d, 1H), 6.38 (s, 1H), 6.39 (d, 2H), 5.43 (br 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 mixture of 1-bromo-3,5-dichlorobenzene (Aldrich, 15.0g, 65.1 mmol) in anhydrous ether (300 mL) at -70 ° C was added A7-butyl lithium (2.5 Mem. hexane, 26.0 ml, 65.0 mmol) in drops for thirty minutes. After five minutes, methyl trifluoroacetate (9.17 g, 71.6 mmol) in ether (7 mL) was added dropwise over 45 minutes. After an additional 45 minutes, the reaction mixture was warmed to 0 ° C and then poured into saturated aqueous potassium dihydrogen phosphate solution (50 g in 200 ml water) and stirred for 30 minutes at room temperature. The layers were separated and the organic layer was washed with saturated sodium chloride (100 mL), dried (MgSO4) and concentrated under reduced pressure to afford the title compound as yellow oil (13.0 g).

1 H NMR (CDCl 3) δ 7.74 (s, 2H), 7.44 (s, 1H). 19 F NMR (CDCl 3): δ -76.82. Step D: Preparation of 2- (3,5-dichlorophenyl-2- (trifluoromethyl) oxirane.

Sodium hydride (60%, 0.36 g, 9.0 mmol) was added to a stirred solution of trimethylsulfoxonium iodide (1.88 g, 8.5 mmol) in dimethyl sulfoxide (17 ml) under a nitrogen atmosphere. . After stirring for half an hour, the solution was added dropwise over five minutes to a solution of 1- (3,5-dichlorophenyl) -2,2,2-trifluoroethanone (i.e. the product of Step C) (1.7 g , 7.0 mmol) in tetrahydrofuran. The resulting yellow syrup was stirred for five minutes and then the reaction mixture was partitioned between ether (100 mL) and water (50 mL). The organic layer was separated and the aqueous layer was extracted with ether (70 ml). The combined ether extracts were washed with water (40ml) and dried (MgSO4). The ether solution was filtered and the solvent was concentrated under reduced pressure to afford the title compound as orange oil (1.71 g). The crude product (70-80% by 1 H NMR) was used without purification.

1 H NMR (CDCl 3): δ 7.42 (m, 3H), 3.43 (d, 1H), 2.91 (m, 1H). NMR 19 F (CDCl 3): δ -74.57.

STEP Ε: 4-rr2- (3,5-DICHLOROPHENYL) -2-HYDROXY-3,3.3-TRIFLUOROPROPYLAMINO1-2-METHYL / V- (2,2,2-TRIFLUOROETHYL) BENZAMIDE.

A solution of 2- (3,5-dichlorophenyl) -2- (trifluoromethyl) oxirane (ie, the product of Step D) (0.82 g) and 4-amino-2-methyl- / V- (2.2 2-trifluoroethyl) benzamide (i.e. the product of Step B) (0.42 g, 1.7 mmol) in anhydrous ethanol (8 ml) was heated at 75 ° C for eighteen hours. After cooling, the solvent was concentrated under reduced pressure. The residue was purified by medium pressure silica gel chromatography using ethyl acetate and hexanes (2: 3) as eluent to afford the title compound as off-white vitreous desolide (0.36 g).

1H NMR (CDCl3): δ 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, 1 Η), 2, 00 (s, 3Η). 19 F NMR (CDCl 3): δ -72.80, -78.47.

Step F: 4- [5- [3,5-Dichlorophenyl] -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2-methyl-N- (2,2,2-trifluoroethyl) benzamide

4 - [[2- (3,5-Dichlorophenyl) -2-hydroxy-3,3,3-trifluoropropyl] amino] -2-methyl-N- (2,2,2-trifluoroethyl) benzamide (or the product of Step E) (0.28 g, 0.57 mmol), 1,1'-carbonyldiimidazole (0.15 g, 0.93 mmol) and PS-DMAP (Riley Co., 1.4 mmol / g ) (0.085 g, 0.12 mmol) in dichloromethane (7 mL) was stirred at room temperature for five hours. Additional 1,1'-carbonyldiimidazole (0.05 g, 0.31 mmol) was added. After stirring for 22 hours, additional 1,1'-carbonyldiimiazole (0.047 g, 0.28 mmol) and PS-DMAP (0.10 g, 0.14 mmol) were added. After stirring for four hours, the reaction mixture was concentrated under reduced pressure and the resulting residue was dissolved in ethyl acetate (60 mL), washed with water (3 x 30 mL), filtered through a ChemElut cartridge filled with diatomaceous earth ( manufactured by Varian) and concentrated under reduced pressure to generate a solid. The crude solid was purified by medium pressure silica gel chromatography using ethyl acetate and hexanes (2: 3) as eluent to afford the title product, compound according to the present invention, as an off-white solid (0.20 g). .

1H NMR (CDCl3): δ 7.48 (m, 3H), 7.41 (d, 1H), 7.37 (d, 1H), 7.31 (s, 1H), 6.38 (br s, 1H), 4.62 (d, 1H), 4.30 (d, 1H), 4.07 (m, 2H), 2.43 (s, 3H). 19 F NMR (CDCl3): δ-72.79 , -81.57.

Example 2

Preparation of 4- (5- (3,5-dichlorophenyl) -2-0x0-5- (trifluoromethyl) -3-oxazolidinyl-2-methyl-N- (2-pyridinylmethyl) benzamide

Step A: Preparation of 4- (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 mmol) and N'-ethylcarbonimidoyl monohydrochloride NN-dimethyl-1,3-ropanediamine (5.2 g, 27.1 mmol) in dichloromethane (250 mL) was stirred at room temperature overnight. Water was then added to the reaction mixture and the two resulting layers were separated. . The dichloromethane layer was passed through a Chem Elut cartridge filled with diatomaceous earth (manufactured by Varian) and concentrated under reduced pressure. The resulting amber oil was triturated with dichloromethane, π-butyl chloride and hexanes to afford the title compound as a pale yellow solid (5.5 g).

1H NMR (CDCl3) δ 8.53 (d, 1H), 7.92 (br 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 (i.e. the product of Step A) (5.5 g, 19.4 mmol) and concentrated hydrochloric acid (100 mL) was stirred and heated under reflux for one hour. After cooling, ice was added and the pH adjusted to 10 by adding aqueous sodium hydroxide (50 wt%). The reaction mixture was filtered to collect the solid precipitate, which was washed with water and dried to afford the title compound as a light yellow solid (4.02 g).

1H NMR (DMSO-cfe) δ 8.49 (d, 1H), 8.41 (br 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-R 2 - (3,5-Dichlorophenyl) -2-Hydroxy-3,3,3-trifluoropropylaminol-2-methyl-A / - (2-pyrrhenylmethyl) benzamide

A solution of 2- (3,5-dichlorophenyl) -2- (trifluoromethyl) oxirane (i.e. the product of Example 1, Step D) (0.75 g) and 4-amino-2-methyl - / - (2-pyridinylmethyl) benzamide (i.e. the product of Step B) (0.39 g, 1.7 mmol) in anhydrous ethanol (6 mL) was heated at 65 ° C for seventy hours. The reaction mixture was concentrated under reduced pressure and the residue was purified by medium pressure silica gel chromatography using ethyl acetate and hexanes (6: 8) as eluent to afford the title compound as off-white solid (0.28 g). .

1H NMR (CDCl3): δ 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 (brt, 1H), 6.37 (s, 1H), 6.36 (d, 1H), 5.02 (br s, 1H), 4, 68 (d, 2H), 3.88 (t, 1H), 3.81 (dd, 1H), 3.61 (dd, 1H), 2.39 (s, 3H). 19M NMR (CDCl3): δ -78.43.

Step D: Preparation of 4- [5- (3,5-Dichlorophenyl) -2-οxο-5- (TRIFLUROMETILE) -3-oxazolidinyl-2-methyl-N- (2-pyridinylmethyl) benzamide.

4 - [[2- (3,5-Dichlorophenyl) -2-hydroxy-3,3,3-trifluoropropyl] amino-2-methyl-N- (2-pyridinylmethyl) benzamide (i.e. the product of Step C) (0.21 g, 0.42 mmol), 1,1'-carbonyldiimidazole (0.13 g, 0.79 mmol), PS-DMAP (Riley Co., 0.065g, 0.12 mmol) and dichloromethane (7 mL ) were combined and stirred at room temperature for five hours. Additional 1,1'-carbonyldiimidazole (0.05 g, 0.31 mmol) was added. After stirring for 22 hours, additional 1,1'-carbonyldiimidazole (0.15 g, 0.92 mmol) and PS-DMAP (0.31 g, 0.43 mmol) were added. After stirring for 24 hours, the reaction mixture was concentrated under reduced pressure and purified by medium pressure silica gel chromatography using ethyl acetate and hexanes (6: 8) as eluent to provide the title product, a compound according to the present. invention as an off-white glassy solid (0.20 g).

1H NMR (CDCl3): δ 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): δ-81.52.

Example 3

Preparation of 4--5- (3,5-dichlorophenyl-2-oxide-5- (trifluoromethyl) -1,2,3-oxathiazolidin-3-IL] -2-methyl-N- (2-pyridinylmethyl) benzamide

To a stirred solution of 4 - [[2- (3,5-dichlorophenyl) -2-hydroxy-3,3,3-trifluoro-propyl] amino] -2-methyl-N- (2-pyridinylmethyl) benzamide (or Example 2, Step C) (0.11 g, 0.22 mmol), triethylamine (0.096 g, 0.95 mmol) and 4- (dimethylamino) pyridine (0.022 g, 0.018 mmol) in dichloromethane (2 mL ), thionyl chloride (0.043 g, 0.36 mmol) was added dropwise. After stirring for one hour at room temperature, more thionyl chloride (0.026 g, 0.22 mmol) was added. After stirring for a further hour, the reaction mixture was concentrated under reduced pressure and the crude product was purified by medium pressure silica gel chromatography using ethyl acetate and hexanes (3: 6) as eluent to afford the title product (mixture 1 : 1 of stereoisomers), a compound according to the present invention, as an off-white solid (0.04 g).

1H NMR (CDCl3) δ 8.50 (m, 1H), 7.69 (brt, 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 (CDCl3): δ -76.31, -79.67.

Example 4

PREPARATION OF 2-NiTR0-5-r2-0X0-5-FENiL-5- (TRiFLU0RQMETiL) -3-OXAZOLIDINYLBENZONITRIL

Step A: Preparation of 5-phenyl-5- (trifluoromethyl) -2-oxazolidine

To a cold solution (below 20 ° C) of tetrahydroaluminate delithium (10.0 ml, 1.0 M solution in diethyl ether) was added a solution of deahydroxy-α- (trifluoromethyl) benzeneacetonitrile (Aldrich, 2 0.1 g, 10.0 mmol) in anhydrous diethyl ether (10 mL). The resulting suspension was stirred at room temperature for three hours. To the reaction mixture was subsequently added water (0.38 ml), aqueous sodium hydroxide solution (15 wt%, 0.38 ml) and more water (1.14 ml). The reaction mixture was filtered through a glass frit and the filtrate was concentrated under reduced pressure to give a white solid (1.89 g). The white solid (1.23 g, 6.0 mmol) was dissolved in dichloromethane (15 mL) and added to a stirred saturated aqueous sodium hydrogen carbonate solution (15 mL). Then a solution of (bis) trichloromethyl triphosgenecarbonate (0.63 g, 2.17 mmol) in dichloromethane was added dropwise over several minutes. The reaction mixture was stirred at room temperature for one hour. The solvent phases were separated and the organic phase was washed with water, 1 N aqueous hydrochloric acid and saturated aqueous sodium chloride solution. The organic extracts were dried (MgSO 4), filtered and the solvent was concentrated under reduced pressure to afford the compound as a white solid (1.35 g).

1H NMR (CDCl3) δ 7.5-7.4 (m, 5H), 5.95 (br s, 1H), 4.26 (d, 1H), 3.93 (d, 1H).

STEP B: PREPARATION OF 2-NITRO-5-R2 <> XO-5-PHENYL-5- (TRIFLUOROMETILE) -3-OXAZOLIDINYLBENZONITRIL.

To a stirred solution of 5-phenyl-5- (trifluoromethyl) -2-oxazolidinone (i.e. the product of Step A) (0.97 g, 4.2 mmol) in t / V, Î ± -dimethylformamide (20 ml ) under nitrogen atmosphere, sodium hydride was added in one portion (60%, 0.21 g, 5.2 mmol). After 0.33 hours, 5-chloro-2-nitrobenzonitrile (1.15 g, 6.3 mmol) was added to the reaction mixture. The reaction mixture was stirred for sixteen hours, diluted with water and extracted with ether (100 ml) and ethyl acetate (100 ml). The combined organic extracts were washed with water (4 χ 75 ml), dried (MgSO4), filtered and concentrated under reduced pressure to give a solid, which was purified by silica gel chromatography and trituration with 20% ether / hexanes to give the title compound. title product, a compound according to the present invention, as a white solid (0.235 g).

1H NMR (CDCl3) δ 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 4- [4- (3,5-Dichlorophenyl) -2-oxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-PYRIDINYLMETHYL) BENZAMIDE

Step A: PREPARATION FOR 3,3,3-TRIFLUORO-2-HYDROXY-N- [PHENYLMETOXY) CARBONYL] ALANINE ESTER

A solution of 3,3,3-trifluoro-2-oxo-propionic acid ethyl ester (Alfa Chem. Co., 12.0 g, 70.6 mmol) and benzyl carbamate (9.78 g, 64.8 mmol ) in methylene chloride (55 ml) was stirred for 66 hours at room temperature under nitrogen. The solvent was removed under reduced pressure. Hexane (100 ml) was added to the crude mixture and the resulting slurry was allowed to stand overnight. The solid was collected by vacuum filtration, washed with hexane and air dried to provide the title compound as white solid (20.4 g).

1H NMR (CDCl3) δ 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 3,3,3-trifluoro-2-

rr (PHENYLMETOXY) ETHYL CARBONYLLINMINQROPANOATE

To a solution of 3,3,3-trifluoro-2-hydroxy-A / - [(phenylmethoxy) carbonyl] alanine ethyl ester (i.e. the product of Step A) (15.4 g, 48 mmol) and pyridine (7.9 g, 50 mmol) in anhydrous diethyl ether (200 mL) at ice temperature, trifluoroacetic anhydride (10.75 g, 51.1 mmol) was added in stock. The resulting syrup was warmed to room temperature and stirred for an hour and a half. The reaction mixture was filtered to remove a white solid. The filtrate was concentrated in vacuo to give a slurry. Hexane (150 mL) was added to the syrup, which was filtered again to remove a white solid. The filtrate was concentrated in vacuo to afford the title product as colorless oil (14.2g).

1H-NMR (CDCl3): δ 7.41 (m, 5H), 5.33 (s, 2H), 4.31 (q, 2H), 1.30 (t, 3Η).

Step C: PREPARATION OF 3,5-DICHLOR-α - [[(PHENYLMETOX1) CARBONYLAMINOl-α-

(TRIFLUOROMETIL) ETHYL BENZENOACTATE.

To a solution of ethyl 3,3,3-trifluoro-2 - [[(phenylmethoxy) carbonyl] imino] propanoate (i.e. the product of Step B) (7.36 g, 24.3 mmol) in anhydrous tetrahydrofuran (10 ml), cooled with a dry ice bath, was added a solution of 3,5-dichlorophenyl magnesium bromide (Aldrich Chem. Co., 0.5 M in tetrahydrofuran, 50 ml, 25 mmol) over 45 minutes. The opaque reaction mixture was stirred for one hour and then warmed to room temperature. To this yellow solution was added 1 hydrochloric acid (37 ml). The volume of tetrahydrofuran was removed in vacuo. The residue was partitioned between ethyl acetate (170 mL) and water (100 mL). The aqueous layer was extracted with ethyl acetate (50 mL). The combined organic layers were filtered through a Terradiatom-filled Chem Elut cartridge (manufactured by Varian) and concentrated under reduced pressure to give the title compound as yellow oil (11.1 g).

1H NMR (CDCl3): δ 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): δ-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-α - [[(phenylmethoxy) carbonyl] amino] -α- (trifluoromethyl) benzeneacetate (i.e. the product of Step C) (1.11 g, 2.5mmol), 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) was heated to 200 ° C by demicrowave irradiation for 350 seconds. Another conduction was performed 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 NMP (2 ml) under the same conditions. The mixtures of the two conductions were combined and diluted with ethyl acetate (100ml), washed with water (3 χ 50ml), filtered through a Chem Elut filled with diatomaceous earth cartridge (manufactured by Varian) and concentrated under reduced pressure to generate a dark oil. This was purified by medium pressure silica gel chromatography using ethyl acetate and hexanes (45% - 85%) as eluent to give the title compound as a brown solid (0.84 g).

1H NMR (DMSO-C6): δ 10.65 (s, 1H), 8.99 (t, 1H), 8.52 (d, 1H), 7.89 (br 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-2-methyl- / v- (2-pyridinylmethyl) benzamide

To a 4- [4- (3,5-dichlorophenyl) -2,5-dioxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide (i.e. the product from Step D) (0.66 g, 1.23 mmol) in methanol (18 mL) at ice bath temperature, sodium borohydride (0.275 g, 7.3 mmol) was added in small batches for three minutes. The resulting orange solution was stirred at room temperature for eighteen hours. The solvent was removed in vacuo and the residue partitioned between ethyl acetate (50 mL) and water (50 mL). The aqueous layer was extracted with ethyl acetate (35 mL). The combined organic layers were filtered through a diatomaceous earth filled Chem Elut cartridge (manufactured by Varian) and concentrated under reduced pressure to give the title compound as a brown solid (0.59 g).

1H NMR (DMSO-q6): δ 9.17 (s, 1H), 8.78 (t, 1H), 8.52 (d, 1H), 7.79 (dt, 1H), 7.75 (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).

Step F: Preparation of 4- (4- (3,5-Dichlorophenyl) -2-oxo-4- (trifluoromethyl) -1-imidazolidinyl-2-methyl-α / (2-pyridinylmethyl) benzamide

To a solution of 4- [4- (3,5-dichlorophenyl) -5-hydroxy-2-oxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-A / - (2-pyridinylmethyl) ben ( the product from Step E) (0.18 g, 0.33 mmol) in trifluoroacetic acid (4 mL) at ice bath temperature, sodium borohydride (0.10 g, 2.6 mmol) was added in two batches. After completion of the initial vigorous reaction, the reaction mixture was stirred at room temperature. An additional batch of sodium borohydride (0.048 g) was added after two hours. The reaction mixture was stirred for eighteen hours and then water (5 ml) was added thereto. The reaction mixture was cooled with an external ice-water bath and then sodium hydroxide solution (4.1 g of 50% aqueous solution and 10 ml of water) was added. The reaction mixture was extracted with ethyl acetate (2 x 25 ml) and the combined organic layers were filtered through a Chem Elut cartridge filled with diatomaceous earth (manufactured by Varian) and concentrated under reduced pressure to give a gum solid. Another conduction was performed using 90 mg of Step E product, 2 ml of trifluoroacetic acid and 67 mg of sodium borohydride under similar conditions. The crude products of these two conditions were combined and purified by medium pressure silica gel chromatography using ethyl acetate. and hexanes (45% - 65%) as eluent to give the title compound, a compound according to the present invention, as an off-white solid (0.18 g).

1H NMR (CDCl3): δ 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-methyl-2-oxo-4- (trifluoromethyl) -1-imidazolidinyl-2-methyl-N- (2-pyridinylmethyl) benzamide

Step A: Preparation of 4- [4- (3,5-dichlorophenyl) -3-meth-2,5-dixy-4-methyl-imidazolidinyl-1-2-methyl-N- (2-pyridinylmethyl) benzamide

To a solution of 4- [4- (3,5-dichlorophenyl) -2,5-dioxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzam (i.e. (Example D, Step D product) (0.39 g, 0.73 mmol) in N, N-dimethylformamide (4 mL) was added sodium hydride (60% oil dispersion, 0.0335 g, 2 0.3 mmol). After stirring for fifteen minutes, dihydromethane (0.179 g, 1.26 mmol) was added. The reaction mixture was stirred for 45 minutes and then partitioned between ethyl acetate (50 mL) and water (25 mL). The organic layer was washed with water (2 x 25 mL) and filtered through a filled Chem Elut cartridge. with diatomaceous earth (manufactured by Varian) and concentrated under reduced pressure to yield the title compound in vitreous desolate form (0.39 g).

1H NMR (DMSOd6) δ 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, 3H), 2, 40 (s, 3H).

Step B: Preparation of 4- [4- (3,5-dichlophenyl) -5-hydroxy-3-methyl-2-oxo-4- (trifluoromethyl) -1-imidazolidinyl-2-methyl-yy- (2-pyridinylmethyl) benzamide

To an opaque solution of 4- [4- (3,5-dichlorophenyl) -3-methyl-2,5-dioxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-A / - (2-pyridinylmethyl) ) benzamide (i.e. Step A product) (0.37 g, 0.67 mmol) in methanol (10 mL), sodium borohydride (0.167 g, 4.42 mmol) was added in small batches over five minutes. . After stirring for 4.5 hours, methanol was removed in vacuo and the residue was partitioned between ethyl acetate (50 mL) and water (50 mL). The aqueous layer was extracted with ethyl acetate (35 ml) and the combined organic layers were filtered through a Terradiatom-filled Chem Elut cartridge (manufactured by Varian) and concentrated under reduced pressure to give the title compound as a brown solid (0.32 g).

1H NMR (DMSO-d6): δ 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) benzamide

To a solution of 4- [4- (3,5-dichlorophenyl) -5-hydroxy-3-methyl-2-oxo-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) ) benzamide (i.e. the product of Step B) (0.25 g, 0.45 mmol) in trifluoroacetic acid (6 ml), sodium borohydride (0.14 g, 3.7 mmol) was added in batches by three minutes. After stirring for one hour at room temperature, additional sodium borohydride (0.104 g, 2.7 mmol) was added. After stirring for an additional eighteen hours, water (10 ml) was added. The reaction mixture was cooled with an external ice water bath and then sodium hydroxide solution (6 ml of 50% aqueous solution and 20 ml of water) was added. The reaction mixture was extracted with ethyl acetate (1 x 50 ml, 1 x 35 ml) and the combined organic layers were filtered through a diatom earth-filled Chem Elut cartridge (manufactured by Varian) and concentrated under reduced pressure to give a solid in degome, which was purified by medium pressure silica gel chromatography using ethyl acetate and hexanes (45% - 65%) as eluent to afford the title compound, compound according to the present invention, as a white solid (0 , 20 g).

1H NMR (CDCl3): δ 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 (br t, 1H), 4.73 (d, 2H), 4.31 (d, 1H), 3.83 (d, 1H), 2, 90 (s, 3H), 2.51 (s, 3H).

By the procedures described herein, together with methods known in the art, the following compounds can be prepared from Tables 1 to 15. The following abbreviations are used in the following Tables: CN indicates cyano, NO2 indicates nitro, Ph indicates phenyl, Py indicates pyridinyl, Me indicates methyl, Et indicates ethyl, Pr indicates isopropyl and MEe indicates methoxy. (R2) m, as shown, means the combination of (R2) n when Z is CR2, as specified for Formula 1.

Table 1

<table> table see original document page 55 </column> </row> <table> <table> table see original document page 56 </column> </row> <table> <table> table see original document page 57 < / column> </row> <table> <table> table see original document page 58 </column> </row> <table>

Table 2

<table> table see original document page 58 </column> </row> <table> <table> table see original document page 59 </column> </row> <table> <table> table see original document page 60 < / column> </row> <table>

Table 3

<formula> formula see original document page 60 </formula>

<table> table see original document page 60 </column> </row> <table> <table> table see original document page 61 </column> </row> <table> <table> table see original document page 62 < / column> </row> <table> <table> table see original document page 63 </column> </row> <table> <table> table see original document page 64 </column> </row> <table> <table> table see original document page 65 </column> </row> <table> <table> table see original document page 66 </column> </row> <table>

<formula> formula see original document page 66 </formula>

<table> table see original document page 66 </column> </row> <table> <table> table see original document page 67 </column> </row> <table>

Table 6

<table> table see original document page 67 </column> </row> <table> <table> table see original document page 68 </column> </row> <table> <table> table see original document page 69 < / column> </row> <table> <table> table see original document page 70 </column> </row> <table>

Table 8

<table> table see original document page 70 </column> </row> <table> <table> table see original document page 71 </column> </row> <table> <table> table see original document page 72 < / column> </row> <table> <table> table see original document page 73 </column> </row> <table> Table 10

<table> table see original document page 74 </column> </row> <table> Table 11

<table> table see original document page 75 </column> </row> <table> Table 12

<table> table see original document page 76 </column> </row> <table> <table> table see original document page 77 </column> </row> <table>

Table 14

<formula> formula see original document page 77 </formula>

where m is 1, 2, 3, 4 or 5.

<table> table see original document page 77 </column> </row> <table> <table> table see original document page 78 </column> </row> <table>

<formula> formula see original document page 78 </formula>

<table> table see original document page 78 </column> </row> <table> <table> table see original document page 79 </column> </row> <table> <table> table see original document page 80 < / column> </row> <table>

Formulation / utility

The compounds of the present invention may generally be used as an active ingredient for pest control in a composition, i.e. formulation, with a carrier suitable for agronomic or non-agronomic uses comprising at least one of a liquid diluent, solid diluent or surfactant. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, humidity and temperature.

Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including micromemulsions and / or suspoemulsions) and the like, which may optionally be thickened as gels. General types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspension, concentrated emulsion, microemulsion and suspoemulsion. General types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates and oil dispersions.

General types of solid compositions are dust, powders, granules, pellets, pills, tablets, filled films (including seed coating) and the like, which may be water dispersible ("wettable") or water soluble. Films and coatings formed from film forming solutions or fluid suspensions are particularly useful for seed treatment. The active ingredient may be (micro) encapsulated and further molded into a suspension or solid formulation, alternatively the entire active ingredient formulation may be encapsulated (or "overcoated"). Encapsulation may control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of an emulsifiable concentrate formulation and a dry granular formulation. High strength compositions can be mainly used as intermediates for further formulation.

Sprayable formulations are typically extended in an appropriate medium prior to spraying. These liquid and solid formulations are designed to be easily diluted in the spray medium, usually water. Spray volumes may range from about one to several thousand liters per hectare, but are most typically in the range of about ten to several hundred liters per hectare. Sprayable formulations may be mixed in a tank with water or another suitable medium for foliar treatment by terrestrial or aerial application, or for application to plant growth medium. Dry eliquid formulations can be measured directly in drip irrigation systems or measured in the pit during planting. Solid liquid formulations can be applied to crop seeds and other desirable vegetation as pre-planting seed treatments to protect developing roots and other parts of underground plants and / or foliage by systemic absorption.

The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the approximate ranges below, which add up to 100% by weight.

<table> table see original document page 82 </column> </row> <table>

Solid diluents include, for example, clays such asobentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, detitanium dioxide, zinc oxide, starch, dextrin, sugars (such as lactose esaccharose), silica, talcum, 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, Second Edition, Dorland Books, Caldwell, New Jersey.

Liquid diluents include, for example, water, N, N-dimethylalkamides (such as N, N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (such as N-methylpyrrolidinone), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (such as white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, triacetin, aromatic hydrocarbons, dearomatized alkenates, alkylbenzenes 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 isobornyl, other esters such as alkylated lactate esters, dibasic esters and γ-butyrolactone, and alcohols, which may be linear, branched, saturated or unsaturated, such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol, 2-ethyl hexanol, n-octanol, decanol, alcoholsodecyl, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleic alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzyl alcohol. Liquid diluents also include glycerol saturated and unsaturated fatty acid esters (typically C6-C22), such as plant seed fruit oils (e.g., olive, castor, flax, sesame, corn, peanut, sunflower, grape seed, turmeric, cottonseed, soybean, rapeseed, coconut and palm kernel), fats from animal sources (such as beef tallow, pork tallow, lard, cod liver oil, fish oil) and mixtures thereof. Liquid diluents also include alkylated fatty acids (such as methylated, ethylated and butylated), wherein the fatty acids may be obtained by glycerol hydride esters from plant and animal sources and may be purified by distillation. Liquid-typical diluents are described in Marsden, Solvents Guide, Second Edition, Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely eWood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. Solid and liquid compositions according to the present invention often include one or more surfactants. When added to a liquid, surfactants (also known as "surface active agents") generally modify, more often reducing surface tension of the liquid. Depending on the nature of the ellipophilic hydrophilic groups in a surfactant molecule, surfactants may be useful as wetting, dispersing, emulsifying or defoaming agents.

Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful for the compositions herein include, but are not limited to: alkoxylated alcohols such as alkoxylated alcohols based on natural and synthetic alcohols (which may be linear or branched) and prepared from alcohols and ethylene oxide, propylene oxide butylene oxide or mixtures thereof; ethoxylated amine, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides, such as ethoxylated soybean, castor oil and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dodecyl phenol ethoxylated dinonyl ethoxylates (prepared from phenols and ethylene oxide, 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 depropylene oxide; ethoxylated fatty acids; ethoxylated fatty oils and esters; ethoxylated methyl esters; ethoxylated triphenylphenol (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof) fatty acid esters, glycerol esters, lanolin-based esters, polyethoxylated esters such as sorbitanpolyethoxylated fatty acid esters, polyethoxylated sorbitol fatty acid and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants, such as random copolymers, block copolymers, alkylated pegylated resins (polyethylene glycol), graft or comb polymers and starry polymers; polyethylene glycols (pegs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.

Useful anionic surfactants include, but are not limited to: alkylalkyl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; Iignin and lignin derivatives, such as lignosulfonates; maleic or succinic acids or their anhydrides; deolefin sulfonates; phosphate esters such as phosphate alkoxylated alcohol esters, phosphate alkylphenol alkoxylated esters and phosphate estyryl phenol ethoxylated esters; protein based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; ethoxylated alkylphenols sulfonate sulfates; sulfates of alcohols; alcohol ethoxylated sulfates; amine and amide sulfonates such as N, N-alkyl taurates; benzene, cumene, toluene, xylene and dodecyl sulfonates and tridecylbenzenes; condensed naphthalene sulfonates; naphthalene and alkylnaphthalene sulfonates; fractionated petroleum sulfonates; sulfussuccinamates; sulfosuccinates and their derivatives, such as salts of dedialkyl sulfosuccinate.

Useful cationic surfactants include, but are not limited to: ethoxylated amides and amides; amines, such as Î ± -alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, diaminethoxylated and propoxylated amines (prepared from 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 alkyl dimethylamine oxides and bis (2-hydroxyethyl) alkylamine oxides.

Also useful for the compositions of the present are anionic and nonionic detensive mixtures or ecathionic nonionic surfactant mixtures. Nonionic, anionic and cationic surfactants and their recommended uses are described in a series of published references including McCutcheon's Emulsifiers and Detergents, annual US and international issues published by McCutcheon's Division, TheManufacturing Confectioner Publishing Co .; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S.Davidson and B. Milwidsky, Synthetie Detergents, Seventh Edition, John Wiley and Sounds, New York, 1987.

Compositions according to the present invention may also contain additives and formulation aids, known to those skilled in the art as formulation aids (some of which may be considered as also functioning as solid diluents, liquid diluents or surfactants). These additives and formulation aids can control: pH (buffers), foaming during processing (defoamers such as polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), microbial growth in containers (antimicrobials), product freezing (antifreeze), color (pigment dyes / dispersions), washing (film-forming or binding agents), evaporation (evaporation retardants) and other formulation attributes. Film formers include, for example, polyvinyl acetate acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone vinyl acetate copolymer, polyvinyl alcohols, and polyvinyl alcohol copolymers and the like. Examples of additives and formulation aids include those related to McCutcheon's Volume 2: Functional Materials, annual international and US editions published by McCutcheon Division, TheManufacturing Confectioner Publishing Co. and PCT Patent No. WO 03/024222.

The compound of Formula 1 and any other active ingredients are typically incorporated into the compositions herein by dissolving the active ingredient in a solvent or by grinding in a dry or liquid diluent. Solutions, which include emulsifiable concentrates, may be prepared by simply mixing the ingredients. Where the solvent of a liquid composition intended for use as a emulsifiable concentrate is immiscible in water, an emulsifier is typically added to emulsify the solvent containing active medium dilution with water. Active ingredient syrups, with departmental diameters up to 2000 μιτι, can be wet milled using media mills to obtain particles with average diameters of less than 3 μιτι. Aqueous syrups can be made up into terminated suspension concentrates (see, for example, the North Patent American No. 3,060,084) or further processed by spray drying to form water dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the range of 2 to 10 μιτι. Dry powders and powders can be prepared by mixing and usually milling (as in hammer mill or fluid energy mill). Granules and pellets may be prepared by spraying the active material on previously formed granular supersicles or by agglomeration methods. See Browning, Agglomeration, Chemical Engineering, December 1967, p. 147-48, Perry's Chemical Engineer's Handbook, fourth edition, McGraw-HiII New York, 1963, p. Following 8-57, and WO 91/13546. Pellets may be prepared as described in US 4,172,714. Water-dispersible, water-soluble granules may be prepared as taught in US 4,144,050, US 3,920,442, and DE 3,246,493. Tablets may be prepared as taught in US 5,180,587, US 5,232,701 and US 5,208,030. Films may be prepared as taught in GB 2,095,558 and US 3,299,566.

For additional information regarding the deformulation method, see TS Woods, The Formulator's Toolbox - Product Forms for Modern Agriculture in Pesticide Chemistry and Bioscience, The Food-Environment Challenge1 T. Brooks and TR Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, p. 120-133. See also US 3,235,361, Col. 6, line 16 to Col. 7, line 19 and Examples 10 to 41, US 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; US 2,891,855, Col. 3, line 66 to Col. 5, line 17 and Examples 1 4; Klingman, Weed Control as Science, John Wiley and Sons, Inc., New York, 1961, p. 81-96; Hance et al, Weed Control Handbook, eighth edition, Blackwell Scientific Publications, Oxford, 1989; and Developments in Formulation Technology, PJB Publications, Richmond, Great Britain, 2000.

In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers designate compounds in the AaD Index Tables. Without further elaboration, it is believed that those skilled in the art, using the above description, can utilize the present invention to the fullest extent possible. The following Examples should therefore be construed as merely illustrative and not limiting the descriptive report in any way. Percentages are by weight unless otherwise indicated. Example A

High Strength 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

Granules

Compound 16 10.0%

attapulgite granules (low volatility matter, 0.71 / 0.30 mm; North American Standard Sieves No. 25-50) 90.0%

Example D

Extruded Pellets

Compound 18 25.0%

Anhydrous sodium sulfate 10.0%

Crude calcium lignin sulfonate 5.0%

Sodium alkylnaphthalenesulfonate 1.0%

Calcium / Magnesium Bentonite 59.0%

Example E

Emulsifiable Concentrate

Compound 19 10.0% Polyoxyethylene sorbitol hexoleate 20.0%

C6-C10 fatty acid methyl ester 70.0%

Example F

Microemulsion

Compound 2 5.0%

Polyvinylpyrrolidone and acetate copolymer

30.0% vinyl

Alkylpolyglycoside 30.0%

Monooleatodeglyceryl 15.0%

Water 20.0%

Example G

Seed Treatment

Compound 18 20.00%

Polyvinylpyrrolidone and vinyl acetate copolymer 5.00%

Montana Acid Wax 5.00%

Calcium Lignosulfonate 1.00%

Polyoxyethylene block copolymers and

polyoxypropylene 1.00% Stearyl alcohol (POE 20) 2.00%

Polyorganosilane 0.20%

Red dye 0.05%

Water 65.75%

Example H

Fertilizer stick

Compound 19 2.5%

Pyrrolidone and styrene copolymer 4.8%

Triestyryl phenyl 16-ethoxylate 2.3%

Talc 0.8% <table> table see original document page 91 </column> </row> <table>

The compounds of the present invention will exhibit activity against a broad spectrum of invertebrate pests. These pests include invertebrates that inhabit a variety of environments, such as leafy plants, roots, soil, harvested crops or other food, building structures or animal integuments. Such pests include, for example, feeding on foliage invertebrates (including leaves, stems, flowers and fruits), seeds, wood, textile fibers or blood or animal tissues to cause injury or damage to, for example, growing or stored harvests , forests, greenhouse crops, ornamental plants, nursery crops, stored food or fiber products or houses or other structures or their contents, or be harmful to animal or 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 compounds and compositions herein are therefore useful agronomically for the protection of field crops against phytophagous invertebrate pests, as well as non-agronomically for the protection of other horticultural crops and plants against phytophagous invertebrate pests. This includes the protection of crops and other (ie agronomic and non-agronomic) plants that contain genetic material introduced by genetic (ie transgenic) engineering or modified by demutagenesis to provide advantageous characteristics. Examples of these characteristics include herbicide tolerance, resistance to phytophagous pests (such as insects, mites, aphids, spiders, nematodes, snails, plant fungospatogens, bacteria and viruses), improved plant growth, increased tolerance to adverse crop conditions such as high temperatures or low, high or low soil moisture and high salinity, increased flower or fruit deformation, higher crop yields, faster maturation, better quality and / or nutritional value of the harvested product or better process or storage properties of harvested products. Plantastransgenic plants can be modified to express various characteristics.Examples of plants that have characteristics provided by genetic engineering or mutagenesis include varieties of corn, cotton, soybeans, and potatoes that express Bacillus thuringiensis insecticide toxin such as YIELD GARD®, KNOCKOUT®, STARLINK® , BOLLGARD®, NuCOTN® and NEWLEAF® and herbicide tolerant varieties of maize, cotton, soybeans and ecolza such as ROUNDUP READY®, LIBERTY LINK®, IMI (S) 1 STS® eCLEARFIELD® as well as / V- acetyltransferase (GAT) to provide resistance to glyphosate herbicide, or crops containing the geneHRA that provide resistance to herbicides that inhibit acetolactate synthase (ALS). The present compounds and compositions may interact in an energetic manner with traits introduced by genetic engineering or modified by mutagenesis in order to increase the phenotypic expression or efficacy of the characteristics or increase the effectiveness of invertebrate control of the present compounds and compositions. , the compounds and compositions herein may interact synergistically with phenotypic expression of proteins or other natural products toxic to invertebrate pests to provide greater than additive control of these pests.

Compositions according to the present invention may also optionally comprise plant nutrients such as a fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium, magnesium, iron, copper, boron, manganese, zinc and molybdenum. Deserve to be aware of compositions comprising at least one fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium and magnesium. Compositions according to the present invention which further comprise at least one plant nutrient may be in the form of liquid or solid. Note solid formulations in the form of granules, small sticks or tablets. Solid formulations comprising a fertilizer composition may be prepared by mixing the composition or composition according to the present invention with fertilizer composition together with formulation ingredients and then preparing the formulation by methods such as granulation or extrusion. Alternatively, solid formulations may be prepared by spraying a solution or suspect of a compound or composition according to the present invention into a volatile solvent over a previously prepared fertilizer composition such as stable sized mixtures such as granules, small sticks or lozenges. and evaporation of the solvent thereafter.

Non-agronomic uses indicate control of invertebrate pests in different areas of crop fields. Non-agronomic uses of the present compounds and compositions include the control of invertebrate pests in grains, cereals and other stored foods and textile products such as clothing and rugs. Non-agronomic uses of the present compounds and compositions also include the control of invertebrate pests on ornamental plants, forests, gardens, along roadside and rail and on-road traffic rights such as grass fields, golf courses and pastures. Nonagronomic uses of the present compounds and compositions also include the control of invertebrate pests in houses and other constructions that may be occupied by humans and / or pets, farm, ranch, zoo or others. Non-agronomic uses of the compounds and compositions herein also include pest control such as termites that can damage wood or other structural materials used in constructions.

Non-agronomic uses of the present compounds and compositions also include the protection of human and animal health through the control of invertebrate pests that are parasitic or transmit infectious diseases. Control of animal parasites includes control of external parasites that are parasitic to the surface of the host animal's body (such as shoulders, armpits, abdomen, inner thighs) and internal parasites that are parasitic to the inner side of the host animal's body ( such as stomach, intestines, lungs, veins, under the skin, lymphatic tissue). Diseases that transmit disease or external parasites include, for example, chic, ticks, lice, mosquitoes, flies, scabies, mites and fleas. Internal parasites include parasites cardiac compounds, hookworms and helminths. Compounds and compositions according to the present invention are suitable for systemic and / or non-systemic control of infestations or parasite infections in animals. Compounds and compositions according to the present invention are particularly suitable for combating disease-transmitting or external parasitic pests. The compounds and compositions according to the present invention are suitable for combating parasites infesting farm animals such as oxen, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese and bees; domestic animals and pets such as dogs, cats, pet birds and aquarium fish; as well as so-called experimental animals such as hamsters, guinea pigs, mice and mice. By combating these parasites, fatalities and reduced performance (in terms of meat, milk, wool, skin, eggs, honey, etc.) are reduced, so that application of a composition comprising a compound according to the present invention allows mating. of simpler and economical animals.

Examples of agronomic or nonagronomic invertebrate pests include eggs, larvae and adults of the order lepidoptera, such as cereal caterpillars, gramiolas, geometrideal larvae, and noctuid family heliotins (eg, pink stem borer (Sesamia inferens, Walker), corn stalks (Sesamia nonagrioides, Lefebvre), southern lizard (Spodoptera eridania, Cramer), autumn cereals caterpillar (Spodoptera fugiperda, JE Smith), sugar beet caterpillar (Spodoptera exigua, Hübner), cotton leaf caterpillar (Spodoptera littoralis) , Boisduval), Yellow-list caterpillar (Spodoptera ornithogalli, Guenée), Cerebral black caterpillar (Agrotis ipsilon, Hufnagel), Velvet Grain Cricket (Anticarsiagemmataiis, Hübner), Green Fruit Worm (Lithophane antennata, Walker), Cabbage Caterpillar (Barathra brassicae, Linnaeus), Soybean Gramiola (, Pseudoplusia includens, Walker), Cabbage Gramiola (Trichoplusia ni, Hübner), Smoke Buds Larva (Heliothis virescens, Fabricius)); weevils, beetles, webworms, conifer worms, cabbage worms and insects of the pyralid family (eg European corn borer (Ostrinia nubilalis, Hübner), navel orange worm (Amyelois transitella, Walker), maize rootwebs (Crambus caliginosellus, Clemens), grassworm worms (pyralids: Crambinae) such as wormgrass (Herpetogramma licarsisalis, Walker)), sugarcane stem borer (Chilo infuscatellus, Snellen), small borer (Neoleucinodeselegantalis, Guenée), Green cigarette (Cnaphalocerus medinalis), Grape moth (, Desmia funeralis, Hübner), Melon worm (Diaphania nitidalis), Cabbage caterpillar (Helluala hydralis, Guenée), Yellow stalk borer ( .Scirpophaga incertulas, Walker), Early Sprouts Drill (Scirpophagainfuscatellus, Snellen), White Stems Drill (Scirpophaga innotata, Walker), Upper Sprouts Drill (Donate Drill) black-headed roz (Chilo polychrysus, Meyrick), cabbage bunch cricket (Croeidolomia binotalis, English)); leafworm, budworm, seedworm and fruitworm of the family of the tortricids (eg, small moth (Cydia pomonella, Linnaeus), grape moth (Endopiza viteana, Clemens), eastern fruit moth (Grapholita molesta, Busck ) citrus false apple moth (Cryptophlebia leueotreta, Meyrick), citrus borer (Eedylotopha aurantiana, Lima), red stripe moth (, Argyrotaenia velutinana, Walker), oblique strip moth (Choristoneurarosaeean, Harris moth) small (Epiphyas postvittana, Walker), European grape moth (Eupoecilia ambiguella, Hübner), apple button moth (Pandemis pyrusana, Kearfott), omnivorous moth (Platynotastultana, Walsingham), striped fruit tree moth (Pandemiseerasana, Hübner) apple brown (Pandemis heparana, Denis &Schiffermüller)); and many other economically important lepidopterans (eg, cruciferous moth (Plutella xylostella, Linnaeus), cotton pink caterpillar (Peetinophora gossypiella, Saunders), ocheria (Lymantria disparis, Linnaeus), peach fruit borer (Carposina brisalis, niponens), peach twigs (Anarsia lineatella, Zeller), tuber dabatata larvae (Phthorimaea opereulella, Zeller), spotted teniform caterpillar (Lithocolletis blaneardella, Fabricius), Asian apple caterpillar (Lithocolletisringoniella, Matsumura), rice cigarette holder (Edodeafala euudala) ), lizard apples (Leueoptera seitella, Zeller)); eggs, nymphs and adults of the order of the blatods, including cockroaches from the blatelid and blatid families (eg Eastern cockroach (Blatta oríentalis, Linnaeus), Asian cockroach (Blatellaasahinai, Mizukubo), German cockroach (Blatella germaniea, Linnaeus), Brown cockroach (Supella longipalpa, Fabricius), American cockroach (Periplanetaamericana, Linnaeus), Brown cockroach (Periplaneta brunnea, Burmeister), Madeira cockroach (Leucophaea maderae, Fabricius)), Opaque brown cockroach (Periplaneta fuliginosa, Service), Australian cockroach (Periplaneta australasiae) , Fabr.), Lobster cockroach (Nauphoeta cinerea, Olivier) and soft cockroach (Symplocepallens, Stephens)); eggs, leaf-feeding, fruit-feeding, root-feeding, seed-feeding larvae, vesicular tissue-feeding, and adult of the coleopteran order, including weevils of the antribid families, ecurculionid bruquids (eg cotton weevil (Anthonomus grandis, Boheman), rice weevil (Lissorhoptrus oryzophilus, Kuschel), cereal weevil (Sitophilus granarius, Linnaeus), rice weevil (Sitophilus oryzae, Linnaeus)); annual blue grass weevil (Listronotusmaculicollis, Dietz), blue grass weevil (Sphenophorus parvulus, Gyllenhal), hunter weevil (Sphenophorus venatus vestitus), DENVER weevil (Sphenophorus cicatristriatus, Fahraeus)); flea beetles, cucumber beetles, root larvae, leaf beetles, potato leaf beetles of the Chrysomelid family (for example, Colorado dabatata beetle (Leptinotarsa decemlineata, Say), western daylike larvae (Diabrotica virgifera virgifera, LeConte)); scarab beetles and other beetles of the scarab family (eg Japanese beetle (Popilliajaponica, Newman), eastern beetle (Anomal orientalis, Waterhouse, Exomala orientalis (Waterhouse), Baraud), Northern masked beetle (Cyclocephala borealis, Arrow) (Cyclocephalaimmaeulata, Olivier, or C. lurida, Bland), Dung Beetle and White Larva (Aphodius spp), Black Blue Grass Larva (Ataenius spretulus, Haldeman), June Green Beetle (Cotinis nitida, Linnaeus), Asian garden (Maladera castanea, Arrow), May and June beetles (Phyllophaga spp) and European beetle (Rhizotrogus majalis, Razoumowsky)); dostapete beetles of the dermestid family; wire larvae of the elaterid family;

beetles of bark beetles of the family of scolithids and beetle beetles of the tenebrionid family. In addition, non-agronomic agronomic and pests include: eggs, adults, and larvae of the order of the dermápteros, including forficulid family (ie, European (Forficula auricularia, Linnaeus), black (Chelisoches morio, Fabricius)); eggs, immatures, adults and nymphs of the order of the hemiptera and homopterans, such as beetles of the myrid family, cicada family cicadas, leaf locusts (eg Empoascaspp.), cicadidae family, bed beetles (eg Cimexlectularius, Linnaeus) of the scimicid family, grasshopper of the family of the fulgoroid and delfacid family, grasshopper of the member of the brachid family, psyllid family psyllid, aphid family whitefly, aphid family phylloxera, phylloxerid family phylloxera pseudococcid family flours, hand-spanners of coccid, diaspidid, and margarodid families, tingid family lace beetles, stinkpentomid family stink beetles, hairy beetle (eg hairy hairy beetle (Blissus Ieucopterus hirtus, Montandon ) and Southern Bark Beetle (Blissusinsularis, Barber)) and other ligeid family seed beetles, cercopid family saliva beetles, choreid family pumpkin beetles, red beetles, and pyrochorid family cotton beetles. Also included are eggs, larvae, nymphs and adults of the order mites (mites) such as spider mites and red tetraniquid mites (eg European red mite (Panonychus ulmi, Koch), two-spotted spider mite (Tetranychus urticae, Koch), McDanieI mite (Tetranychus mcdanieli, McGregor)), flatfish mites of the dostenuipalpidae family (eg citrus flat mite (Brevipalpus lewisi, McGregor)), rust and bud mites of the eriophid-eating family, other leaf-eating mites and mites important for human and animal health, ie epidermoptid family dust mites, demodicide family defolicle mites, ixodid family cereal mites, known as hard ticks (eg deer tick ( Ixodes scapularis, Say), Australian paralysis tick (Ixodes holocyclus, Neumann), American dog tick (Dermacen tor variabilis, Say), solitary star tick (Amblyomma amerícanum, Linnaeus) and argasid family ticks, commonly known as soft ticks (such as febrerecurrent tick (Ornithodoros turicata), common bird tick (Argasradiatus)); crust and itch mites from families of psoroptids, piemotids and sarcoptids; eggs, adults and immatures of the order of the orthoptera, including grasshoppers, yocustas and crickets (eg migratory locusts (eg Melanoplus sanguinipes, Fabricius, M. differentialis, Thomas), american locusts (eg Schistocerca americana, Drury), Desert Grasshopper (Schistocerea gregaría, Forskal), Migratory Grasshopper (, Migratory Loeusta, Linnaeus), Shrub Grasshopper (Zonoeerus spp), House Grouse (Aeheta domestieus, Linnaeus), Mole Crickets (such as grilotoupeus fulseusulea) and Southern Mole Cricket (Seapteriseus borellii, Giglio-Tos)), adult, immature eggs of the order Diptera, including caterpillars (eg Liriomyza spp as a serpentine caterpillar (Liriomyza sativae, Blanchard)), gnats, flies fruits (tephritids), fries flies (eg Oseinella frit, Linnaeus), soil fly larvae, houseflies (eg Museadomestica, Linnaeus), smaller houseflies (po (eg Fanniacanicularis, Linnaeus, F. femoralis, Stein), Stable flies (eg Stomoxys calcitrans, Linnaeus), Face flies, Horn flies, Blow flies (eg Chrysomya spp, Phormia spp), and other pests; horse flies (eg Tabanus spp), berne flies (eg Gastrophilus spp, Oestrus spp), cattle caterpillars (eg Hypoderma spp), deer flies (eg Chrysops spp), lice (eg , Meiophagus ovinus, Linnaeus) and other brachycerus, mosquitoes (eg, Aedes spp, Anopheies spp, Cuiex spp), blackflies (eg Prosimulium spp, Simulium spp), sandflies, sand flies, mushroom flies and other nematocers ; dostisanopteran eggs, immatures and adults, including onion tripods (Thrips tabaci, Lindeman), flower tripods (Frankliniella spp) and other leaf-feeding tripods; insect pests of the order Hymenoptera, including ants of the family of the formicides, including the Florida Carpenter Ant (Camponotusfloridanus, Buckley), Red Carpenter Ant (Camponotus ferrugineus, Fabricius), Black Carpenter Ant (Camponotus pennsylvanicus, De Geer) (Technomyrmex albipes fr. Smith), large-headed ant (Pheidole sp), phantom ant (Tapinoma melanocephalum, Fabricius); pharaoh ant (Monomorium pharaonis, Linnaeus), red-bellied ant (Wasmannia auropunctata, Roger), red ant (Solenopsisgeminata, Fabricius), red imported red ant (Solenopsis invicta, Buren), Argentine ant (Iridomyrmex humiliga, Mayr) (Paratrechina longicornis, Latreille), Pavement ant (Tetramoriumcaespitum, Linnaeus), Cornfield ant (Lasius alienus, Forster) and odorous domestic ant (Tapinoma sessile, Say). Other hymenopterans include bees (including carpenter bees), hornets, hornets, wasps and saw flies (Neodiprion spp; Cephus spp); insect pests of the isopteran disorder, including termites of the termicid families (such as Macrotermes sp, Odontotermes obesus, Rambur), calotermicides (such as Cryptotermes sp) and rhinotermicides (such as Reticulitermes sp, Coptotermessp, Heterotermes tenuis, Hagen) , Kollar), Western underground termite (Reticulitermes hesperus, Banks), Taiwan underground termite (Coptotermes formosanus, Shiraki), West Indian drywood termite (Ineisitermes immigrans, Snyder), Powder termite (Cryptotermes brevis, Walker), termite drywood (Ineisitermes snyderi, Light), southeastern subterranean termite (Retieulitermes virginieus, Banks), western drywood termite (Ineisitermes minor, Hagen), tree termites, such as Nasutitermes sp and other economically important termites; pest insects of the order of tisanúreos, such as book moths (Lepismasaeeharina, Linnaeus) and earwigs (Thermobia domestica, Packard); insect pests of the order malophagus, including human louse (Pedieulus humanuseapitis, De Geer), body louse (Pedieulus humanus, Linnaeus), lice (Menaeanthus stramineus, Nitszch), dog louse (Triehodeetescanis, De Geer) Goniocotes gallinae, De Geer), Dander louse (Bovicola ovis, Schrank), Short-nosed louse (Haematopinuseurysternus, Nitzsch), Long-nosed louse (Linognathus vituli, Linnaeus) and other sucking and biting parasitic lice that attack oh animals; insect pests of the order Siphonoptera, including eastern rat blight (Xenopsylla cheopis, Rothschild), cat flea (Ctenocephalides felis, Bouche), dog flea (Ctenocephalides canis, Curtis), bird flea (Ceratophyllus gallinae, Schrank) chickens (Echidnophaga gallinacea, Westwood), human fleas (Pulex irritans, Linnaeus) and other fleas that afflict mammals and birds. Covered arthropod pests include: spiders of the order of the spiders, such as the brown recluse spider (Loxosceles reclusa, Gertsch and Mulaik) and the black spider (Latrodectus mactans, Fabricius) and scutigeromorphic centipedes, such as the domestic centipede (Scutigera coleopeus). ). The compounds according to the present invention also exhibit activity on members of the nematode, cestode, trematoid and acanthocephalus classes, including economically important members of the orders of strongylides, ascaridides, oxyurides, rhabditids, spirurides and enolides, such as, but not limited to economically important agricultural pests (ie root knot nematodes Meloidogyne, lesions of the genus Pratylenchus, thick root nematodes of the genus Trichodorus etc.) and human and animal health pests (ie all worms, solitary and worms) , such as Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofilariaimmitis Leidy in dogs, Anoplocephala perfoliata in horses, Fasciola hepaticaLinnaeus in ruminants etc.).

The compounds according to the present invention exhibit particularly high activity against lepidopteran pests (eg, Alabama argillaeea Hübner (cottonworm), Arehipsargyrospila Walker, A. rosanaLinnaeus (European leafworm). ) and other species of Arehips, Chilosupressalis Walker (rice stalk borer), Cnaphalocrosis medinalisGuenée (rice leaf caterpillar), Crambus ealiginosellus Clemens (maize root worm), Crambus teterrellus Zincken (field grassworm) , Cydia pomonella Linnaeus (fruit moth), Earias insulanaBoisduval (spiny moth larva), Earias vittella Fabricius (spotted moth larva), Helieoverpa armigera Hübner (Helieoverpa zea Boddie (Helipot larvae), Helieoverpa zea Boddie (smoke bud worm), Herpetogramma liearsisalisWalker (lawn web worm), Lobesia botrana Den is and Schiffermüller (grape moth), Pectinophora gossypiella Saunders (pink moth larva), Phyllocnistis citrella Stainton (citrus caterpillar), Pieris brassicae Linnaeus (large white butterfly), Pieris rapae Linnaeus (small white butterfly), Plutella xylostella Linyl (Moth of the cruciferous), Spodoptera exigua Hübner (beet caterpillar), Spodoptera Iitura Fabricius (smoke gramiola, lizards bunches), Spodoptera frugiperda JE Smith (autumn caterpillar), Trichoplusia ni Hübner (cabbage larva) and Tuta Absolute Meyrick (lagoon). dotomate)).

The compounds according to the present invention also exhibit significant activity on members of the order of homopterans, including: Acyrthosiphon pisum Harris (pea aphid), Aphis craccivoraKoch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi DeGeer (apple aphid), Aphis spiraecola Patch (top aphid), Aulacorthum solani Kaltenbach (foxglove aphid), Chaetosiphon fragaefoliiCockerell (Strawberry aphid), noxia Kurdjumov / Mordvilko (Russian dotrigo aphid), Dysaphis plantaginea Paaserini (pink apple aphid), Eriosoma Ianigerum Hausmann (woolly apple aphid), Hyalopterus pruniGeoffroy (Farinaceous plum aphid), Lipaphis erysimi donophidridi walkerbach (cereal aphid), Maerosiphumeuphorbiae Thomas (potato aphid), Myzus persieae Sulzer (peach dabatata aphid, aphid aphid) green peach), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigus spp. (root aphids and gall aphids), Rhopalosiphum maidis Fitch (corn leaf aphid), Rhopalosiphum padiLinnaeus (bird cherry aphid), Sehizaphis graminum Rondani (green beetle), Sitobion avenae Fabricius (English cereal aphid) , Therioaphis maeulata Buckton (spotted alfalfa aphid), Fonscolombe Toxoptera aurantiiBoyer (citrus black aphid) and Kirkaldy citrus toxoptera (brown aphid); Adelges spp. (adelgids); Phylloxera devastatríxPergande (Pecan Phylloxera), Bemisia tabaci Gennadius (Smoke Whitefly, Sweetpotato Whitefly), Bemisia argentifolii Bellows and Perring (Silver Leaf Whitefly), Dialeurodes citri Ashmead (Citrus Whitefly Fly) and Trialeurodes vaporariorum Westwood (Greenhouse Whitefly); Empoasca fabae Harris (Potato Leaf Grasshopper), Laodelphax striatellusFallen (Lesser Brown Plant Grasshopper), Macrolestes quadrilineatusForbes (Aster Leaf Grasshopper), Nephotettix cinticeps Uhler (Leaf Grasshopper Nepigret), Nephotettix cinticeps Stál (rice leaf grasshopper), Nilaparvata Iugens Stál (brown plant grasshopper), Peregrinus maidisAshmead (corn plant grasshopper), Sogatella furcifera Horvath (White-backed plant grasshopper), Sogatodes orizicola Muir (rice delfacid), Typhlocyba pomaria McAtee (White Apple Leaf Grasshopper), Erythroneoura spp. (locusts of grape leaves); Magicidada septendecim Linnaeus (seasonal cicada); Icerya purchasiMaskell (cotton palm), Quadraspidiotus perniciosus Comstock (San Jose palm), Planococcus citri Risso (Dairy Farinaceous Beetle), Pseudoeoceus spp. (another farinaceous beetle complex), Cacopsylla pyrieola Foerster (Pear Psila), Trioza diospyri Ashmead (Diospiro Psila).

The compounds according to the present invention also have activity on members of the order of the hemiptera, which include: Aerosternum hilare Say (foul green beetle), Anasa tristis De Geer (pumpkin beetle), Blissus leueopterus Say (besouropercevejo), Cimex Ieetularius Linnaeus (Bed Beetle), Corythuea gossypiiFabricius (Cotton Lace Beetle), Cyrtopeltis Modest Distant (Tomato Beetle), Dysdereus suturellus Herrich-Schaffer (Cotton Beetle), Euchistus servus Say (Euchiusotus variol) de Beauvois (stink beetle), Graptosthetusspp. (seed beetle complex), Leptoglossus corculus Say (leaf pine seed beetle), Lygus Iineolaris Palisot deBeauvois (spotted plant beetle), Nezara viridula Linnaeus (southern stink beetle), Oebalus pugnax Fabricius bad smelling rice), Oncopeltus fasciatus Dallas (large milky beetle), Pseudatomoscelis seriatus Reuter (cottonseed flea). Other compound-controlled insect orders according to the present invention include tisanoptera (eg, Frankliniella occidentalisPergande (western flower tripod), Scirthothrips citri Moulton (oscillary tripod), Sericothrips variabilis Beach (soybean tripod) and Thrips tabaci Lindeman (soybean tripod). onion)); and the order of beetles (eg Leptinotarsadeeemlineata Say (Colorado potato beetle), Epilaehna varivestisMulsant (Mexican bean beetle) and wire larvae of the genus Agriotes, Athous or Limonius).

It should be noted that some contemporary classification systems place the homoptera as a suborder of the order of the heteroptera.

Note the use of compounds according to the present invention for the control of cruciferous moths (Plutella xylostella). Note the use of compounds according to the present invention to control autumn cereal caterpillar (Spodoptera frugiperda). Note the use of compounds according to the present invention for the control of the western flower tripod (Frankliniella occidentalis). Note the use of compounds according to the present invention for the control of potato grasshopper (Empoasca fabae). The use of compounds according to the present invention for the control of the melon and cotton (Aphis gossypii) deserves observation. The use of the present invention to control green peach aphid (Myzus persicae) is of note.

The compounds of the present invention may also be mixed with one or more different biologically active agents or compounds, which include insecticides, fungicides, nematicides, bactericides, acaricides, herbicides, growth regulators such as rooting stimulants, chemoesterilizers, semiochemicals, repellents, attractants. , pheromones, dietary stimulants, other biologically active compounds or entomopathogenic viruses, fungi or bacteria to form a multi-component pesticide, providing an even broader spectrum of agronomic and non-agronomic utility. Accordingly, the present invention also relates to a composition comprising a biologically effective amount of a compound of Formula 1, its N-oxide or salt and an effective amount of at least one additional biologically active agent or compound and may further comprise at least one of the surfactants. , solid diluents or liquid diluents. For mixtures according to the present invention, the other biologically active agents or compounds may be formulated together with the compounds of the present, including the compounds of Formula 1, to form a premix, or the other biologically active agents or compounds may be formulated separately from the compounds of the present invention. present, including the compounds of Formula 1 and the two formulations combined prior to application (as in a spray tank) or alternatively applied successively.

Other biologically active agents or compounds useful in the compositions according to the present invention may be selected from invertebrate pest control agents that have a different mode of action or a different chemical class, including lactonasmacrocyclics, neonicotinoids, octopamine receptor binders, ryanodine receptors , ecdisone agonists, disodium channel modulators, chitin synthesis inhibitors, nereisotoxin analogs, mitochondrial electron transport inhibitors, cholinesterase inhibitors, decyclodiene insecticides, exudate inhibitors, GABA (γ-aminobut acid) -regulated chloride channel blockers , juvenile hormone mimics, lipid biosynthesis inhibitors, and biological agents including nucleopoliedrovirus (NPV) 1 members of Bacillus thuringiensis, encapsulated delta-endotoxins of Bacillus thuringiensis; and other naturally occurring or genetically modified insecticidal viruses.

Additional biologically active agents or compounds selected from the insecticides of the group consisting of pyrethroids, carbamates, neonicotinoids, sodioneuronal channel blockers, insecticidal macrocyclic Iactones, γ-aminobutyric acid antagonists, urea insecticides and juvenile hormone mimics deserve to be noted. thuringiensis, a Bacillusthuringiensis delta-endotoxin and a naturally occurring or genetically modified insecticide.

Examples of such biologically active agents or compounds with which the compounds according to the present invention may be formulated are: insecticides such as abamectin, acefate, acetamiprid, acetoprol, amidoflumet (S-1955), avermectin, azadiractin, azinfos-methyl, bifenthazine, bifenazate , bistrifluron, buprofezin, carbofuran, cartap, chlorfenapyr, chlororfuazuron, chlorantraniliprol (DPX-E2Y45), chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidine, cyflumruth, beta-cyrothruthin, beta-cyrothruthin, beta-cyrothruthin, cyromazine, deltamethrin, diafentiuron, diazinon, dieldrin, diflubenzuron, dimeflutrin, dimethoate, dinotefuran, diophenolan, emamectin, endosulfan, etiprol, fenotiocarb, phenoxycarb, fenoxycarb, fenpropatrin, fluvulaminate, fluvinamide UR-50701), flufenoxuron, phonophos, halofenozide, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, isofenphos, lufenuron, m alation, metaflumizone, metaldehyde, metamidophos, metidation, methomyl, metoprene, methoxychlor, metofluthrin, monocrotophos, methoxyphenozide, monocrotophos, nitenpyram, nitiazine, novaluron, noviflumuron (XDE-007), oxamalone paratonin, , fosmet, phosphamidon, pirimicarb, profenophos, profluthrin, protrifenbuta, pimetrozine, pirafluprol, pyrethrin, pyridalyl, pyrifluquinazon, pyriprole, pyriproxifen, rotenone, rianodine, spinin, spinosad, spirodiclofen, spiromesefen tiben, sulphenefen, tb tefluthrin, terbufos, tetrachlorvinphos, tiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpirad, tralometrine, triazamate, trichlorphon and triflumuron; fungicides, such as acibenzolar, aldimorf, amisulbrom, azaconazole, azoxystrobin, benalaxyl, benomyl, bentiavalicarb, bentiavalicarb-isopropyl, binomial, biphenyl, bitertanol, blasticidin-S, Bordeaux mixture (bipasomal birbucidum, bifalidum, sulphenazole, , butiobate, carboxin, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonyl, clozolinate, clotrimazole, copper oxychloride, copper salts such as copper sulfate and copper hydroxide, ciazofamid, ciflunamid, cimoxanil, ciproconazole, dicyclidyl , diclomezine, dichloran, dietofencarb, diphenoconazole, dimetomorph, dimoxystrobin, diniconazole, diniconazole-M, dinocap, dicostrobin, dithianon, dodemorf, dodine, econazole, ethaconazole, edifenphos, etaboxam, phenidimidazole, ethadoxazol, ethadoxazole , fencaramid, fenfuram, fenhexamide, fenoxanil, fenpiclonil, fenpropidine, fenpropimorf, fentin acetate, fentin hydroxide, ferbam, ferfurazo act, ferinzone, fluazinam, fludioxonil, flumetover, fluopicolide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl aluminum, fuberidazole, furalaxil, furametapyr, hexaconazole, himexazole, imazicarbazole, ixazalazole, ipconazole, iprobenfos, iprodione, iprovalicarb, isoconazole, isoprothiolane, casugamycin, cresoxim-methyl, mancozeb, mandipropamid, maneb, mapanipyrine, mefenoxam, mepronil, metallaxyl, metconazole, metasulfocarb, metiram, metominostrobin / mepanitrinone, mepanitrinone neo-asozine (ferric methanarsonate), nuarimol, octylinone, ofurace, orisastrobin, oxadixil, oxolinic acid, oxpoconazole, oxicarboxin, paclobutrazol, penconazole, pencicuron, pentiopirad, perforate acid, phthazidazole, picalidone, procalidone , propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazid, protioconazole, piraclo strobin, priazophos, pyrifenox, pyrimetanil, pyrifenox, pyrolnitrin, pyrokylon, quinconazole, quinoxifen, quintozene, siltiofam, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, tecrazene, keyboardophthalam, technazene, tetraconazole, thetraconazole, tetraconazole tiram, thiadinyl, tolclofos-methyl, tolifluanid, triadimephon, triadimenol, triarimol, triazoxide, tridemorf, trimorfamide, tricyclazole, trifloxystrobin, triforine, triticonazole, uniconazole, validamycin, vinclozoline, zineb, ziram and zoxamide; nematicides such as aldicarb, imicyaphos, oxamyl efenamiphos; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzylate, cyhexatin, dicofol, dienochlor, ethoxazole, phenazaquin, fenbutatin oxide, fenpropatrin, fenpyroximate, hexithiazox, propargite, pyridaben and tebufenpyrad; and biological agents including pathogenic bacteria, such as Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki and the encapsulated Bacillus thuringiensis delta-endotoxins (such as Cellcap, MPV1 MPVII); pathogenic fungi, such as green muscardine fungus; and pathogenic viruses including bacilloviruses, nucleopoliedvirus (NPV) such as Helicoverpa zea nucleopoliedvirus (HzNPV) 1 Anagrapha falcifera nucleopoliedrovirus (AfNPV); and granulose virus (GV) such as Cydia pomonella granular virus (CpGV).

The compounds according to the present invention and their compositions may be applied to genetically transformed plants to express toxic proteins for invertebrate pests (such as Bacillus thuringiensis delta-endotoxins). The effect of exogenously applied invertebrate control compounds according to the present invention may be synergistic with the expressed toxin proteins. General references for these agricultural protectors (ie insecticides, fungicides, nematicides, acaricides, herbicides and biological agents) include The Pesticide Manual, 13th edition, CDS Tomlin, ed., British Crop Protection Council, Farnham1 Surrey, United Kingdom, 2003, and TheBioPesticide Manual, second edition, LG Copping, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2001.

A composition according to the present invention in which at least one additional biologically active agent or compound is selected from the group consisting of abamectin, acephate, acetamiprid, acetoprol, aldicarb, amidoflumet, amitraz, avermectin, azadiractin, azinphos-methyl, deserves observation. bifenthrin, bifenazate, bistrifluron, buprofezin, carbofuran, cartap, chinomethionat, chlorfenapyr, chlorfluazuron, chlorantraniliprol, chlorpyrifos, chlorpyrifos-methyl, chlorobenzylate, chromaphenzid, cyphlumethrin, ciflumethrin, cifluthrin, cifluthrin cyhexatin, cypermethrin, cyromazine, deltamethrin, diafentiuron, diazinon, dicofol, dieldrin, dienochlor, diflubenzuron, dimeflutrin, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, sphenvarelate, phenazolate, phenazolate, phenazolate, phenolate fenpropatrin, fenpyroximate, fenvarelate, fipronil, flonicamid, flubendiamide, flucitrinate, tau-fluvalinate, flufenerim, flufenoxuron, phonophos, halofenozide, hexaflumuron, hexithiazox, hydramethylnon, imiciaphos, imidacloprid, indoxacarb, isophenphos, lufenuron, malation, metaflumizone, methoidophenophenate, methamidophosphate, methamidophosphonate nitenpiram, nitiazine, novaluron, noviflumuron, oxamyl, paration, paration-methyl, permethrin, forate, fosalone, fosmet, phosphamidon, pirimicarb, profenophos, profluthrin, propargite, protrifenbute, pimetrozine, pirafluprol, pyrethrin, pyrethyridine, pyrethrin pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spiridiclofen, spiromesifen, spirotetramat, sulprofos, tebufenozide, tebufenpirad, teflubenzuron, teflutrin, tetrachlorvinphos, tiacloprid, tiamethoxytriophonate, thiatrophenolate Bacillus thuringiensissubsp. Aizawai, Bacillus thuringiensis subsp. kurstaki, nucleopoliedrovirus, Bacillus thuringiensis encapsulated delta-endotoxin, bacillovirus, entomopathogenic bacteria, entomopathogenic viruses and entomopathogenic fungi.

Of particular note is a composition according to the present invention wherein at least one additional biologically active agent or compound is selected from the group consisting of abamectin, acetate, acetamiprid, acetoprol, amidoflumet (S-1955), avermectin, azadiractin, azinphosphine. methyl, bifenthrin, bifenazate, bistrifluron, buprofezin, carbofuran, cartap, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clotianidine, cyfluthrin, beta-cyfluthrin, gamma cyrothruthinine, cyrothruthinine, diafentiuron, diazinon, dieldrin, diflubenzuron, dimethoate, dinotefuran, diophenolan, emamectin, endosulfan, sphenvarelate, etiprol, fenothiocarb, fenpropicarin, fenvarelate, fenprelil, fipronil, flonictruvate, flubufenulfate, flubendaminate, flubendaminate, flubendaminate, flubendaminate, , halofenozide, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, isofenphos, lufenuron, malation, metaflumizone, metalldehyde of, metamidophos, metidation, methomyl, metoprene, methoxychlor, methoxyphenozide, metofluthrin, monocrotophos, nitenpiram, nitiazine, novaluron, noviflumuron (XDE-007), oxamyl, paration, paration-methyl, permethrin, phosphatonate, phosphamone , profenophos, profluthrin, protrifenbute, pimetrozine, pyrethrin, pyridalyl, pyriproxyfen, rotenone, ryanodine, S1812 (VaIent) 1 spinosad, spiridiclofen, spiromesifen (BSN 2060), sulprofos, tebufenozide, teflubenzyron, teflubenzuron, teflubenzuron thiodicarb, thiosultap-sodium, tolfenpyrad, tralometrine, triazamate, trichloron, triflumuron, aldicarb, fenamiphos, amitraz, chinomethionat, chlorobenzylate, cyhexatin, dicofol, dienochlor, ethoxazole, phenazaquine, oxido fenbutyrate, tetrahydrate, tetrahydrate aizawai thuringiensis, Bacillus thuringiensis kurstaki, delta endotoxinade Bacillus thuringiensis, bacillovirus, entomopathogenic bacteria, entomopath virus ogenic and entomopathogenic fungi.

Also of note is a composition according to the present invention wherein at least one additional biologically active agent or compound is selected from the group consisting of abamectin, acetamiprid, amitraz, avermectin, azadiractin, bifentrin, buprofezin, cartap, chlorantraniliprol, chlorphenapyr, chlorpyrifos , clotianidine, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diophenolan, emamectin, endosulfan, sphenvarelate, etiprol, fenotiendonuron, fluvumphonate, fluvofenamide hydramethylnon, imidacloprid, indoxacarb, lufenuron, metaflumizone, methomyl, metoprene, methoxyphenzide, nitenpiram, nitiazine, novaluron, oxamyl, pimetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxifen, rianodiclen, sphenofenamide, tibenamide , thiodicarb, thiosultap-sodium, tralometrine, triazamate, triflum uron, Bacilius thuringiensis subsp. aizawai, Bacillus thuringiensis subsp.kurstaki, nucleopoliedrovirus and encapsulated Bacillusthuringiensis delta endotoxin.

Further note is a composition according to the present invention wherein the at least one additional or compostobiologically active agent is selected from the group consisting of decipermethrin, cyhalothrin, cyfluthrin and beta-cyfluthrin, sphenvarelate, fenvarelate, tralomethrin, phenothiocarb, methomyl, oxamyl , thiodicarb, acetamiprid, clotianidine, imidacloprid, tiametoxam, tiacloprid, indoxacarb, spinosad, abamectin, avermectin, emamectin, endosulfan, ethiprol, fipronil, flufenoxuron, triflumuron, diphenylan thipropane, pyrazine thiocyanate Bacillusthuringiensis and entomophagous fungi.

For embodiments where one or more of these various mixing partners are used, the weight ratio between these various mixing partners (in total) and the compound of Formula 1 is typically from about 1: 3000 to about 3000: 1. Note weight ratios of from about 1: 300 to about 300: 1 (such as ratios of about 1:30 to about 30: 1). Those skilled in the art can readily determine by simple experimentation the biologically effective amounts of active ingredients required for the desired spectrum of biological activity. It will be apparent that the inclusion of such additional components may expand the spectrum of controlled invertebrate pests beyond the spectrum controlled by the compound of Formula 1 alone.

In certain cases, combinations of a compound according to the present invention with other biologically active agents or compounds (i.e. active ingredients) (particularly in the control of invertebrate pests) may result in a greater effect than the additive (i.e. synergistic). It is always desirable to reduce the amount of active ingredients released into the environment while ensuring effective pest control. When synergy of active invertebrate pest control ingredients is found at application rates that generate satisfactory agronomic levels of invertebrate pest control, these combinations may be advantageous in reducing crop production costs and reducing environmental burden.

Note a combination of a Formula 1 compound with at least one other active pest control ingredient. Of particular note is a combination in which the other active invertebrate pest control ingredient has a different site of action than the compound of Formula 1. In certain cases, a combination of at least one other active invertebrate pest control ingredient that has a similar control spectrum but Different site of action will be particularly advantageous for resistance administration. Accordingly, a composition according to the present invention may additionally comprise a biologically effective amount of at least one additional active invertebrate pest control ingredient having a similar control spectrum but different site of action. Contacting a genetically modified plant to express a pragainvertebrate compound (such as protein) or the plant site with a biologically effective amount of a compound according to the present invention may also provide a broader spectrum of plant protection and is beneficial for resistance administration.

Table A lists specific combinations of a Formula 1 compound with other invertebrate pest control agents illustrating the mixtures, compositions and methods according to the present invention. The first column of Table A lists specific invertebrate control agents (such as "abamectin" in the first row). The second column of Table A lists the mode of action (where known) or chemical class of invertebrate pest control agents. The third column of Table A relates to the realization (s) of relative weight ratio ranges where the invertebrate pest control agent may be applied to a compound of Formula 1, its N-oxide or salt (such as "50: 1"). a: 1:50 "abamectin with respect to a compound of Formula 1 by weight).

Thus, for example, the first row of Table A specifically describes that the combination of a compound of Formula 1 withbamectin may be applied by weight ratio from 50: 1 to 1:50. The remaining lines of Table A should be interpreted similarly. It is further noted that Table A relates specific decomposed combinations of Formula 1 with other illustrative invertebrate pest control agents of the mixtures, compositions and methods according to the present invention and includes additional embodiments of weight ratio ranges for application rates.

Table a

<table> table see original document page 115 </column> </row> <table> <table> table see original document page 116 </column> </row> <table> <table> table see original document page 117 < / column> </row> <table> <table> table see original document page 118 </column> </row> <table> <table> table see original document page 119 </column> </row> <table>

An embodiment of invertebrate pest control agents (such as insecticides and acaricides) for admixture with compounds of the present invention includes sodium channel modulators such asobifenthrin, cypermethrin, cyhalothrin, lambda-cyhalothrin, cyfluthrin, beta-cyfluthrin, deltamethrin, dimeflutrin, sphenvarelate, fenvarelate, indoxacarb, metofluthrin, profluthrin, pyrethrin and tralomethrin; cholinesterase inhibitors such as chlorpyrifos, methomyl, oxamyl, thiodicarb and triazamate; neonicotinoids, such as acetamprid, clotianidine, dinotefuran, imidacloprid, nitempiram, nitiazine, thiacloprid and thiametoxam; Insecticidal macrocyclic lactones such as sputum, spinosad, abamectin, avermectin and emamectin; GABA (γ-aminobutyric acid) -regulated chloride channel blockers such as endosufan, etiprol and fipronil; chitin synthesis inhibitors such as buprofezin, cyromazine, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron and triflumuron; juvenile hormone mimics such as diofenolan, phenoxycarb, metoprene and pyriproxyfen; Deoctopamine receptor binders such as amitraz; ecdisone agonists such as azadiractin, methoxyphenozide and tebufenozide; Ryanodine receptor binders such as comorianodine, anthranilic diamides such as chlorantraniliprol (see U.S. Patent No. 6,747,047, PCT Publications WO 2003/015518 and WO2004 / 067528) and flubendiamide (see U.S. Patent No. 6,603,044) nereistoxin analogs such as cartap; mitochondrial electron transport inhibitors such as chlorfenapyr, hydramethylnon and pyridaben; lipid diosynthesis inhibitors such as spirodiclofen and spiromesifen; decyclodiene insecticides such as dieldrin; ciflumetofen; fenothiocarb; flonicamid; metaflumizone; pirafluprol; pyridalyl; pyriprole; pymetrozine; spirotetramat etiosultap-sodium. An embodiment of compounding biological agents according to the present invention includes nucleopolydoviruses such as HzNPV and AfN PV; Bacillus thuringiensis and delta-endotoxins encapsulated from Bacillus thuringiensis, such as Cellcap, MPV and MPVII; as well as genetically modified and naturally occurring viral insecticides that include members of the bacillovirid family as well as fungi-phages. Of note is the composition according to the present invention wherein the at least one additional biologically active agent or compound is selected from the Invertebrate Pest Control Agents listed in Table A above.

The weight ratios between a compound including a Formula 1 compound, its N-oxide or salt, and the additional invertebrate pest control agent are typically from 1000: 1 to 1: 1000, where an embodiment is from 500: 1 to 1. : 500, another embodiment is from 250: 1 to 1: 200 and the other embodiment is from 100: 1 to 1: 50. Listed below are embodiments of specific decompositions comprising compound of Formula 1 (compound numbers designate compounds in the Index Tables A to C) and additional invertebrate pest control agent.

Table B

<table> table see original document page 121 </column> </row> <table> <table> table see original document page 122 </column> </row> <table> <table> table see original document page 123 < / column> </row> <table> <table> table see original document page 124 </column> </row> <table>

Specific mixtures listed in Table B typically combine the compound of Formula 1 with the other invertebrate pest agent for the reasons specified in Table A.

Invertebrate pests are controlled in agronomic and non-agronomic applications by applying one or more compounds according to the present invention, typically in the form of decomposition, in a biologically effective amount, to the pest environment, including the site of agronomic infestation and / or non-agronomic, the area to be protected or directly over the pests to be controlled.

Accordingly, the present invention comprises a method of controlling invertebrate pests in agronomic and / or nonagronomic applications comprising contacting the invertebrate pest or its environment with a biologically effective amount of one or more of the compounds according to the present invention or a A composition comprising at least one such compound or a composition comprising at least one such compound and a biologically effective amount of at least one additional biologically active agent or compound. Examples of suitable compositions comprising a compound according to the present invention and a biologically effective amount of at least one additional biologically active agent or compound include granular compositions, wherein the additional active compound is present on the same granule as the compound according to the present invention or above. separate granules of the compound according to the present invention.

In order to achieve contact with a compound or composition according to the present invention to protect a field crop against invertebrate pests, the compound or composition is typically applied to the crop before planting, to foliage (such as leaves, stems, flowers, fruits). plant or soil plants or other growth media before or after crop planting.

One embodiment of a contact method is by means of spraying. Alternatively, a granular composition comprising a composition according to the present invention may be applied to plant foliage or soil. The compounds according to the present invention may also be effectively provided by absorbing the plant by contacting the plant with a composition comprising a compound according to the present invention applied in the form of soil soaking with a liquid formulation, a granular soil formulation, treatment of a seedling box or transplant dipping. A composition according to the present invention is in the form of a liquid formulation for soaking soil. Also of note is an invertebrate pest control method comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound according to the present invention or with a composition comprising a biologically effective amount of a compound according to the present invention. Deserves further observation is the method in which the environment is soil and the composition is applied to the soil in the form of soil drenching. It deserves further observation that compounds according to the present invention are also effective by localized application to the infestation site. Other contact methods include the application of a compound or composition according to the present invention by direct and residual sprays, aerial sprays, gels, seed coatings, microencapsulations, systemic absorption, bait, ear tags, mixtures, nebulizers, fumigants, aerosols, and many others. One contact method embodiment is a stable size fertilizer granule, stick or pad comprising a compound or composition according to the present invention. The compounds according to the present invention may also be impregnated with materials for fabrication of invertebrate control devices (such as counter-insects).

The compounds of the present invention are also useful in seed treatments to protect seeds against invertebrate pests. In the context of the present disclosure and claims, seed treatment indicates contact of the seed with a biologically effective amount of compound according to the present invention, which is typically formulated as a composition according to the present invention. This seed treatment protects the seed against soil invertebrate pests and can generally also protect roots and other parts of the plant in contact with the soil from seedlings that develop from the germinating germination. Seed treatment can also provide foliage protection by translocating the compound according to the present invention or second active ingredient into the developing plant. Seed treatments can be applied to all types of seeds, including those from which genetically transformed plants will germinate. express specialized characteristics. Representative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis toxin or those expressing herbicide resistance such as glyphosate acetyltransferase, which provides agglosphosate resistance.

One method of treating seeds is by spraying or dusting the seed with a compound according to the present invention (i.e., in formulated composition form) prior to seed planting. Compositions formulated for seed treatment generally comprise an adhesive or film-forming agent.

Therefore, a seed coating composition according to the present invention typically comprises a biologically effective amount of a compound of Formula 1, its N-oxide or salt and a film former or adhesive agent. The seeds may be coated by spraying a fluid suspension concentrate directly onto a seed tipping bed and then drying the seeds.

Alternatively, other types of formulation such as wet powders, solutions, suspoemulsions, melt concentrates and water emulsions may be sprayed onto the seed. This process is particularly useful for applying seed film coatings. Various processes and coating machines are available to those skilled in the art. Suitable processes include those listed in P. Kosters et al, SeedTreatment: Progress and Prospects, Monograph BCPC 1994 No. 57, and related references.

The treated seed typically comprises a compound according to the present invention in an amount of from about 0.1 g to 1 kg per 100 kg of seeds (i.e. about 0.0001 to 1% by weight of the seeds after treatment). A fluid suspension formulated for seed treatment typically comprises about 0.5 to about 70% of the reactive ingredient, about 0.5 to about 30% of a film-forming adhesive, about 0.5 to about 20% of an active ingredient. dispersing agent, 0 to about 5% of a thickener, 0 to about 5% of pigment and / or paint, 0 to about 2% of a defoaming agent, 0 to about 1% of a preservative and 0 to about 75 % of a volatile liquid diluent.

The compounds of the present invention may be incorporated into a bait composition that is consumed by invertebrate pests or used in a device such as a trap, bait station and the like. Such a bait composition may be in the form of granules comprising (a) active ingredients, namely a biologically effective amount of a compound of Formula 1, its A / -oxide or salt, (b) one or more food materials, optionally (c) an attractive and optionally (d) one or more humectants. Note that granules or bait compositions comprising about 0.001 to 5% of active ingredients, about 40 to 99% of food and / or attractive material and optionally about 0.05 to 10% of humectants, which are effective in controlling Invertebrate soil pests at very low application rates, particularly at active ingredient doses that are lethal by ingestion rather than by direct contact. Some food materials may work as food sources and as attractive. Food materials include carbohydrates, proteins and lipids. Examples of food materials are vegetable flour, sugar, starches, animal fat, vegetable oil, yeast extracts and milk solids. Examples of attractants are odorants and flavorants such as plant or fruit extracts, perfume or other animal or plant components, pheromones or other agents known to target target invertebrate pests. Examples of humectants, ie moisture retaining agents, are glycols and other polyols, glycerin and sorbitol. Note a bait composition (and a method of using this bait composition) used to control at least one selected invertebrate pest from the group consisting of ants, termites and cockroaches. An invertebrate pest control device may comprise gift bait assembly and a shelter adapted for receiving bait arrangement, wherein the shelter has at least one dimensioned opening to allow the invertebrate pest to pass through the opening so that the invertebrate pest may have access to composition is from a location outside the shelter and where the shelter is further adapted for placement in a known or potential invertebrate pest site.

The compounds according to the present invention may be applied without other adjuvants, but most often the application will be of a formulation comprising one or more active ingredients with appropriate carriers, diluents and surfactants and possibly in combination with a food, depending on the intended end use. One method of application involves spraying a dispersion in water or refined oil solution of a compound according to the present invention. Combinations with spray oils, spray oil concentrations, spreading adhesives, adjuvants, other solvents and synergists such as piperonyl butoxide often increase compound effectiveness. For non-agronomic uses, these sprays may be applied from spray containers such as a can, bottle or other container, either by means of a pump or by releasing a pressurized container such as an aerosolpressurized spray can. Such spray compositions may take various forms, such as sprays, mists, foams, fumes or fog. Such spray compositions may therefore further comprise propellants, foaming agents etc., as the case may be. Note a spray composition comprising a biologically effective amount of a compound or composition according to the present invention and a carrier. One embodiment of such a spray composition comprises a biologically effective amount of a compound or composition according to 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 above. A spray composition (and a method using such a spray composition released from a spray container) that is used to control at least one selected invertebrate pest from the group consisting of mosquitoes, black flies, stable flies, deer flies, flies deserves observation. of horses, wasps, hornets, hornets, ticks, spiders, ants, and similar mosquitoes, including individually or in combinations.

Non-agronomic applications include the protection of animals, particularly vertebrates, more particularly homeothermic vertebrates (such as mammals or birds), and even more particularly mammals, against invertebrate parasitic pests by administering an effective amount as a parasiticide (ie biologically effective). ) of a compound according to the present invention, typically in the form of a compound formulated for veterinary use, to the animal to be protected. A method of animal protection which comprises administering to the animal a parasiticidal effective amount of a compound according to the present invention deserves observation. As indicated in the present descriptive report and the claims, the terms "parasiticide" and "as parasiticide" indicate observable effects on invertebrate parasitic pests to provide protection of an animal against the pest. Parasiticidal effects typically refer to a reduction in the occurrence or activity of target invertebrate pragaparasitic. These effects on the pest include necrosis, death, retarded growth, reduced mobility or reduced ability to stay in or on the host animal, reduced feeding and inhibition of reproduction. These effects on parasitic invertebrate pests provide control (including prevention, reduction or elimination) of parasitic infestation or infection of the animal. Examples of invertebrate parasitic pests controlled by administering an effective parasiticidal amount of a compound according to the present invention to animals to be protected include ectoparasites (arthropods, mites etc.) and endoparasites (helminths such as nematodes, trematodes, cantodes, acanthocephalus etc. .). In particular, the compounds according to the present invention are effective against ectoparasites, including: flies such as Haematobia (Lyperosia) irritans (horn fly), Stomoxys calcitrans (threaded stables), Simulium spp (black fly), Glossina spp (tse-tse fly) ), Hydrotaea irritans (head fly), Musca autumnalis (face fly), Musca domestica (house fly), Moreliia simplex (sweat fly), Tabanus spp (horse fly), Hypoderma bovis, Hypoderma lineatum, Lucilia sericata, Lucilia cuprina (green breath fly), Cailiphora spp (musk breath), Protophormia spp, Oestrus ovis (nasal berne fly), Culicoidesspp (mosquito gunpowder), Hippobosca equine, Gastrophilus intestinalis, Gastrophilus haemorrhoidalis and Gastrophilus naslis; lice such as Bovieola (DamaIinia) bovis, Bovieola equi, Haematopinus asini, Felieola subrostratus, Heterodoxus spiniger, Lignonathus setosus and Trichodeetes eanis such as Melophagus ovinus; mites, such as Psoroptes spp, Sareoptes seabei, Chorioptes bovis, Demodex equi, Cheyletiella spp, Notoedres cati, Trombiculaspp and Otodectes cyanotis (ear mites); bed bugs such as Ixodesspp, Boophilus spp, Rhipicephalus spp, Amblyomma spp, Dermacentor spp, Hyalomma spp and Haemaphysalis spp; and fleas such as Ctenocephalides felis (cat flea) and Ctenocephalides canis (dog flea).

Non-agronomic applications in the veterinary sector take place by conventional means, such as by enteral administration in the form of, for example, tablets, capsules, beverages, soaking preparations, granules, pastes, mixtures, feeding procedures, suppositories; by parenteral administration, such as by injection (including intramuscular, subcutaneous, intravenous, intraperitoneal), implants; by nasal administration; by local administration, such as by dipping or dipping, spraying, washing, dusting or applying to a small area of the animal and by means of articles such as collars, ear tags, tail straps, limb measuring tapes or halters which comprise compounds or compositions according to the present invention.

Typically, a parasiticidal composition according to the present invention comprises a mixture of a compound of Formula 1, its A / oxide or salt, with one or more pharmaceutically or veterinarily acceptable carriers comprising excipients and auxiliaries selected with respect to the intended route of administration (such as as oral, local or parenteral administration as injection) and according to standard practice. In addition, an appropriate vehicle is selected based on compatibility with one or more active ingredients in the composition, including considerations such as pH stability and moisture content. Therefore, an animal parasitic pest protection composition comprising a parasiticidal effective amount of a compound according to the present invention and at least one vehicle deserves observation.

For parenteral administration, including intravenous, intramuscular and subcutaneous injection, a compound according to the present invention may be formulated in suspension, solution or emulsion in oily or aqueous vehicles and may contain adjuncts such as suspending, stabilizing and / or dispersing agents. Pharmaceutical compositions for injection include aqueous solutions of water-soluble forms of active ingredients (such as a salt of an active compound), preferably in physiologically compatible buffers containing other excipients or auxiliaries, as known in the pharmaceutical formulation art.

For oral administration including solutions (the most readily available form of absorption), emulsions, suspensions, pastes, gels, capsules, lozenges, mixtures, powders, granules, retention blocks and feed / water / licking blocks, a compound according to The present invention may be formulated with art-known binders / fillers that are suitable for compositions for oral administration, such as sugars (such as lactose, sucrose, mannitol, sorbitol), starch (such as cornstarch, wheat starch, rice starch, potato), derived cellulose (such as methylcellulose, carboxymethylcellulose, ethyl hydroxycellulose), protein derivatives (such as zein and gelatin) and synthetic polymers (such as polyvinyl alcohol, polyvinylpyrrolidone). If desired, lubricants (such as magnesium stearate), disintegrating agents (such as cross-linked polyvinylpyrrolidinone, agar, alginic acid) and dyes or pigments may be added. Pastes and gels often also contain adhesives (such as acacia, alginic acid, bentonite, cellulose, xanthan gum, aluminum silicate and colloidal magnesium) to help keep the composition in contact with the oral cavity without being easily ejected.

If the parasiticidal compositions are in food-centric form, the carrier is typically selected from high performance foods, food cereals or protein concentrates. Such feed concentrate compositions may comprise, in addition to the parasiticidal active ingredients, additives that promote animal health or growth, improve the quality of animal slaughter or otherwise useful for breeding. These additives may include, for example, vitamins, antibiotics, chemotherapeutic agents, bactericides, fungicides, coccidicides and hormones.

The compounds according to the present invention have been found to possess unfavorable pharmacokinetic and pharmacodynamic properties, providing systemic availability from administration or ingestion. After ingestion by the animal to be protected, therefore, parasiticidal effective concentrations of compounds of the present invention in blood flow protect the treated animal against blood pests such as fleas, mice and lice. Therefore, an animal protection composition against invertebrate pests in a form for oral administration deserves observation (i.e. comprising, in addition to a parasiticidal effective amount of a compound according to the present invention, one or more vehicles selected from binders and loads suitable for oral administration and food concentrate vehicles).

Formulations for local administration are typically in the form of powder, cream, suspension, spray, emulsion, foam, paste, aerosol, ointment, ointment or gel. More typically, a local formulation is a water soluble solution, which may be in the form of a concentrate that is diluted prior to use. Parasiticidal compositions suitable for local administration typically comprise a compound of the present invention and one or more vehicles suitable for local use. In applications of a parasiticidal composition locally to the external side of animals such as line or dot (i.e. "dot" treatment), the active ingredient is expected to migrate over the active surface to cover all or most of it. , its external extension. As a result, the treated animal is particularly protected against invertebrate pests that seal the animal's epidermis, such as bed bugs, fleas and lice. Formulations for localized administration therefore often comprise at least one organic solvent to facilitate active transport on the skin and / or penetration into the epidermis of the animal. Commonly used solvents as carriers in such formulations include propylene glycol, paraffins, aromatics, esters such as deisopropyl myristate, glycol ethers and alcohols such as ethanol and n-propanol.

The application rate required for effective control (ie "biologically effective amount") will depend on factors such as the invertebrate species to be controlled, the pest life cycle, life stage, size, location, time of year, animal or host crop, feeding behavior, mating behavior, environmental humidity, temperature and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but up to 0.0001 kg / hectare may be sufficient or up to 8 kg / hectare may be required. For non-agronomic applications, effective use rates will range from about 1.0 to 50 mg / square meter, but up to 0.1 mg / square meter may be sufficient or up to 150 mg / square meter may be required. easily the biologically effective amount required for the desired level of invertebrate pest control.

Generally, for veterinary use, a compound of Formula 1, its N-oxide or salt is administered in a parasiticidal effective amount to a animal to be protected against invertebrate parasitic pests. An effective amount as a parasiticide is the amount of active ingredient required to achieve an observable effect of reducing the occurrence or activity of the target invertebrate parasitic pest. Those skilled in the art will appreciate that the effective dose for parasiticide may vary for the various compounds and compositions according to the present invention, the parasiticidal effect and desired duration, the target pest species, the animal to be protected, the mode of application and the like. The amount required to achieve a specific result can be determined by simple experimentation.

For oral administration to homeothermic animals, the daily dosage of a compound according to the present invention typically ranges from about 0.01 mg / kg to about 100 mg / kg, more typically about 0.5 mg / kg to about 100 mg. / kg body weight of the animal. For local administration (such as dermal), divers and sprays typically contain from about 0.5 ppm to about 5000 ppm, more typically about 1 ppm to about 3000 ppm, of a compound according to the present invention.

The following abbreviations are used in the following Index Tables AaD: CF3 indicates trifluoromethyl, -CN is cyano and -NO2 is nitro. "Ex." represents "Example" and is followed by a number indicating which example is prepared the compound. In Index Tables A, B, and C, (R2) is the combination of (R2) n as shown in the case where Z is CR2 as specified for Formula 1.

Table Index A

<formula> formula see original document page 136 </formula> <table> table see original document page 137 </column> </row> <table>

m.p ° 0

See Table C index for 1H NMR data.

See synthesis example for 1 H NMR data.

Table Index B

<formula> formula see original document page 137 </formula>

See Table C index for 1H NMR data.

Table Index C <formula> formula see original document page 138 </formula>

* See synthesis example for 1H NMR data. Table Index D

<table> table see original document page 138 </column> </row> <table> <table> table see original document page 139 </column> </row> <table>

1H NMR data are in ppm from

tetramethylsilane. Couplings are referred to as (s) isolated, (d) double, (t) trio, (m) multiple, (br s) wide isolated, (br d) double isolated, (br t) triple wide, (dd) even of doubles and (dt) triplets.

Biological Examples of the Invention

The following Tests demonstrate the efficacy of control decomposed in accordance with the present invention on specific pests. "Control effectiveness" represents the inhibition of the development of invertebrate pests (including mortality) that causes significantly reduced feeding. The pest control protection offered by the compounds is not limited, however, to these species. See tables indexA through D for compound descriptions.

Test A

To evaluate the control of cruciferous moths (Plutella xylostellá), the test unit consisted of a small open container with a twelve to fourteen day old radish plant inside. It was previously infested with ten to fifteen neonatal larvae on an insect-feeding piece, using a central sampler to remove a bump from a hardened multi-larva insect food leaf growing on it and transfer the larvae-containing bung to the test unit. . The larvae moved to the test plant as the food bung dried.

Test compounds were formulated using a solution containing 10% acetone, 90% water and 300 ppm nonionic surfactant Formula X-77® Spreader Lo-Foam containing alkylaryl polyoxyethylene, free fatty acids, glycols and isopropanol (Loveland Industries, Inc., Greeley, Colorado, United States). The formulated compounds were applied to 1 ml of liquid by means of a 1 / 8JJ custom body SUJ2 atomizer nozzle (Spraying Systems Co., Wheaton, Illinois, United States) positioned at 1.27 cm above the top of each test unit. All experimental compounds in these tests were sprayed at 50 ppm, which was repeated three times. After spraying of the formulated test compound, each test unit was kept to dry for one hour and then a black screen cap was placed over the top. The test units were maintained for six days in a growth chamber at 25 ° C and 70% relative humidity. The control efficacy level of the test compound was then visually determined based on leaf 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 plant protection (20% or less dietary damage or 80% or more mortality): 1, 2, 6, 10, 12, 13, 15,16 , 18, 19 and 102.

Test B

For evaluation of caterpillar control of autumn cereals (Spodoptera frugiperda), the test unit consisted of a small open container with a four to five day old maize plant inside. It was previously infested (using a central sampler) with ten to fifteen day old larvae on a piece of insect food.

Test compounds were formulated and sprayed at 250ppm as described for Test A and reproduced three times. After spraying, the test units were kept in a decreasing chamber and then visually evaluated as described for Test A.

Of the compounds of Formula 1 tested, the following provided very good to excellent levels of plant protection (20% or less dietary damage or 80% or more mortality): 1,2, 16, 18 and 19.

C test

For evaluation of the tripod control of western flowers (Frankliniella occidentalis) by contact and / or systemic means, the test unit consisted of a small open container with a five to seven day old Long defect plant inside.

Test compounds were formulated and sprayed at 250ppm and repeated three times as described for Test A. After spraying, the test units were kept to dry for one hour and then 22 to 27 adult tripods were added each unit and a black screen cover was then placed on it. The test units were kept for seven days at 25 ° C and relative humidity 45 to 55%. A mortality assessment was determined for each test unit.

Of the compounds tested, the following provided very good levels of plant protection (20% or less of food damage or 80% or more of mortality): 2, 12, 18 and 19.

Test D

For evaluation of potato grasshopper (Empoascafabae Harris) control by contact and / or systemic means, the test unit consisted of a small open container with a six-day-old Soleil comcinco bean plant (primary leaves emerged) on its interior.White sand was added to the top of the soil and one of the primary leaves was excised before application. Test compounds were formulated and sprayed at 250 ppm and the test was reproduced three times as described for Test A. After spraying, the test strips were kept to dry for one hour before they were post-infested with potato cycoforms. 18 to 21 days old). A black cover with screen was placed over the cylinder. The test units were kept for six days in a growth chamber at 19-21 ° C and 50 to 70% relative humidity. The control efficacy of each test unit was assessed visually and then by insect mortality.

Of the compounds of Formula 1 tested, the following provide very good to excellent control efficacy (70% or greater mortality): 2, 12, 16, 18, 19 and 103.

Test E

For evaluation of green peach (Myzuspersicae) aphid control by contact and / or systemic means, the test unit consisted of a small open container with a radish plant twelve to fifteen days old inside. This was previously infested by placing on a leaf of the test plant thirty to forty aphids on a piece of extirpated leaf from a crop plant (cut leaf method). The larvae moved to the test plant as the leaf seed dissected. After the previous infestation, the soil of the detesting unit was covered with a layer of sand.

All test compounds were formulated and sprayed at 250 ppm as described for Test A and repeated three times. After spraying of the formulated test compound, each test unit was kept to dry for one hour and then a black cap with screen was placed over the top. The test units were maintained for six days in a growth chamber at 19-21 ° C and 50 to 70% relative humidity. Each test unit then determined the mortality of insects.

Of the compounds of Formula 1 tested, the following resulted in 50% or more mortality: 2, 18, and 19. Test F

For evaluation of the control of aphid of melon and cotton (Aphysgossypii) by contact and / or systemic means, the test unit consisted of a small open container with a seven-day-old cotton plant in its interior. It was previously infested with thirty insects on a piece of leaf according to the cut leaf method described for the Test and the soil of the test unit was covered with a layer of sand. Test compounds were formulated sprayed at 250 ppm as described for Test A. Applications were repeated three times. After spraying of the formulated test compound, each test unit was kept to dry for one hour and then a black screen cap was placed over it. Test units were maintained for six days in a growth chamber at 19-21 ° C and a relative humidity of 50 to 70%. Each test unit was then visually evaluated to determine insect mortality.

Of the compounds of Formula 1 tested, the following resulted in 50% or more mortality: 16, 18 and 19.

G test

For evaluation of cat flea control (Ctenocephalidesfelis, Bouche), a CD-1® mouse (about 30 g male, obtained from Charles River Laboratories, Wilmington MA) received oral dosing of a 30 ppm test compound solubilized in propylene glycol / glycerol formal (60:40). Two hours after oral administration of the test compound, about eighteen to sixteen adult fleas were applied to each mouse. Fleas were then evaluated to determine mortality 48 hours after flea application to the mouse.

Of the compounds tested, the following compounds caused mortality of 50% or more: 1, 2, 12, 13, 16, 18, 19 and 102.

Claims (27)

1. Compound of formula 1, its N-oxide or salt: <formula> formula see original document page 145 </formula> where: - G is O or NR3; U is C (= 0), S (= 0 ), C (= S) or S (O) 2; Z is N or CR2; - A1 is CR4 or N; - A2 is CR5 or N; - A3 is CR6OuN; - A4 is CR7 or N; Q is a heterocycle. saturated or unsaturated five-membered optionally substituted with one or more substituents independently selected from halogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C6 halocycloalkyl, C1-C6 haloalkoxy, C 1 -C 6 alkylthio halo C 1 -C 6 alkylsulfinyl C 1 -C 6 alkylsulfinyl C 1 -C 6 alkylsulfonyl C 1 -C 6 haloalkylsulfonyl C 1 -C 6 alkyl C 2 -C 8 dialkylamino cyano, nitro, C (= 0) NR 8 wherein each phenyl or pyridinyl is optionally substituted by one or more substituents independently selected from R 11, or Q is C (O) NR 12 R 13 C (S) NR 12 R 13 S (O) 2 NR 14 R 15 or R 16; or C 1 -C 6 alkyl C 2 -C 6 alkenyl C 2 -C 6 alkynyl C 3 -C 6 cycloalkyl C 4 -C 6 alkylcycloalkyl C 4 -C 7 cycloalkyl alkyl optionally substituted with one or more substituents independently selected from R 17, each R 2 is independently H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl C 1 -C 6 alkylamino C 2 -C 8 dialkylamino, C 2 -C 4 alkoxycarbonyl C 2 -C 4 alkylaminocarbonyl, C 3 -C 6 dialkylaminocarbonyl, cyano or nitro R 3 is H 1 cyano or -CHO; or C 1 -C 6 alkyl C 2 -C 6 alkenyl, C 2 -C 6 alkynyl C 3 -C 6 cycloalkyl, C 4 -C 7 alkylcycloalkyl C 4 -C 7 cycloalkylalkyl phenyl, C 1 -C 6 alkylcarbonyl C 1 -C 6 alkoxycarbonyl C 1 -C 6 alkylamino or C 3 -C 6 dialkylamino common or more substituents independently selected from R18; R41 R51 R6 and R7 are independently selected from H1 halogen, C1-C61 alkyl halo C1-C61 cycloalkyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C1-6 haloalkoxy C6, C1-C61 alkylthio C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl C1-C61 alkylsulfonyl C1-C61 haloalkyl C1-C6 alkylamino, C2-C8l dialanoamino cyano; or R 6 and R 7 are taken together to form a fused aromatic ring, wherein the fused aromatic ring contains as dean members, in addition to the bridgehead atoms A3 and A41 three atoms selected from one to two carbon atoms, zero to two atoms nitrogen to zero to one oxygen atom and zero to one sulfur atom or four atoms selected from two to four carbon atoms and zero to two nitrogen atoms; each R8, R12 and R14 is independently H, C1-C6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl C 2 -C 6 alkynyl C 3 -C 6 cycloalkyl, C 4 -C 7 alkylcycloalkyl C 4 -C 7 cycloalkyl alkyl, C 2 -C 6 alkylcarbonyl or C 2 -C 10 alkoxycarbonyl R 13; C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 4 -C 7 alkylcycloalkyl or C 4 -C 7 cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from R 19; 23 and R24 is independently halogen, C1 -C6 alkyl, C1 -C6 haloalkyl, C1 -C6 alkoxy, C1 -C6 haloalkoxy C1 -C6 alkylthio, C1 -C6 haloalkylthio, C1 -C61 alkylsulfonyl C1 -C61 alkylsulfonyl C1 -C6 alkylsulfonyl C1-6 alkylsulfonyl C 2 -C 4 alkylamino C 2 -C 6 alkylamino C 2 -C 4 alkoxycarbonyl, cyano or nitro R 16 is halogen, C 1 -C 6 alkyl halo C 1 -C 6 cycloalkyl C 3 -C 6 haloalkyl C 3 -C 6 alkoxy C 1 -C 6 alkyl halo C 1 -C 6 alkyl C 1 -C 6 alkyl halo C1-C61 haloalkylsulfinyl C1-C61alkylsulfonyl C1-C61 haloalkylsulfonyl C1-C61 C1-C6 alkylamino, dialkylamino C2-Cs1 cyano or nitro; C61 -C61 alkylsulfonyl cyanoor nitro; each R19 is independently halogen, C1-C61 alkyl C1-C61 alkylthio C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C2-C61 alkylcarbonyl C2-C6 alkoxycarbonyl 1 trimethylsilyl, cyano, nitro or Q1; each Q1 is independently a five or six membered phenyl or unsaturated or unsaturated, each optionally substituted with one or more substituents independently selected from halogen, C1-C6 alkyl, C1-C6 haloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylamino -C6, C2 -C8 dialkylamino cyano, nitro, phenyl or pyridinyl, wherein each phenyl or pyridinyl is optionally substituted with one or more substituents independently selected from R23, each R20 is independently H1 alkyl C 1 -C 6, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 4 -C 7 alkylcycloalkyl C 2 -C 7 alkylcarbonyl alkyl or C 2 -C 7 alkoxycarbonyl are each independently H 21 and R 21; C 1 -C 6 alkylhaloC 1 -C 6 alkyl C 2 -C 6 alkenyl C 2 -C 6 alkynyl C 3 -C 6 cycloalkyl C 4 -C 7 alkyl cyclo C 4 C 7 cycloalkyl C 4 C 7 alkyl phenyl or pyridinyl; wherein each phenyl or pyridinyl is optionally substituted by one or more substituents independently selected from R 24; eη is 1, 2, 3 or 4, provided that R 16 is other than methoxy. A compound according to claim 1 wherein: Q is a pyridinyl ring, pyrimidinyl ring, triazinyl ring, ringpyrazolyl ring, triazolyl ring, imidazolyl ring, oxazolyl ring, isoxazolyl ring, ringthiazolyl ring or isothiazolyl ring, wherein each ring is optionally substituted common or more substituents independently selected from halogen, C 1 -C 6 alkyl halo C 1 -C 6 alkyl cycloalkyl C 3 -C 6 halocycloalkyl C 3 -C 6 alkoxy C 1 -C 6 haloalkoxy C 1 -C 6 haloalkyl C 1 -C 6 haloalkyl C 1 -C 6 alkylsulfinyl C 1 -C 6 alkyl C1-C61haloalkylsulfonyl C1-C61 alkylamino C1-C61 dialkylamino C2-C8, cyano, nitro, C (O) NR8R9, C (O) OR10, phenyl and pyridinyl, wherein each phenyl or pyridinyl is optionally substituted with one or more substituents independently selected from from R11; or Q is C (O) NR 12 R 13 S (O) 2 NR 14 R 15 or R 16; Z is CR 2; R 1 is C 1 -C 3 alkyl optionally substituted with one or more substituents independently selected from R 17; each R 2 is independently selected from H, halogen or C1-C2 haloalkyl: R3 is H or cyano; or optionally substituted C1-C4 alkyl with one or more substituents selected from halogen; - R4 and R5 are independently selected from halogen, C1-Ca alkyl, C1-C3 haloalkyl, cyano and nitro; R6 and R7 are independently selected from dehalogen, C1-C3 alkyl, C1-C3 haloalkyl, cyano and nitro; or R 6 and R 7 are taken together to form a fused aromatic ring, wherein the fused aromatic ring contains as ring members, in addition to the bridgehead atoms A3 and A4, four atoms selected from three to four carbon atoms and zero to one. nitrogen atom; each R 8 is independently H, C 1 -C 6 alkyl, C 2 -C 7 alkylcarbonyl or C 2 -C 7 alkoxycarbonyl; - each R 9 and R 10 is independently H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, cycloalkyl C3 -C4, C4 -C7 alkylcycloalkyl or C4 -C7 cycloalkylalkyl each optionally substituted with one or more substituents selected from R19, R12 and R14 are independently H, C1-C6 alkyl, C2-C7 alkylcarbonyl or C2-C7 alkoxycarbonyl and R15 is independently H, C1 -C4 alkyl, C2 -C4 alkenyl, C2 -C4 alkynyl, C3 -C4 cycloalkyl, C4 -C7 alkylcycloalkyl or C4 -C7 cycloalkylalkyl each optionally substituted with one or more substituents selected from R19; it's halog sodium, C1-C6 haloalkyl, C2-C4 dialkylamino, cyano or nitro; each R19 is independently selected from halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfonyl, cyano, nitro and Q1 each Q1 is independently selected from defenyl, pyridinyl and thiazolyl, each optionally substituted with one or more substituents independently selected from halogen, C1-C3 alkyl, C1-C3 haloalkyl, cyano, phenyl and pyridinyl; eη is 1 or 2, provided that at most 1 out of A1, A2, A3 and A4 is N. A compound according to claim 2 wherein: R 1 is halogen substituted C 1 -C 3 alkyl; e- U is C (= 0). A compound according to claim 3 wherein: Q is a pyrazolyl ring, triazolyl ring or imidazolyl ring, wherein each ring is nitrogen bonded and optionally substituted with one or more substituents independently selected from halogen, C1-alkyl -C4, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, cyano, nitro, C (O) NR8 R9 and C (O) OR10; or Q is C (O) NR 12 R 13; R 1 is CF 3; R 6 and R 7 are independently selected from H 1 halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyano and nitro; or R 6 and R 7 are taken together to form a fused aromatic ring, wherein the fused aromatic ring contains four carbon atoms as ring members in addition to the bridgehead atoms A3 and A4, each R 8 is H, each R 9 and R 10 is independently alkyl C 1 -C 4 optionally substituted with a Q 1 and optionally substituted with one or more substituents selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfonyl and R 12 is H; optionally substituted with one or more substituents selected from R19; e- each R19 is independently selected from halogen and Q1. A compound according to claim 4 wherein: - each R 2 is independently H, halogen or CF 3; and R 3 is CH 3, CH 2 CH 3 or CH 2 CF 3. A compound according to claim 5 wherein: G is O, provided that A1, A21 A3 and A4 are different from N. A compound according to claim 1 which 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-4- (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide; 4- [4- (3,5-dichlorophenyl) -3-methyl-2-oxo-4 - (trifluoromethyl) -1-imidazolidinyl] -2-methyl-N- (2-pyridinylmethyl) benzamide; 4- [5- (3,4-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl ] -2-methyl-N- (2-pyridinylmethyl) benzamide; -5- [5- (3,5-dichlorophenyl) -2-oxo-5- (trifluoromethyl) -3-oxazolidinyl] -2- (1 H-1,2,4-triazol-1-yl) benzonitrile; 4- [5- (3,5-dichlorophenyl) -2,2-dioxide-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. A composition comprising a compound according to claim 1 and at least one additional component selected from the group consisting of surfactant, solid diluent and liquid diluent, wherein said composition optionally further comprises at least one additional biologically active agent or compound. An invertebrate pest control composition comprising a biologically effective amount of a compound according to claim 1 and at least one additional component selected from the group consisting of surfactant, diluent solid and liquid diluent, wherein said composition optionally further comprises a biologically effective amount of at least one additional or biologically active compound or compound. A composition according to claim 9 wherein at least one additional biologically active agent or compound is an insecticide selected from the group consisting of macrocyclic lactones, neonicotinoids, octopamine receptor binders, derianodine receptor binders, ecdisone agonists, modulators. sodium channel inhibitors, chitin synthesis inhibitors, nereisotoxin analogs, mitochondrial electron transport inhibitors, cholinesterase inhibitors, cyclodiene insecticides, exudate inhibitors, γ-aminobutyric acid chloride channel blockers, juvenile hormone imitators, inhibitors of biosynthesis delipids and biological agents that include nucleopoliedrovirus, members of Bacillus thuringiensis, encapsulated Bacillus thuringiensise delta-endotoxins other naturally occurring or genetically modified insecticidal viruses. A composition according to claim 9 wherein at least one additional biologically active agent or compound is selected from the group consisting of abamectin, acefate, acetamiprid, acetoprol, aldicarb, amidoflumet, amitraz, avermectin, azadiractin, azinphosphine. methyl, bifenthrin, bifenazate, bistrifluron, buprofezin, carbofuran, cartap, chinomethionat, chlorfenapyr, chlorfluazuron, chlorantraniliprol, chlorpyrifos, chlorpyrifos-methyl, chlorobenzylate, chromafenozide, clotianidine, cyphaltruthrin, beta-cytothruthin, beta-cyrothruthin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, diafentiuron, diazinon, dicofol, dieldrin, dienochlor, diflubenzuron, dimeflutrin, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, phenazuthoxide, fenbutyrate, phenothiophene fenoxycarb, fenpropatrin, fenpyroximate, fenvarelate, fipronil, flonicamid, flubendiamide, flucitrinate, tau-fluvalinate, flufenerim, flufenoxuron, phonophos, halofenozide, hexaflumuron, hexithiazox, hydramethylnon, imiciaphos, imidacloprid, indoxacarb, isofenphos, lufenuron, malation, metaflumizone, methoidophos, methidophenophoridine, methidophenate, methionophenate novaluron, noviflumuron, oxamyl, paration, paration-methyl, permethrin, forate, fosalone, fosmet, phosphamidon, pirimicarb, profenophos, proflutrin, propargite, protrifenbute, pimetrozine, pirafluprol, pyrethrin, pyridaben, pyrazol, pyrifenol, pyrifenol rianodine, spinach, spinosad, spiridiclofen, spiromesifen, spirotetramat, sulprofos, tebufenozide, tebufenpirad, teflubenzuron, teflutrin, terbufos, tetrachlorvinphos, tiacloprid, tiodetoxam, tiodicarbis trisulfonate, triosulfonate Aizawai, Bacillus thuringiensis subsp. kurstaki, nucleopoliedrovirus, Bacillus thuringiensis encapsulated delta-endotoxin, bacillovirus, entomopathogenic bacteria, entomopathogenic viruses and entomopathogenic fungi. A composition according to claim 11, wherein at least one additional biologically active agent or compound is selected from the group consisting of abamectin, acetamiprid, amitraz, avermectin, azadiractin, bifentrin, buprofezin, cartap, chlorantraniliprol, chlorphenapyr, chlorpyrifos , clotianidine, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diophenolan, emamectin, endosulfan, sphenvarelate, etiprol, fenotiendonuron, fluvumphonate, fluvofenamide , hydramethylnon, imidacloprid, indoxacarb, iufenuron1metaflumizone, methomyl, metoprene, methoxyphenzide, nitenpiram, nitiazine, novaluron, oxamyl, pimetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxifen, rhinodenophenophenidine, tibenamide , thiosultap-sodium, tralometrine, triazamate, triflumuron, Bacillus thuringiensi s subsp. aizawai, Bacillus thuringgiensis subsp.kurstaki, nucleopoliedrovirus and encapsulated Bacillusthuringgiensis delta-endotoxin. Composition according to Claim 9, in the form of liquid soil-soak formulation. A spray composition for invertebrate control, comprising: (a) a biologically effective amount of the compound according to claim 1 or the composition according to claim 9, and (b) a propellant. Bait composition for controlling invertebrate pests comprising: (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 attractive one; and (d) optionally a humectant. Trap device for controlling invertebrate pests comprising: (a) the bait composition according to claim 15; and (b) a shelter adapted to receive the bait composition, wherein the shelter has at least one opening sized to allow the invertebrate pest to pass through the opening, so that the invertebrate pest can gain access to the bait composition from a location. outside the shelter and where the shelter is further adapted to be placed at or near a known or potential site of the invertebrate pest. Control method of invertebrate pests comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound according to claim 1. An invertebrate pest control method comprising contacting the invertebrate pest or its environment with a composition according to claim 9. The method of claim 18 wherein the environment is soil and the composition is applied to the soil in the form of soil-soaking formulation. A method of control of cockroaches, ants or termites, which comprises contacting the cockroach, ant or termite with the shell composition in a trap device according to claim 16. 21. METHOD OF CONTROL, mosquitoes, black flies, stable flies, deer flies, horse flies, wasps, hornets, hornets, ticks, spiders, ants or mosquitoes which comprises the contact of mosquitoes, black flies, stable flies , deer flies, horse flies, wasps, wasps, hornets, ticks, spiders, ants or mosquitoes with the spray composition according to claim 14 released from a spray container. A seed protection method against invertebrate pests comprising contacting the seed with a biologically effective amount of a compound according to claim 1. A method according to claim 22, wherein it is roughly coated with the compound of claim 1 formulated as a composition comprising an adhesive film or agent. A treated seed comprising a compound according to claim 1 in an amount of from about 0.0001 to 1% by weight of the seed prior to treatment. The animal protection composition against invertebrate pests which comprises an effective parasiticidal amount of a compound according to claim 1 and at least one vehicle. Composition according to Claim 25 in a form for oral administration. Method of protection of animals against invertebrate pests, comprising administering to the animal a parasiticidal effective amount of a compound according to claim 1.