Synergistic insecticidal compositions

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

Background of the invention Insecticides and pesticide compositions have been developed to control pests such as agricultural and horticultural pests, hygienic pests, or wood-eating pests, in fact as single or mixed pests. Has been used. However, economically efficient and ecologically safe insect control compositions are still being sought. Insecticidal compositions that allow for reduced effective dose ratios, increased environmental safety and reduced incidence of insect resistance are highly desirable. Cyclic application of insect control agents with different modes of action can be adopted for good pest management practices, but this approach does not always provide satisfactory insect control. Moreover, even though combinations of insect control agents have been studied, high synergies have not always been observed. Obtaining pesticide compositions that do not exhibit cross-resistance to existing pesticides, toxicity issues and negative environmental impacts is extremely difficult. [0002]

Therefore, an object of the present invention is to provide a synergistic insecticide composition which exhibits a high control effect accompanied by a reduction in crop production cost and a reduction in environmental load. [0003]

Another object of the present invention is to provide a method for synergistic insect control and enhanced crop protection. [0004]

Outline of the invention The present invention presents in a synergistically effective amount of a neuronal sodium channel antagonist as an essential active ingredient and a recombinant nucleopolyhedrovirus, organic phosphate, carbamic acid capable of expressing pyrethroids, pyrethroid compounds, insect toxins. Provided is a synergistic pesticide composition comprising an ester, formamidine, a large cyclic lactone, amidinohydrazone, a GABA (γ-aminobutyric acid) antagonist, and one or more compounds selected from the group consisting of an acetylcholine receptor ligand. .. [0005]

The present invention also presents recombinant nucleopolyhedroviruses, organic phosphate esters, carbamate esters, formamidines capable of expressing pyrethroids, pyrethroid compounds, insect toxins with synergistically effective amounts of neural cell sodium channel antagonists. Also provided are methods for synergistic insect control involving contacting an insect with one or more compounds selected from the group consisting of a large cyclic lactone, an amidinohydrazone, a GABA antagonist, and an acetylcholine receptor ligand. [0006]

In addition, the present invention provides methods for enhancing plant defense from insect invasion and attack. [0007]

Detailed explanation Definition As used in this application, "acetylcholine receptor ligand compound" means a compound capable of binding to an acetylcholine receptor site. [0008]

"Group A" used in this application is for insecticidal use. 1) Pyrethroid compounds, 2) Pyrethroid compounds, 3) Recombinant nucleopolyhedrovirus, which can express insect toxins, 4) Organophosphate compounds, 5) Carbamate compound, 6) Form amidine compound, 7) Macrocyclic lactone compound, 8) Amidino hydrazone compound, 9) GABA antagonist compound and 10) Acetylcholine receptor ligand compound, Means. [0009]

The "haloalkyl" used in this application is an alkyl group C having 1 to 2X + 1 halogen atoms, which may be the same or different._XH_{2X + 1}Means. Similarly, terms such as "haloalkenyl," "haloalkynyl," "haloalkoxy," and "halophenyl" mean substitutions from mono-to perhalogen, and the halogens may be the same or different. [0010]

As used in this application, "halogen" means Cl, Br, I or F. [0011]

As used in this application, "neuronal sodium channel antagonist" means a compound that can inhibit the ability of a neuron to carry sodium ions across the cell membrane. [0012]

As used in this application, the "pyrethroid-type compound" means a compound characterized by a non-ester-bonded aryl-phenoxybenzyl moiety. [0013]

As used in this application, "synergistic action" means a collaborative action that occurs when two or more biologically active ingredients are combined, in which case the combined activity of the two or more components is each component. It exceeds the sum of the activities of a single substance. [0014]

Surprisingly, a composition comprising a combination of a neuronal sodium channel antagonist and a second insecticidal component, when used with the combination active agent at a lower concentration, is a neuronal sodium channel antagonist or a second insecticidal component. It has been found to provide better insect control than achieved when the insecticidal component is applied alone. [0015]

As mentioned above, a neuronal sodium channel antagonist refers to a compound that can inhibit the ability of a neuron to carry sodium ions across the cell membrane. Thus, affected neurons are unable to excite, resulting in paralysis in the target host and ultimately death. Descriptions of sodium channel antagonists in neurons and their modes of action can be found in Pesticide Biochemistry and Physiology, 60: 177-185 or Archives of Insect Biochemistry and Physiology, 37: 91-103. [0016]

Nerve cell sodium channel antagonists include, among others, compounds such as those described in US 5,543,573, US 5,708,170, US 5,324,837 and US 5,462,938. Typical neuronal sodium channel antagonist compounds useful in the compositions of the present invention have the structural formula:<img file="JP2003517455A_D0001.tif" />[In the formula, A is CR₄R₅Or NR₆And W is O or S; X, Y, Z, X', Y'and Z'are independently H; halogen; OH; CN; NO₂One or more halogens, C₁-C₃Alkoxy, C₁-C₃Haloalkoxy, C₃-C₆Cycloalkyl, C₂-C₆C which may be substituted with an alkenyloxy or a sulfonyloxy group₁-C₆Alkyl; One or more halogens, C₁-C₃Alkoxy or C₃-C₆C which may be substituted with a cycloalkyl group₁-C₆Alkoxy; One or more halogens, C₁-C₄Alkyl or C₁-C₄C which may be substituted with an alkoxy group₁-C₆Alkoxycarbonyl, C₃-C₆Cycloalkylcarbonyloxy, phenyl; One or more C₁-C₃Aminocarbonyloxy optionally substituted with an alkyl group; C₁-C₆Alkoxycarbonyloxy; C₁-C₆Alkylsulfonyloxy; C₂-C₆Alkenyl; or NR₁₂R₁₃Is; m, p and q are independently integers of 1, 2, 3, 4, or 5; n is an integer of 0, 1 or 2; r is an integer of 1 or 2; t is an integer of 1, 2, 3, or 4; R, R₁, R₂, R₃, R₄And R₅Are independently H or C₁-C₄Alkyl; R₆Is H, C₁-C₆Alkyl, C₁-C₆Haloalkyl, C₁-C₆Alkoxyalkyl, C₁-C₆Alkoxy, C₁-C₆Haloalkoxy, C₂-C₆Alkenyl, C₂-C₆Alkyne, C₁-C₆Alkylcarbonyl, C₁-C₆Alkoxycarbonyl, C₁-C₆Alkylthio, or C₁-C₆Haloalkylthio; R₇And R₈Are independently H; halogen; C₁-C₆Alkyl; C₁-C₆Alkylcarbonyloxy; or one or more halogens, CN, NO₂, C₁-C₆Alkyl, C₂-C₆Haloalkyl, C₁-C₆Alkoxy or C₁-C₆Phenyl which may be substituted with a haloalkoxy group; R₉And R₁₀Are independently H or C₁-C₄Alkyl; R₁₁Is H, C₁-C₆Alkyl, C₁-C₆Haloalkyl, C₁-C₄Alkylcarbonyl, C₁-C₆Alkoxycarbonyl or C₁-C₆Haloalkoxycarbonyl; R₁₂And R₁₃Are independently H or C₁-C₆Alkyl; G is H; one or more halogens, C₁-C₄Alkoxy, C₁-C₆Haloalkoxy, CN, NO₂S (O)_uR₁₄, COR₁₅, CO₂R₁₆, Phenyl or C₃-C₆C which may be substituted with a cycloalkyl group₁-C₆Alkyl; C₁-C₆Alkoxy; C₁-C₆Haloalkoxy; CN; NO₂; S (O)_uR₁₇; COR₁₈; CO₂R₁₉One or more halogens, CN, C₁-C₃Haloalkyl, or C₁-C₃Phenyl optionally substituted with haloalkoxy groups; C₃-C₆Cycloalkyl; or phenylthio; Q is one or more halogens, CN, SCN, NO₂, S (O)_uR₂₀, C₁-C₄Alkyl, C₁-C₄Haloalkyl, C₁-C₄Alkoxyalkyl, C₁-C₆Alkoxy, C₁-C₆Haloalkoxy or NR₂₁R₂₂Phenyl which may be substituted with a group; u is an integer of 0, 1 or 2 R₁₄, R₁₅, R₁₆, R₁₈, R₁₉, R₂₁And R₂₂Are independently H or C₁-C₆Alkyl; R₁₇And R₂₀Are independently C₁-C₆Alkyl or C₁-C₆Haloalkyl; R₃₃Is CO₂R₃₄Is; R₃₄Is H, C₁-C₆Alkyl, C₁-C₆Haloalkyl, phenyl or halophenyl; as well as the dotted line configuration<img file="JP2003517455A_D0002.tif" />Indicates a double bond or a single bond (ie, CN or C = N)] It is a compound represented by or a stereoisomer thereof. [0017]

Preferred neuronal sodium channel antagonists suitable for use in the compositions of the present invention have a dotted line arrangement.<img file="JP2003517455A_D0003.tif" />Is a compound of formula I, formula II or formula III that exhibits a double bond. [0018]

A more preferred neuronal sodium channel antagonist suitable for use in the compositions of the present invention is a compound of formula I or formula III in which the dotted line arrangement exhibits a double bond. [0019]

Particularly preferred neuronal sodium channel antagonists suitable for use in the compositions of the present invention are W is O; X is trifluoromethoxy at 4-position; Y is trifluoromethyl at 3-position. Z is CN in 4th place; A is CH₂Is; n is 0; m, p and q are 1 respectively; R and R₁Are H; Z'is C₁Is; R₃₃And G are CO₂CH₃And Q is p- (trifluoromethoxy) phenyl; dotted line arrangement<img file="JP2003517455A_D0004.tif" />Is a compound of formula I or formula III or a stereoisomer thereof, which exhibits a double bond. [0020]

Additional neuronal sodium channel antagonist compounds include, among others, those described in US 5,116,850 and US 5,304,573. Typical additional neuronal sodium channel antagonist compounds suitable for use in the compositions of the present invention have structural formulas:<img file="JP2003517455A_D0005.tif" />[In the formula, W is O or S; X'' and Y'' are independently H; halogen; CN; SCN; one or more halogens, NO₂, CN, C₁-C₄Alkoxy, C₁-C₄Alkylthio, phenyl, halophenyl, C₁-C₄Alkylsulfonyl, C₁-C₄Haloalkylsulfonyl, or C₁-C₄C which may be substituted with an alkoxycarbonyl group₁-C₆Alkyl; C₂-C₄Alkenyl; C₂-C₄Haloalkenyl; C₂-C₄Alkyne; C₂-C₄Halo alkynyl; C₃-C₆Cycloalkyl; C₃-C₆Halocycloalkyl; one or more halogens, CN, NO₂, C₁-C₄Alkyl, C₁-C₄Haloalkyl, C₁-C₄Alkoxy, C₁-C₄Haloalkoxy, C₁-C₄Alkylthio, C₁-C₄Alkylsulfonyl or C₁-C₄Phenyl optionally substituted with a haloalkylsulfonyl group; C₁-C₄Alkylcarbonyl; C₁-C₄Haloalkylcarbonyl; or NR₂₈R₂₉Is; m is an integer of 1, 2, 3, 4 or 5; G'may be substituted with one or more groups selected from X'' that may be the same or different; A 5-membered complex aromatic ring containing 0 or 1 oxygen atom, 0 or 1 sulfur atom and 1 or 2 heteroatoms selected from 0, 1 or 2 nitrogen atoms (the 5-membered complex aromatic ring). The rings are bonded via carbon and may be substituted with one or more groups selected from X'' that may be the same or different); or A 6-membered complex aromatic ring containing 0 or 1 oxygen atom, 0 or 1 sulfur atom and 1 or 2 heteroatoms selected from 0, 1 or 2 nitrogen atoms (the 6-membered complex aromatic ring). The rings are bonded via carbon and may be substituted with one or more groups selected from X'' that may be identical or different); Q'is H; one or more halogens, CN, C₁-C₃Alkoxy, C₁-C₆Alkoxycarbonyl, or one or more halogens, CN, NO₂, C₁-C₄Alkyl, C₁-C₄Haloalkyl, C₁-C₄Alkylsulfonyl or C₁-C₄May be substituted with an alkylsulfinyl group May be substituted with phenyl C₁-C₆Alkyl; C₂-C₆Alkenyl; C₂-C₆Alkynyl; or phenyl selected from X'', which may be substituted with 1 to 3 groups, which may be the same or different; R₂₃, R₂₄, R₂₅, R₂₆, R₂₇, R₂₈And R₂₉Are independently H or C₁-C₄Alkyl; as well as dotted line arrangement<img file="JP2003517455A_D0006.tif" />Indicates a double bond or a single bond (ie, CN or C = N] It is a compound represented by or a stereoisomer thereof. [0021] [0021]

More preferred neuronal sodium channel antagonist compounds of the present invention have a dotted line arrangement.<img file="JP2003517455A_D0007.tif" />Is a compound of formula IV or V showing a double bond. [0022]

Other preferred neuronal sodium channel antagonist compounds suitable for use in the compositions of the present invention have W of O; X'' and Y'' of H or C, respectively.₁-C₆Haloalkyl; m is 1; R₂₃, R₂₄, R₂₅, R₂₆And R₂₇Are each H; G is a phenyl optionally substituted with one or more halogen atoms; Q'may be substituted with one phenyl or halophenyl group, halophenyl or C.₁-C₄Alkyl and dotted line arrangement<img file="JP2003517455A_D0008.tif" />Is a compound of formula IV or V or a stereoisomer thereof, which exhibits a double bond. [0023]

As the second active ingredient of the insecticide composition of the present invention, group A: 1) Pyrethroid compounds known to have insecticidal activity such as cypermethrin, cihalomethrin, cypermethrin, permethrin; 2) Pyrethroid compounds known to have insecticidal activity such as etofenprox and silafluofen; 3) Recombinant nucleopolyhedrovirus capable of expressing neurotoxins such as insect toxins, preferably Androctonus australis insect toxins (AaIT), such as Hz NPV-AaIT; 4) Organic phosphate compounds known to have insecticidal activity such as profenophos, acephate, sulprofos, malathion, diazinone, methyl parathion, terbufos; 5) Carbamic acid ester compounds known to have insecticidal activity such as methomyl, thiodicalve, phenothiocarb; 6) Form amidine compounds known to have insecticidal activity such as amitraz, chlordimeform, hydramethylnon, chlorfenamidine; 7) Macrocyclic lactone compounds known to have insecticidal activity such as spinosad, avermectin, emamectin, milbemectin, nemadetin, moxidectin; 8) Amidinohydrazone compounds known to have insecticidal activity such as hydramethylnon; 9) GABA antagonist compounds known to have insecticidal activity such as fipronil and endosulfan; 10) Acetylcholine receptor ligand compounds known to have insecticidal activity such as imidacloprid, acetamiprid, nitenpyram, thiamethoxam; One or more compounds selected from. [0024]

A description of the commercially available compounds listed above can be found in particular in The Pesticide Manual, 11th Edition, British Crop Protection Council (1997). Descriptions of recombinant nucleopolyhedroviruses capable of expressing insect toxins include Treacy et al., Proceedings Beltwide Cotton Conference (1999), pp 1076-1083. [0025]

The preferred composition of the present invention is a composition containing a combination of a sodium channel antagonist compound of a nerve cell of formula I or formula III and one or more compounds selected from group A. [0026]

A more preferred composition of the invention is W for O; X for trifluoromethoxy at 4-position; Y for trifluoromethyl at 3-position; Z for CN at 4-position; A. Is CH₃Is; n is 0; m, p and q are 1 independently; R and R₁Are H independently; Z'is Cl; R₃₃And G are CO independently₂CH₃And Q is p- (trifluoromethoxy) phenyl; dotted line arrangement<img file="JP2003517455A_D0009.tif" />Is a composition comprising a combination of a compound of formula I or formula III, which exhibits a double bond, and one or more compounds selected from group A. [0027]

Each of the compounds of formulas I, II, III, IV and V contains an asymmetric center that can be represented sterically in the R or S form. The present invention also includes R-forms, S-forms or mixtures containing R-forms and S-forms in any ratio. For compounds of formula III, the S form is preferred. [0028]

Advantageously, a sodium channel antagonist compound of neurons of formulas I, II, III, IV or V or a mixture thereof can be formulated with a second insecticidal active ingredient and optionally other conventional pharmaceutical adjuvants. .. The formulation can be dispersed in a solid or liquid diluent as a diluent spray or solid powder or powder concentrate for application to insects, their food supplies, breeding grounds or habitats. [0029]

The active ingredient of the compositions of the invention can be a moistening powder, an emulsion concentrate, an aqueous or liquid fluid suspension concentrate, or a conventional formulation used as an insect control agent. As such, they can be formulated separately and can also be tank mixed in the field with water or other inexpensive liquids for application as a liquid spray mixture. Separately formulated compositions can also be applied continuously. [0030]

Advantageously, the compositions of the invention are combined in synergistically effective amounts of neuronal sodium channel antagonists, one or more compounds selected from Group A, and solid or liquid edible nutrients. It can be formulated as a bait composition containing. Preferred bait compositions may contain 0.01% to 20% by weight of active ingredient, preferably a neuronal sodium channel antagonist in combination with hydramethylnon. [0031]

In practical use, the compositions of the present invention may be applied to plant leaves or plant stems, or insect habitats, or hygienic pest locations, in a diluted spray prepared from any of the above formulations. Can be applied as. The ratio of the essential active ingredient in the composition of the present invention is one or more compounds selected from group A of about 0.01 to 100 parts by weight of the sodium channel antagonist of nerve cells in an amount of about 1 part by weight. [0032]

The compositions of the present invention are excellent pesticide compositions and are particularly useful in controlling crop horticultural pests, hygienic pests, or wood-eating pests. The composition includes legumes such as soybeans, pods, pea and kidney beans, as well as flowering ornamental plants such as cotton, forage crops, abrana crops, leafy vegetables, tobacco, hops, tomatoes, potatoes and kiku. Protection of growing and harvested plants from insect damage, including vine crops such as grapes, pumpkins, pumpkins or melons, and fruit trees such as cherry, peach, apple or citrus. Very effective for. [0033]

The synergistic pesticide compositions of the present invention are Helicoverpa zea (cotton bollworm), Heliothis virescens (tobacco budworm), Leptinotarsa desemrineata ( Against a wide range of lepidopteran and coleopteran insects such as Leptinotarsa decemlineata (Colorado potato beetle), Diabrotica spp. (Corn rootworm) It is known to have high activity. [0034]

Beneficially, the compositions of the present invention include Diptera (eg, fly, mosquito, etc.), Hymenoptera (eg, ants, parasitic bees, bees, etc.), Cockroach (Blattaria, etc.). ) (For example, cockroach) and other hygienic or public hymenopteral pests are useful for prevention and control. [0035]

Furthermore, the compositions of the present invention are particularly useful for the prevention and control of wood-eating insects such as termites (Isoptera), carpenter ants (Dictyoptera), and tree-destroying beetles (Coleoptera). Is. [0036]

These and other advantages of the present invention will become more apparent from the examples described below. These examples are provided merely as an explanation of the present invention and are not intended to be construed as limiting the present invention. [0037]

Example Example 1 Phase of combination of neuronal sodium channel antagonist and second pesticide Evaluation of riding insecticidal effect In this evaluation, Heliothis zea, Heliothis virescens, and pyrethroid-resistant Heliothis virescens larvae to be used are obtained from laboratory colonies. Pyrethroid-resistant H. virescens is derived from the PEG strain [Campannola &amp; Plapp, Proceedings of Beltwide Cotton Conference (1988)]. [0038]

The cotton leaves are soaked in an acetone / water (1: 1) solution of the test compound or a solution of the test compound combination for about 3 seconds. After soaking, the leaves are air dried for 2-3 hours. A plastic bioassay tray (4.0 x 4.0 x 2.5 cm) containing multiple open wells is used as the test area. Cut pieces of treated leaves, moistened cotton dental gauze, and one 3rd instar larva were placed in each well and covered with a sticky, perforated, clear plastic sheet, approximately. Hold at 27 ° C for a predetermined period of time under constant fluorescence. Larval mortality / morbidity is assessed 5 days after treatment. All treatments are repeated 4-5 times in a randomized complete block design with 16-32 larvae per treatment. LC of each process using normal log probit analysis₅₀To measure. [0039]

Using the above protocol, neuronal sodium channel antagonists (Compound A) are evaluated alone in dose ratios of 0.1 ppm, 1.0 ppm and 10.0 ppm, and in combination with a second pesticide compound of 1.0 ppm. The processes that can be used are shown in Table 1. [0040]

[table 1]

<img file="JP2003517455A_D0010.tif" /> 【0041】

Example 2 Nerve cell sodium channel antagonist in combination with amidinohydrazone Evaluation of synergistic insecticidal effect A mature male German cockroach (Blattella germanica) is used in this evaluation. For each test, 4.0 g of ground Purina Dog Chow (Hi-Pro Glo®) is treated with an acetone solution of the test compound alone or in combination with a second test compound. After treatment, acetone was evaporated and the treated dog solid feed was made from a folded sheet of blotting paper placed in a plastic box (16''L x 11''W x 6''H). Place in a 3/4 ounce plastic cup placed in the harborage). Fit an ounce narrow-mouthed bottle with two pieces of dental gauze in the mouth into this plastic box (test area). A control box is prepared in the same manner using ground dog solid feed treated with reagent grade acetone. Repeat each process 3 times. Each test area contains 20 healthy mature male cockroaches bred in an insect laboratory. The obtained data are shown in Table 2. [0042]

[Table 2]

<img file="JP2003517455A_D0011.tif" /> As can be seen from the data shown in Table 2, the combination of neuronal sodium channel antagonists and amidinohydrazone pesticides exhibits synergistic insect control. [0043]

Example 3 Nerve cell sodium channel antagonists and recombination capable of expressing insect toxins Evaluation of synergistic insecticidal effect in combination with nucleopolyhedrovirus In this evaluation, Helicoverpa zea larvae are obtained from laboratory colonies. Dissolve the test compound in 1: 1 v / v acetone / water. A plastic bioassay tray (CD International, Pitman, NJ) is used as the test area. Each tray contains 32 opening wells (4.0 x 4.0 x 2.5 cm). Inject a portion (5 ml) of wheat malt-soybean powder-based artificial feed (Southland Products, Lake Village, AR) into each well. After solidifying the feed, pipette 0.4 ml of the test solution onto the surface of the feed in each well. Lift the tray and gently tilt it from side to side to spread the test solution evenly over the surface of the feed. The tray is then held in the aerated area for about 2 hours until the feed surface is depleted of water. Then one 4-day-old H. Place zea larvae on the feed surface of each well. After the invasion of the larvae, each well is covered with a sticky, perforated, clear plastic sheet. [0044]

All test areas are kept at a temperature of about 27 ° C. under constant fluorescence during the assay. Larval mortality is measured on days 2, 3, 4 and 7 of treatment. If the larvae hardly moved when shaken in the feed tray, the larvae were considered dead. A total of 32 insects were tested for each treatment. The obtained data are shown in Table 3. [0045]

[Table 3]

<img file="JP2003517455A_D0012.tif" /> As can be seen from the data shown in Table 3, the combination of neuronal sodium channel antagonists and recombinant nucleopolyhedrovirus capable of expressing insect toxins exhibits synergistic insect control.