Improved Insecticide Composition and Pest Control Method

Abstract

The present invention relates to a method for controlling winged insect pests, comprising exposing the pests to an effective amount of a combination of a β-diketone compound and at least one second insecticide selected from pyrethroids or pyrethrins, wherein both the β-diketone compound and the at least one second insecticide are used in sub-effective amounts. The present invention also relates to a composition for controlling winged insect pests, comprising a β-diketone compound and at least one second insecticide selected from pyrethroids or pyrethrins, wherein both the β-diketone compound and the at least one pyrethroid or pyrethrin are included in sub-effective amounts.

Description

Technical Field

[0001] Related Applications

[0001] This application claims the benefit of Australian Provisional Patent Application No. 2022901767, filed on June 24, 2022, and Australian Provisional Patent Application No. 2023901199, filed on April 23, 2023, the entire contents of both applications being incorporated herein by reference.

[0002]

[0002] The present invention generally relates to methods and compositions for controlling winged insect pests. More specifically, the present invention relates to methods and compositions for controlling winged insect pests that involve using a combination of a β-diketone compound and at least one second insecticide selected from pyrethroids or pyrethrins.

Background Art

[0003]

[0003] Effective insect control is essential in many industries, particularly agriculture in food and livestock production. Ineffective insect control or the spread of insects can lead to complete crop destruction or a significant reduction in animal populations due to insect feeding, diseases, and the spread of infections. Insect control within the home is similarly essential to reduce the spread of insect-borne infections and diseases.

[0004]

[0004] In particular, winged insects are the focus of many insect control strategies. Winged insects with the ability to fly can be particularly problematic as they have the ability to invade a wider area and move to new regions. Winged insects often reproduce throughout their life cycle, including larvae, which can have a devastating impact on crops through feeding and can parasitize animal populations, causing health concerns in the home environment. Winged insects also carry many infections and diseases that are dangerous to humans and animals. A typical example is the mosquito, which is considered to be the leading cause of human death worldwide through the infections and diseases it carries and transmits.

[0005]

[0005] Synthetic insecticides are most commonly used for insect control. Synthetic insecticides with various modes of action have been used for decades to control insect pests. However, synthetic insecticides are associated with many problems, such as the development of resistance in target pest populations, toxicity to animals and humans, non-biodegradability, environmental persistence, and environmental toxicity due to water pollution. As a result, many insecticides that were effectively used in the past are now used less frequently or not at all. This has reduced the number of insecticides available for controlling insect pests.

[0006]

[0006] Resistance in target populations is a particular problem. Since 1945, it is estimated that up to 1,000 pest species have acquired resistance to one or more insecticides. Attempts to counter this include increasing the amount of insecticide used to overcome the development of new resistance, but this only exacerbates other problems including toxicity and may be an effective strategy temporarily, but ultimately may accelerate the development of resistance in insect populations.

[0007]

[0007] A good example is the use of pyrethroids. Insect control has long been highly dependent on pyrethroids, and resistance has now become apparent and is increasing in many insect species. In fact, some species and strains of insects are reported to be completely resistant to one or more pyrethroids. Suitable alternatives are few, either existing or newly available.

[0008]

[0008] Therefore, it is advantageous to provide new alternative insecticide compositions and methods that can improve the control of insects, particularly winged insects, for example, at potentially reduced application rates, to address at least one of the above problems.

Summary of the Invention

Means for Solving the Problems

[0009]

[0009] The present invention is based at least in part on the discovery that the β-diketone compounds described herein are particularly effective in controlling winged insects when used in combination with a pyrethroid or pyrethrin. This discovery has been practiced in the pest control compositions and methods described herein.

[0010]

[0010] In one aspect, the present invention provides a method for controlling pests with a compound of formula (I):

[0011]

Chemical formula

[0012] (wherein, X and Y are each independently selected from oxygen, sulfur, -N-R4, or one of C=X and C=Y is CH2; A is (C=O)R1, (C=S)R1, OR2, SR2, (CR3NR4R5), C(R3)2OR2, NR4R5, (C=N-R4)R1, N=O, N(=O)2, NR4OR2, or SO4R2; B is H, C1-C 10 alkyl, C2-C 10 alkenyl, aryl or heteroaryl; C, D, E and F are each independently H, C1-C 10 alkyl, C2-C 10 arylalkyl, C3-C6 cycloalkyl, C2-C 10 alkenyl, C2-C 10 heteroarylalkyl, C2-C 10 haloalkyl, C2-C 10 dihaloalkyl, C2-C 10 trihaloalkyl, C2-C 10 haloalkoxy, OR2, SR2, (CR3NR4R5), NR4R5, (C=N-R4)R1, N=O, N(=O)2, NR4OR2 and SO4R2; R1 is H, C1-C 10 alkyl, C2-C 10 arylalkyl, C3-C6 cycloalkyl, C2-C 10Alkenyl, C2-C 10 Heteroarylalkyl, C1-C 10 Haloalkyl, C1-C 10 Dihaloalkyl, C2-C 10 Trihaloalkyl, C2-C 10 Haloalkoxy, C1-C 10 Hydroxyalkyl, C1-C 10 Thioalkyl, C1-C 10 Selected from nitroalkyl, OR2, SR2, (CR3NR4R5), NR4R5, (C=N-R4)R6, N=O, N(=O)2, NR4OR7 and SO4R7; R2 is H, C1-C 10 Alkyl, C2-C 10 Arylalkyl, C3-C6 cycloalkyl, C2-C 10 Alkenyl, C2-C 10 Heteroarylalkyl, C2-C 10 Haloalkyl, C2-C 10 Dihaloalkyl, C2-C 10 Selected from trihaloalkyl, (CR3NR4R5), NR4R5, (C=N-R4)R6, N=O, N(=O)2 and NR4OR7; R3 is H, C1-C 10 Alkyl, C2-C 10 Arylalkyl, C3-C6 cycloalkyl, C2-C 10 Alkenyl, C2-C 10 Heteroarylalkyl, C2-C 10 Haloalkyl, C2-C 10 Dihaloalkyl, C2-C 10 Trihaloalkyl, C2-C 10 Selected from haloalkoxy, OR7, SR7, (CR8NR4R5), NR4R5, (C=N-R4)R6, N=O, N(=O)2, NR4OR7 and SO4R7; R4 and R5 are independently H, C1-C 10 Alkyl, C2-C 10 Arylalkyl, C3-C6 cycloalkyl, C2-C 10 Alkenyl, C2-C 10 Heteroarylalkyl, C2-C 10Haloalkyl, C2-C 10 Dihaloalkyl, C2-C 10 Trihaloalkyl, OR7, or SR7; R6 is H, C1-C 10 Alkyl, C2-C 10 Arylalkyl, C3-C6 cycloalkyl, C2-C 10 Alkenyl, C2-C 10 Heteroarylalkyl, C2-C 10 Haloalkyl, C2-C 10 Dihaloalkyl, C2-C 10 Trihaloalkyl, C2-C 10 Haloalkoxy, OR7, SR7, (CR8NR9R 10 ), NR9N 10 and NR9OR7; R7 is H, C1-C 10 Alkyl, C2-C 10 Arylalkyl, C3-C6 cycloalkyl, C2-C 10 Alkenyl, C2-C 10 Heteroarylalkyl, C2-C 10 Haloalkyl, C2-C 10 Dihaloalkyl, C2-C 10 Trihaloalkyl; R8 is H, C1-C 10 Alkyl, C2-C 10 Arylalkyl, C3-C6 cycloalkyl, C2-C 10 Alkenyl, C2-C 10 Heteroarylalkyl, C2-C 10 Haloalkyl, C2-C 10 Dihaloalkyl, C2-C 10 Trihaloalkyl, OR 11 , SR 11 and NR9R 10 ; R9 and R 10 are independently H, C1-C 10 Alkyl, C2-C 10 Arylalkyl, C3-C6 cycloalkyl, C2-C 10 Alkenyl, C2-C 10Heteroarylalkyl, C2-C 10 Haloalkyl, C2-C 10 Dihaloalkyl, C2-C 10 Trihaloalkyl, OR 12 and SR 12 selected from; R 11 and R 12 are independently H, C1-C 10 alkyl, C2-C 10 arylalkyl, C3-C6 cycloalkyl, C2-C 10 alkenyl, C2-C 10 heteroarylalkyl, C2-C 10 haloalkyl, C2-C 10 dihaloalkyl and C2-C 10 trihaloalkyl selected from; and at least one second insecticide is selected from pyrethroid or pyrethrin) A method for controlling winged insect pests, comprising exposing to an effective amount of a combination of a β-diketone compound of formula (I) and at least one second insecticide, wherein both the β-diketone compound of formula (I) and at least one second insecticide are used in less than an effective amount.

[0013] In another aspect, the present invention provides a composition for controlling winged insect pests, comprising a β-diketone compound of formula (I) as defined herein and at least one second insecticide selected from pyrethroid or pyrethrin, wherein both the β-diketone compound and at least one pyrethroid or pyrethrin are included in less than an effective amount.

[0014]

[0012] In another aspect, the present invention provides a kit for use in a method of controlling winged insect pests, comprising a β-diketone compound of formula (I) as defined herein, at least one second insecticide selected from a pyrethroid or a pyrethrin, and instructions for exposing a winged insect pest to a combination of the β-diketone compound of formula (I) and at least one pyrethroid or pyrethrin using less than an effective amount of both the β-diketone compound and the pyrethroid or pyrethrin.

Brief Description of the Drawings

[0015]

Figure 1

[0013] Figure 1 is a graph showing the toxicity of the Qcide formulation and permethrin (SP positive control) against L3 larvae of the Aedes aegypti LVP (SP susceptible) strain in a larval dose-response assay after 24, 48, and 72 hours.

Figure 2

[0014] Figure 2 is a graph showing the toxicity of the Qcide formulation and permethrin (SP positive control) against L3 larvae of the Aedes aegypti PRS (SP resistant) strain in a larval dose-response assay after 24, 48, and 72 hours.

Figure 3

[0015] Figure 3 is a graph showing the toxicity of the Qcide formulation and permethrin (SP positive control) against 3- to 5-day-old adult female mosquitoes of the Aedes aegypti LVP (SP susceptible) strain at 24 and 48 hours.

Figure 4

[0016] Figure 4 is a graph showing the toxicity of the Qcide formulation and permethrin (SP positive control) against 3- to 5-day-old adult female mosquitoes of the Aedes aegypti PRS (SP resistant) strain at 24 and 48 hours.

Figure 5

[0017] Figure 5 is a graph showing the toxicity of the Qcide formulation, permethrin, and deltamethrin (SP positive control) against L3 larvae of the Aedes aegypti LVP (SP susceptible) and PRS (SP resistant) strains in a mortality time assay.

Figure 6

[0018] Figure 6 is a graph representing a dose-mortality assay evaluating the synergistic effect of combined administration of the synthetic pyrethroid, permethrin (5 dose points), and Qcide (500 EW) at a single dose point of LC10 on Aedes aegypti L3 larvae LVP (SP-sensitive) strain at 24 and 48 hours after exposure.

Figure 7

[0019] Figure 7 is a graph representing a dose-mortality assay evaluating the synergistic effect of combined administration of the synthetic pyrethroid, permethrin (5 dose points), and Qcide (500 EW) at a single dose point of LC10 on Aedes aegypti L3 larvae PRS (SP-resistant) strain at 24 and 48 hours after exposure.

Figure 8

[0020] Figure 8 is a graph representing a dose-mortality assay evaluating the synergistic effect of combined administration of the synthetic pyrethroid, permethrin (5 dose points), and Qcide (500 EW) at a single dose point of LC20 on Aedes aegypti L3 larvae LVP (SP-sensitive) strain at 24 and 48 hours after exposure.

Figure 9

[0021] Figure 9 is a graph representing a dose-mortality assay evaluating the synergistic effect of combined administration of the synthetic pyrethroid, permethrin (5 dose points), and Qcide (500 EW) at a single dose point of LC20 on Aedes aegypti L3 larvae PRS (SP-resistant) strain at 24 and 48 hours after exposure.

Figure 10

[0022] Figure 10 is a graph showing the KD50 value, KD90 value, and 24-hour mortality of Musca domestica.

Figure 11

[0023] Figure 11 is a photograph of a plastic storage container with mesh attached to each opening (left, side view on the base of the Potter Tower spray platform, right, top view).

Figure 12

[0024] Figure 12 is a graph showing the average knockdown rate, moribund rate, and mortality rate of Musca domestica after spraying a combination of Qcide and pyrethrin over 96 hours, compared with the case of spraying Qcide and pyrethrin individually.

Mode for Carrying Out the Invention

[0016]

[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field of the present invention. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described. For the purposes of the present invention, several terms are defined throughout this specification.

[0017]

[0026] The present invention contemplates a method and a composition for controlling winged insect pests using a β-diketone compound of formula (I) described herein and at least one second insecticide selected from a pyrethroid or pyrethrin. β-diketone compound of formula (I)

[0027] The β-diketone compound of formula (I) is defined as follows.

[0018]

Chemical formula

[0019] (In the formula, X and Y are each independently selected from oxygen, sulfur - N - R4, or one of C = X and C = Y is CH2; A is (C = O)R1, (C = S)R1, OR2, SR2, (CR3NR4R5), C(R3)2OR2, NR4R5, (C = N - R4)R1, N = O, N(=O)2, NR4OR2, or SO4R2; B is H, C1 - C 10 alkyl, C2 - C 10 alkenyl, aryl or heteroaryl; C, D, E, and F are each independently H, C1-C 10 alkyl, C2-C 10 arylalkyl, C3-C6 cycloalkyl, C2-C 10 alkenyl, C2-C 10 heteroarylalkyl, C2-C 10 haloalkyl, C2-C 10 dihaloalkyl, C2-C 10 trihaloalkyl, C2-C 10 haloalkoxy, OR2, SR2, (CR3NR4R5), NR4R5, (C=N-R4)R1, N=O, N(=O)2, NR4OR2, and SO4R2; R1 is H, C1-C 10 alkyl, C2-C 10 arylalkyl, C3-C6 cycloalkyl, C2-C 10 alkenyl, C2-C 10 heteroarylalkyl, C1-C 10 haloalkyl, C1-C 10 dihaloalkyl, C2-C 10 trihaloalkyl, C2-C 10 haloalkoxy, C1-C 10 hydroxyalkyl, C1-C 10 thioalkyl, C1-C 10 nitroalkyl, OR2, SR2, (CR3NR4R5), NR4R5, (C=N-R4)R6, N=O, N(=O)2, NR4OR7, and SO4R7; R2 is H, C1-C 10 alkyl, C2-C 10 arylalkyl, C3-C6 cycloalkyl, C2-C 10 alkenyl, C2-C 10 heteroarylalkyl, C2-C 10 haloalkyl, C2-C 10 dihaloalkyl, C2-C 10 trihaloalkyl, (CR3NR4R5), NR4R5, (C=N-R4)R6, N=O, N(=O)2, and NR4OR7; R3 is H, C1-C 10 alkyl, C2-C10 Arylalkyl, C3-C6 cycloalkyl, C2-C 10 Alkenyl, C2-C 10 Heteroarylalkyl, C2-C 10 Haloalkyl, C2-C 10 Dihaloalkyl, C2-C 10 Trihaloalkyl, C2-C 10 Selected from haloalkoxy, OR7, SR7, (CR8NR4R5), NR4R5, (C=N-R4)R6, N=O, N(=O)2, NR4OR7 and SO4R7; R4 and R5 are independently H, C1-C 10 Alkyl, C2-C 10 Arylalkyl, C3-C6 cycloalkyl, C2-C 10 Alkenyl, C2-C 10 Heteroarylalkyl, C2-C 10 Haloalkyl, C2-C 10 Dihaloalkyl, C2-C 10 Selected from trihaloalkyl, OR7 and SR7; R6 is H, C1-C 10 Alkyl, C2-C 10 Arylalkyl, C3-C6 cycloalkyl, C2-C 10 Alkenyl, C2-C 10 Heteroarylalkyl, C2-C 10 Haloalkyl, C2-C 10 Dihaloalkyl, C2-C 10 Trihaloalkyl, C2-C 10 Haloalkoxy, OR7, SR7, (CR8NR9R 10 )、NR9N 10 And selected from NR9OR7; R7 is H, C1-C 10 Alkyl, C2-C 10 Arylalkyl, C3-C6 cycloalkyl, C2-C 10 Alkenyl, C2-C 10 Heteroarylalkyl, C2-C 10 Haloalkyl, C2-C 10 Dihaloalkyl, C2-C 10 Selected from trihaloalkyl; R8 is selected from H, C1-C 10 alkyl, C2-C 10 arylalkyl, C3-C6 cycloalkyl, C2-C 10 alkenyl, C2-C 10 heteroarylalkyl, C2-C 10 haloalkyl, C2-C 10 dihaloalkyl, C2-C 10 trihaloalkyl, OR 11 and SR 11 and NR9R 10 and is selected from; R9 and R 10 are independently selected from H, C1-C 10 alkyl, C2-C 10 arylalkyl, C3-C6 cycloalkyl, C2-C 10 alkenyl, C2-C 10 heteroarylalkyl, C2-C 10 haloalkyl, C2-C 10 dihaloalkyl, C2-C 10 trihaloalkyl, OR 12 and SR 12 and is selected from; R 11 and R 12 are independently selected from H, C1-C 10 alkyl, C2-C 10 arylalkyl, C3-C6 cycloalkyl, C2-C 10 alkenyl, C2-C 10 heteroarylalkyl, C2-C 10 haloalkyl, C2-C 10 dihaloalkyl and C2-C 10 trihaloalkyl (selected from).

[0020]

[0028] As used herein, the term "alkyl" refers to a straight-chain or branched saturated hydrocarbon group having 1 to 10 carbon atoms. An alkyl group may have the specified number of carbon atoms. For example, C1-C6 alkyl includes alkyl groups having 1, 2, 3, 4, 5, or 6 carbon atoms in a straight-chain or branched arrangement. Examples of suitable alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 4-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 5-methylpentyl, 2-ethylbutyl, 3-ethylbutyl, heptyl, octyl, nonyl, and decyl.

[0021]

[0029] As used herein, the term "cycloalkyl" refers to a saturated cyclic hydrocarbon. A cycloalkyl group may have the specified number of carbon atoms. For example, C3-C6 cycloalkyl includes cycloalkyl groups having 3, 4, 5, or 6 carbon atoms. Examples of suitable cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0022]

[0030] As used herein, the term "alkenyl" refers to a straight-chain or branched hydrocarbon group having one or more double bonds between carbon atoms and having 2 to 10 carbon atoms. An alkenyl group can have a specific number of carbon atoms. For example, C2-C6 alkenyl includes alkenyl groups having 2, 3, 4, 5, or 6 carbon atoms in a straight-chain or branched arrangement. Examples of suitable alkenyl groups include, but are not limited to, ethenyl, propenyl, isopropenyl, butenyl, butadienyl, pentenyl, pentadienyl, hexenyl, hexadienyl, heptenyl, octenyl, nonenyl, and decenyl.

[0023]

[0031] As used herein, the term "aryl" refers to a stable monocyclic, bicyclic, or tricyclic carbocyclic ring system having up to 7 atoms in each ring and at least one ring being aromatic. Examples of such aryl groups include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, indanyl, fluorenyl, phenanthrenyl, biphenyl, and binaphthyl.

[0024]

[0032] As used herein, the term "heteroaryl" refers to a stable monocyclic, bicyclic, or tricyclic ring having up to 7 atoms in each ring, at least one ring being aromatic, and at least one ring containing 1 to 4 heteroatoms selected from the group consisting of O, N, and S. Examples of suitable heteroaryl groups include, but are not limited to, acridinyl, carbazolyl, cinnolinyl, quinoxalinyl, quinazolinyl, pyrazolyl, indolyl, isoindolyl, 1H,3H-1-oxoisoindolyl, benzotriazolyl, furanyl, thienyl, thiophenyl, benzothienyl, benzofuranyl, benzodioxane, benzodioxin, quinolinyl, isoquinolinyl, oxazolyl, isoxazolyl, imidazolyl, pyrazinyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl, tetrahydroquinolinyl, thiazolyl, isothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,4-oxadiazolyl, 1,2,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,4,5-tetrazinyl, and tetrazolyl. Certain heteroaryl groups have 5- or 6-membered rings such as pyrazolyl, furanyl, thienyl, oxazolyl, indolyl, isoindolyl, 1H,3H-1-oxoisoindolyl, isoxazolyl, imidazolyl, pyrazinyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl, thiazolyl, isothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,4-oxadiazolyl, and 1,2,4-thiadiazolyl.

[0025]

[0033] As used herein, the term "haloalkyl" refers to an alkyl group in which one or more hydrogen atoms are replaced by halogen atoms. A haloalkyl group can have a specified number of halogen substituents, such as, for example, dihaloalkyl (2) or trihaloalkyl (3). Examples of suitable haloalkyl groups include, but are not limited to, fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 2,2-fluoroethyl, 1,1,2-trifluoroethyl, 2,2,2-trifluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, 4-fluorobutyl, 4,4-difluorobutyl, 4,4,4-trifluorobutyl, 5-fluoropentyl, 5,5-difluoropentyl, 5,5,5-trifluoropentyl, 6-fluorohexyl, 6,6-difluorohexyl or 6,6,6-trifluorohexyl, chloromethyl, dichloromethyl, trichloromethyl, 1-chloroethyl, 2-chloroethyl, 1,1-dichloroethyl, 2,2-chloroethyl, 1,1,2-trichloroethyl, 2,2,2-trichloroethyl, 3-chloropropyl, 3,3-dichloropropyl, 3,3,3-trichloropropyl, 4-chlorobutyl, 4,4-dichlorobutyl, 4,4,4-trichlorobutyl, 5-chloropentyl, 5,5-dichloropentyl, 5,5,5-trichloropentyl, 6-chlorohexyl, 6,6-dichlorohexyl or 6,6,6-trichlorohexyl, bromomethyl, dibromomethyl, tribromomethyl, 1-bromoethyl, 2-bromoethyl, 1,1-dibromoethyl, 2,2-dibromoethyl, 1,1,2-tribromoethyl, 2,2,2-tribromoethyl, 3-bromopropyl, 3,3-dibromopropyl, 3,3,3-tribromopropyl, 4-bromobutyl, 4,4-dibromobutyl, 4,4,4-tribromobutyl, 5-bromopentyl, 5,5-dibromopentyl, 5,5,5-tribromopentyl, 6-bromohexyl, 6,6-dibromohexyl or 6,6,6-tribromohexyl, etc.

[0026]

[0034] The term "halo" refers to fluorine, chlorine, bromine and / or iodine.

[0035] As used herein, the terms "hydroxyalkyl", "thioalkyl" and "nitroalkyl" each refer to an alkyl group in which one or more hydrogen atoms are replaced by a hydroxyl group, a thiol group or a nitro group, respectively.

[0027]

[0036] As used herein, the term "alkoxy" refers to an oxygen substituent substituted with an alkyl group. Examples of suitable alkoxy groups include, but are not limited to, -OCH3, -OCH2CH3, -O(CH2)2CH3, -OCH(CH3)2, -O(CH2)3CH3, -OCH2CH(CH3)2, -OC(CH3)3, -O(CH2)4CH3 and -O(CH2)5(CH3).

[0028]

[0037] Compounds of formula (I) classified as β-diketones herein refer to the core cyclohexene β-dione motif of the structural formula defining the compounds of formula (I). Nevertheless, the β-diketone compounds of formula (I) may exist in the form of tautomers containing the core cyclohexene β-dione motif, and many can exist as different geometric isomers and diastereomers. The β-diketone compounds of the present invention are to be construed as including all tautomers, individual isomers and mixtures of isomers.

[0029]

[0038] Similarly, the β-diketone compound of formula (I) may exist as a solvate such as a hydrate and / or a salt. Examples of suitable salts include monovalent metal salts such as sodium salts and potassium salts, divalent metal salts such as calcium salts, magnesium salts, iron salts, and copper salts, and ammonium salts such as isopropylammonium salts, trialkylammonium salts, and tetraalkylammonium salts, but are not limited thereto. Examples of suitable salts include agriculturally acceptable salts including salts of agriculturally acceptable inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, carbonic acid, boric acid, sulfamic acid, and hydrobromic acid, or salts of agriculturally acceptable organic acids such as acetic acid, propionic acid, butyric acid, tartaric acid, maleic acid, hydroxymaleic acid, fumaric acid, maleic acid, citric acid, lactic acid, mucic acid, gluconic acid, benzoic acid, succinic acid, oxalic acid, phenylacetic acid, methanesulfonic acid, toluenesulfonic acid, benzenesulfonic acid, salicylic acid, sulfanilic acid, aspartic acid, glutamic acid, edetic acid, stearic acid, palmitic acid, oleic acid, lauric acid, pantothenic acid, tannic acid, ascorbic acid, and valeric acid. All solvates and salts of the β-diketone compound of the present invention are intended to be included.

[0030]

[0039] The β-diketone compound of the present invention can be produced according to a method similar to the methods known in the art. Exemplary methods are disclosed, for example, in European Patent Application Publication No. 338992, European Patent Application Publication No. 336898, U.S. Patent No. 4,202,840, U.S. Patent No. 4,869,748, European Patent Application Publication No. 186118, European Patent Application Publication No. 186119, European Patent Application Publication No. 186120, U.S. Patent No. 4,695,673, U.S. Patent No. 4,780,127, U.S. Patent No. 4,921,526, U.S. Patent No. 5,006,150, U.S. Patent No. 5,545,607, U.S. Patent No. 5,925,795, U.S. Patent No. 5,990,046, U.S. Patent No. 6,218,579, European Patent Application Publication No. 249150, European Patent Application Publication No. 137963, European Patent Application Publication No. 394889, European Patent Application Publication No. 506907, and European Patent No. 135191.

[0031]

[0040] The β-diketone compounds of the present invention can be obtained from natural sources, particularly plants containing volatile oils, for example by extraction. When available, this is preferred. Volatile oil-containing plants that may produce the β-diketone compounds of formula (I) may be plants of the Myrtaceae family, particularly of the genera Eucalyptus, Baeckea and Melaleuca. Representative and preferred plant species include (in the case of tasmanone) Eucalyptus tenuiramis, Baeckea frutescens (also called agglomeron), Eucalyptus risdonii and Eucalyptus cloeziana, (in the case of lateriticone) Eucalyptus lateritica and (in the case of platyphyllol) Melaleuca cajuputi. Extraction methods are known to those skilled in the art and include, for example, steam distillation of the plant biomass.

[0032]

[0041] In a preferred embodiment for producing an extract containing tasmanone, the plant is selected from one or more of the Eucalyptus cloeziana varieties designated BGTECLD29, BGTECLD14 and BGTECLD30, which are the subject of Australian Plant Breeder's Rights application numbers 2022 / 268 filed on 29 November 2022, 2022 / 267 filed on 29 November 2022 and 2022 / 266 filed on 26 November 2022, respectively. Samples of BGTECLD29, BGTECLD14 and BGTECD30 are stored at James Cook University, Smithfield, Cairns, QLD4870 and Plant Biotech, 41 Menary Road, Coes Creek, QLD4560.

[0033]

[0042] The β-diketone compound of formula (I) can be used as a substantially purified synthetic compound, a substantially purified isolated compound, or a crude extract, and can be used as it is directly obtained by the methods described herein, or can be incorporated into a composition for use by the methods described herein. When used as a crude extract, preferably, the β-diketone compound of formula (I) is present in a high proportion in the crude extract. That is, at least about 70% by weight, preferably at least about 80% by weight, 85% by weight or 90% by weight, preferably at least about 91% by weight, 92% by weight, 93% by weight, 94% by weight, more preferably at least about 95% by weight. "Substantially purified" means that the β-diketone compound of formula (I) is present in an amount of at least about 97% by weight, preferably at least about 98% by weight, 99% by weight, 99.5% by weight, 99.8% by weight, preferably at least about 99.9% by weight.

[0034]

[0043] Often, the plant extract is a liquid (often an oil), in which case the plant extract may contain the β-diketone compound of formula (I) in an amount of at least about 50% by volume (500 g / L), preferably at least about 55% by volume (550 g / L), 60% by volume (600 g / L), 65% by volume (650 g / L), 70% by volume (700 g / L), 75% by volume (750 g / L), preferably 80% by volume (800 g / L). In some embodiments, the β-diketone compound of formula (I) can be extracted from the plant in an amount of at least about 81% by volume (810 g / L), 82% by volume (820 g / L), 83% by volume (830 g / L), 84% by volume (840 g / L), and even 85% by volume (850 g / L).

[0035]

[0044] Plant extracts may contain other components and are extracted from plants together with the β-diketone compounds of formula (I), so such plant extracts are often compositions. In a preferred embodiment, the plant extract is a phytochemical extract. By "phytochemical extract" is meant a composition in which the plant extract contains at least one phytochemical compound extracted from the plant in addition to and other than any one β-diketone compound of formula (I). The preference for phytochemical extracts, although not intending to be bound by theory, is because additional phytochemicals may help in the control of unhatched pests and the reduction of the survival rate of unhatched pests by enhancing the activity of the β-diketone compounds of formula (I) even slightly. The at least one other phytochemical compound can be one or more of α- / β-farnesene, cis- / trans-menth-2-en-1-ol, 1,8-cineole, eudesmol, eucalyptol, α-pinene, p-cymene, terpineol, terpinene, globulol, limonene, β-myrcene, citronellal, linalool.

[0036]

[0045] In a preferred embodiment, the β-diketone compound of formula (I) is selected from compounds of the following structural formula:

[0037]

Chemical formula

[0038]

[0046] In a more preferred embodiment, the β-diketone compound of formula (I) is selected from tasmanone (1-isobutyroyl-4-methoxy-3,5,5-trimethylcyclohex-3-ene-2,6-dione), aglomerone (1-isobutyroyl-4-methoxy-5,5-dimethylcyclohex-3-ene-2,6-dione), lateriticone (1-valeroyl-4-methoxy-3,5,5-trimethylcyclohex-3-ene-2,6-dione), isolateriticone (1-isovaleroyl-4-methoxy-3,5,5-trimethylcyclohex-3-ene-2,6-dione) and platypherol (6,6-dimethyl-2-acetyl-5-methoxycyclohex-4-ene-1,3-dione).

[0039]

[0047] In the most preferred embodiment, the β-diketone compound of formula (I) is tasmanone (1-isobutyroyl-4-methoxy-3,5,5-trimethylcyclohex-3-ene-2,6-dione). This is because among the β-diketone compounds of formula (I), tasmanone is considered to exhibit the highest activity against winged insect pests when used in combination with a pyrethroid or pyrethrin. Pyrethroids and pyrethrins

[0048] As used herein, "pyrethrin" refers to a compound identical to the known natural pyrethrins produced by the plant species Chrysanthemum cinerariaefolium or C. coccineum, including salts, solvates and geometric isomers thereof. Natural pyrethrins include the compounds pyrethrin I, cinerin I, jasmolin I, pyrethrin II, cinerin II and jasmolin II.

[0040]

[0049] In certain preferred embodiments, the one or more second insecticides are pyrethrins, preferably a mixture of pyrethrins, preferably containing at least pyrethrin I and pyrethrin II, preferably containing all six pyrethrins. When all six pyrethrins are mixed and used, it is preferred that pyrethrin I and pyrethrin II occupy the majority (i.e., about 50% by weight or more) of the mixture.

[0041]

[0050] As used herein, "pyrethroid" refers to a synthetic compound having a chemical structure similar to pyrethrin and having the same insecticidal mechanism of action as pyrethrin. Examples include acrinathrin, allethrin, bifenthrin, bioallethrin, bioallethrin-S-cyclopentyl, biopermethrin, cycloprothrin, cyfluthrin, β-cyfluthrin, cyhalothrin, γ-cyhalothrin, λ-cyhalothrin, cypermethrin, α-cypermethrin, β-cypermethrin, θ-cypermethrin, ζ-cypermethrin, cyphenothrin, deltamethrin, dimefluthrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, flubutinate, tau-flubutinate, halfenprox, imiprothrin, metofluthrin, permethrin, phenothrin, prallethrin, profenofos, pyrethrin (pyrethrum), resmethrin, RU15525, silafluofen, tefluthrin, tetramethrin, tralomethrin, transfluthrin, and ZX18901 compounds.

[0042]

[0051] In certain preferred embodiments, the one or more second insecticides are pyrethrin, preferably selected from at least pyrethrin I and pyrethrin II, and most preferably a mixture of pyrethrin comprising at least pyrethrin I and pyrethrin II.

[0043]

[0052] In certain preferred embodiments, the one or more second insecticides are pyrethroids, preferably selected from permethrin, deltamethrin, and cypermethrin, and most preferably permethrin. Method of the invention

[0053] The present invention provides a method for controlling winged insect pests, comprising exposing the pests herein to an effective amount of a combination of a β-diketone compound of formula (I) described herein and at least one second insecticide selected from pyrethrin or pyrethroid, wherein the β-diketone compound of formula (I) and the at least one second insecticide are used in less than effective amounts.

[0044]

[0054] As used herein, the term "combination" means that the β-diketone compound of formula (I) and at least one pyrethroid or pyrethrin are used simultaneously in a single composition or in separate compositions, or sequentially in separate compositions, such that the biological activities of both compounds in the winged insect pests overlap or occur simultaneously. In a preferred embodiment, the β-diketone compound of formula (I) and at least one pyrethroid or pyrethrin are used together in a single composition described herein.

[0045]

[0055] As used herein, the term "control" refers to inhibiting a winged insect pest from participating in activities in the environment at a population level that would cause it to be a pest in that environment. Control can be effected by expelling the winged insect pest from its environment and / or by disabling the winged insect pest. Expelling the winged insect pest from the environment includes reducing or suppressing invasion and driving the winged insect pest out of the environment. Disabling the winged insect pest includes causing knockdown (KD), death, or a moribund state.

[0046]

[0056] Controlling winged insect pests does not necessarily require completely eliminating the winged insect pests from the environment or disabling all the winged insect pests in the environment. Reducing the active population can be sufficient to control the pests by arresting their toxicity, even if a portion of the population remains active. What constitutes control of winged insect pests depends on the specific winged insect pest, its population, and the environment and can be determined by one skilled in the art.

[0047]

[0057] In a preferred embodiment, winged insect pests are controlled by being incapacitated. The winged insect pests are preferably incapacitated by knockdown and / or death, and death is desirable.

[0048]

[0058] The incapacitation of winged insect pests can be expressed in terms of the time to knockdown (or near death). This is the time it takes after exposing a population of winged insect pests to an amount of insecticide effective to knockdown a certain percentage of the insect population at that amount, to effectively knockdown a certain percentage of the insect population. The time to KD can depend, for example, on the particular winged insect pest, the amount of insecticide used, the environment, and the number of winged insect pests, but generally speaking, the time to KD for a combined amount is shorter than the time to KD when using the β-diketone compound of formula (I) and at least one pyrethroid or pyrethrin in equal amounts each.

[0049]

[0059] Winged insect pests can be controlled by applying to the pests or the environment in which the pests live or potentially live a combination of a β-diketone compound of formula (I) described herein and at least one second insecticide selected from pyrethrin or a pyrethroid, thereby exposing the pests to the β-diketone compound of formula (I) and at least one second insecticide selected from pyrethrin or a pyrethroid. As used herein, the term "environment" refers to an environment in which a combination of a β-diketone compound of formula (I) and at least one pyrethroid or pyrethrin can be applied to expose winged insect pests to the combination and control the winged insect pests. The environment can be an agricultural environment, a domestic environment, an industrial environment, or any other environment in which winged insect pests live or potentially live. The agricultural environment includes environments for cultivating commercially important crops, trees, and other plants, including the plants, soil and its surrounding areas, and storage facilities and areas for agricultural products. The domestic environment includes environments in which humans and animals live, including indoor environments and outdoor environments such as gardens, and including fixtures and furniture. The industrial environment includes environments used for industrial purposes such as manufacturing, storage, and retail of products, such as warehouses, manufacturing factories, and retail stores, and is usually an indoor environment. Other environments can include leisure areas such as parks and stadiums, water areas such as rivers, lakes, and ponds, or places where water can accumulate, flow slowly, or stagnate. In a preferred embodiment, the environment is a domestic environment or an industrial environment, preferably an indoor environment.

[0050]

[0060] In an environment, winged insect pests may be exposed to a combination of a β-diketone compound of formula (I) and at least one pyrethroid or pyrethrin by applying the combination to the environment, and the application can be carried out, for example, by dispersion in air, application to a surface, or application to an animal by, for example, dipping, spraying, pouring, washing, spraying or misting, irrigation, droplet application, or other aerial application methods. When applying to an animal, the animal may be, for example, livestock such as cows, sheep, goats, deer, pigs, camels, llamas, alpacas, chickens, etc., or pet animals such as dogs, cats, rabbits, guinea pigs, hamsters, mice, horses, etc. In a preferred embodiment, the combination of the β-diketone compound of formula (I) and at least one pyrethroid or pyrethrin is applied by being dispersed in air.

[0051]

[0061] As used herein, the term "effective amount" in the context of a combination of a β-diketone compound of formula (I) and at least one pyrethroid or pyrethrin means an amount of the combination sufficient to control winged insect pests. For example, when disabling winged insect pests, the effective amount of the combination can be expressed as an LC amount or an LD amount. This is the concentration or dosage that is respectively effective to kill or knockdown (sometimes called the KD amount expressed as a concentration, or applicable to a dying state) a sufficient proportion of the insect population to eliminate the pests. The LC, LD and / or KD amounts for any winged insect pest can be determined by those skilled in the art through routine tests. For example, depending on the specific winged insect pest, environment and number of winged insect pests, this can be, for example, LC 10 、LC 15 、LC 20 、LC 25 、LC 30 、LC 35 、LC 40 、LC 45 、LC 50 、LC 55 、LC 60 、LC 65 、LC 70 、LC 75 、LC 80 、LC 85, LC 90 and LC 95 can be a combination of amounts (or similarly the amounts of LD or KD). For the control of winged insect pests, if it is necessary to kill (or knockdown or render moribund) all the insects within the insect population, this can be the LC 100 amount (or the LD 100 or KD 100 amount).

[0052]

[0062] In a preferred embodiment, especially in the case of particularly dangerous and nuisance winged insect pests (such as mosquitoes and houseflies), the effective amount of the combination of the β-diketone compound of formula (I) and at least one pyrethroid or pyrethrin is at least the LC 90 amount, which can be the LC 90 , LC 91 , LC 92 , LC 93 , LC 94 , LC 95 , LC 96 , LC 97 , LC 98 , LC 99 or LC 100 amount, but is preferably at least the LC 95 amount, more preferably at least the LC 100 amount and including at least the LC 99 amount (and is similarly applicable to the LD or KD amounts). The same principle can also be applied to exclude winged insect pests from the environment. That is, the amount by which at least 90% of the exposed insect population is excluded is used. This can be 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 100%, preferably at least 95%, more preferably at least 99%.

[0053]

[0063] The physical quantities of the combination that constitute the effective amount of the combination depend on the specific winged insect pest, the level of infestation, the susceptibility to the combination, the type of control desired, and the environment to which the combination is applied, and can be determined by those skilled in the art. Generally speaking, in an agricultural environment where spray application is commonly required, the amount of the combination in the agricultural environment may be, for example, in the range of about 0.01 to 200 kg / ha, or 0.1 to 150 kg / ha, or 1 to 100 kg / ha in the case of spray application. In certain preferred embodiments, the amount of the combination may be in the range of about 50 to 200 kg / ha, or 75 to 150 kg / ha, or 90 to 130 kg / ha, or an amount of about 95 kg / ha or 130 kg / ha, for example, in the range of about 90 kg / ha to 100 kg / ha, or about 125 to 135 kg / ha. In a household or industrial environment, this combination can be applied in an amount in the range of 1 ng / m 3 ~1 g / m 3 、 or 1 μg / m 3 ~500 mg / m 3 and can also be applied, for example, in the case of air application, in an amount in the range of 1 mg / m 3 ~100 mg / m 3 .

[0054]

[0064] As used herein, the term "less than an effective amount" with respect to each of the β-diketone compound of formula (I) and at least one pyrethroid or pyrethrin means an amount that is not effective in controlling winged insect pests when used alone. That is, less than an effective amount means less than the effective amount. For example, when disabling winged insect pests, using the same example as above based on the LC amount, if the effective amount of the combination in controlling winged insect pests is the LC 100 amount, the amount less than the effective amount of each of the β-diketone compound of formula (I) and at least one pyrethroid or pyrethrin is less than the LC 100 amount, which is the LC <100 amount, which is, for example, LC 99 、 LC 95 、 LC 90 、 LC 85 、 LC80 , LC 75 , LC 70 , LC 65 , LC 60 , LC 55 , LC 50 , LC 45 , LC 40 , LC 35 , LC 30 , LC 25 , LC 20 , LC 15 , or LC 10 It may also be an amount. Similarly, when the effective amount of the combination is an LC 50 amount, the effective amount of each of the β-diketone compound of formula (I) and at least one pyrethroid or pyrethrin is less than the LC 50 less than the amount, LC <50 is an amount, which is, for example, LC 45 , LC 40 , LC 35 , LC 30 , LC 25 , LC 20 , LC 15 , or LC 10 It may also be an amount. The same principle applies equally to the amounts of LD or KD. A similar principle can also be applied to eliminating winged insect pests from the environment. That is, if 100% of the insect population is eliminated by the effective amount of the combination for controlling winged insect pests, the effective amount of each of the β-diketone compound of formula (I) and at least one pyrethroid or pyrethrin is an amount that, when used alone, results in less than 100% control of the insect population.

[0055]

[0065] In a preferred embodiment, the effective amount of each of the β-diketone compound of formula (I) or at least one pyrethroid or pyrethrin is less than the added amount.

[0066] As used herein, "less than the addition amount" with respect to each of the β-diketone compounds of formula (I) or at least one pyrethroid or pyrethrin means an amount of each that is not effective in controlling winged insect pests even when the effects of using each alone are added together. In other words, an effective combination for controlling winged insect pests that contains less than the addition amount of each of the β-diketone compounds of formula (I) or at least one pyrethroid or pyrethrin is a synergistic combination, i.e., supra-additive. For example, when disabling winged insect pests, using the same example as above based on the LC amount, when the effective amount of the combination in controlling winged insect pests is the LC 100 amount, less than the addition amount of each of the β-diketone compound of formula (I) and at least one pyrethroid or pyrethrin is an amount that is less than the LC 100 amount when the effects of using each alone are added together. In other words, generally speaking, the percentage of the insect population killed when each of the β-diketone compounds of formula (I) and at least one pyrethroid or pyrethrin is used alone does not correspond to the amount for controlling winged insect pests. The same principle applies equally to the LD or KD amounts. A similar principle can also be applied to excluding winged insect pests from the environment. That is, when 100% of the insect population is excluded by the effective amount of the combination for controlling winged insect pests, less than the addition amount of each of the β-diketone compound of formula (I) and at least one pyrethroid or pyrethrin is an amount such that the total percentage of the population excluded when each is used alone results in less than 100% control of the insect population.

[0056]

[0067] In a preferred embodiment, the amount of the β-diketone compound of formula (I) used in the combination is from about LC5 to about LC 25 amount, preferably from about LC 10 to about LC 20 amount. In some preferred embodiments, the LC 10 or LC 20 amount is used. From about LC5 to about LC 25In these embodiments using the amount of, the amount of at least one pyrethrin or pyrethroid is preferably about LC 40 ~ about LC 60 amount, preferably about LC 45 ~ about LC 55 amount. In some preferred embodiments, the LC 50 amount is used. The same principle also applies to the LD or KD amounts, and the same principle regarding the ratio of the number of insects can also be applied when eliminating winged insect pests from the environment.

[0057]

[0068] In other preferred embodiments, the amount of the β-diketone compound of formula (I) used in combination is about LC 15 ~ about LC 60 amount, preferably about LC 20 ~ about LC 55 amount, or about LC 20 ~ about LC 30 amount, or about LC 45 ~ about LC 55 amount. In some preferred embodiments, the LC 25 or LC 50 amount is used. In these embodiments using the about LC 15 ~ about LC 60 amount of the β-diketone compound of formula (I), the amount of at least one pyrethrin or pyrethroid is also about LC 15 ~ about LC 60 amount, preferably about LC 20 ~ about LC 55 amount, or about LC 20 ~ about LC 30 amount, or about LC 45 ~ about LC 55 amount, and in some preferred embodiments, it is the LC 25 or LC 50 amount. In certain preferred embodiments of the combination, the LC 25 amount of the β-diketone compound of formula (I) and the LC 25 amount of at least one pyrethrin or pyrethroid, the LC 25 amount of the β-diketone compound of formula (I) and the LC 50The amount of the β-diketone compound of formula (I) and LC 50 The amount and the LC of at least one pyrethrin or pyrethroid 25 are included. These embodiments may result in a maximum synergistic effect. The same principle applies equally to the amounts of LD or KD, and the same principle regarding the insect population ratio can also be applied when eliminating winged insect pests from the environment.

[0058]

[0069] In certain preferred embodiments, the amount of the β-diketone compound of formula (I) used in combination is greater than the amount of at least one pyrethrin or pyrethroid used in combination. Depending on the specific winged insect pest, its susceptibility to the combination, the type of control desired, and the environment to which the combination is applied, the amount may be determined as the amount per insect. In the case of the β-diketone compound of formula (I), this can be an amount of about 500 ng to about 100 μg, or about 1 μg to about 70 μg, or about 10 μg to about 55 μg. In the case of at least one pyrethrin or pyrethroid, this can be an amount of about 0.05 ng to about 50 μg, or about 10 ng to about 7 μg, or about 50 ng to about 3 μg.

[0059]

[0070] The amount may be determined as a mixing ratio, for example, in the case of spraying or aerial application to an environmental area. For example, when the area application rate of the formulation is 100 L / ha, the β-diketone compound of formula (I) may be included in an amount of about 0.5 g / L to about 500 g / L, or about 10 g / L to about 250 g / L, or about 25 g / L to about 200 g / L. In some preferred embodiments, the β-diketone compound of formula (I) may be included in an amount within the range of about 60 g / L or about 125 g / L, for example, about 50 or 55 g / L to about 65 or 70 g / L, or about 115 or 120 g / L to about 130 or 135 g / L. In these embodiments, at least one pyrethrin or pyrethroid may be included in an amount of about 0.1 g / L to about 50 g / L, or about 1 g / L to about 25 g / L, or about 5 g / L to about 20 g / L. In some preferred embodiments, at least one pyrethrin or pyrethroid is included in an amount within the range of about 8 g / L or about 12 g / L, for example, about 5 to about 10 g / L, or about 10 to about 15 g / L. In the case of an area application rate of 100 L / ha of the formulation, in certain embodiments, the β-diketone compound of formula (I) is included in an amount of about 60 g / L or 90 g / L, and at least one pyrethrin or pyrethroid is included in an amount of about 8 g / L or about 12 g / L. The same applies to different application rates. For example, in the case of an area application rate of 200 L / ha which is twice or 50 g / L for a half area application rate, the amounts can be halved or doubled respectively according to the situation.

[0060]

[0071] The ratio of the β-diketone compound of formula (I) to at least one pyrethrin or pyrethroid used may be from about 100:50 to 100:0.01 parts, or from about 100:10 to 100:0.1 parts, or from about 100:0.5 parts to 100:5 parts. In certain preferred embodiments, the ratio of the β-diketone compound of formula (I) to at least one pyrethrin or pyrethroid used is from about 100:30 to 100:0.5 parts, preferably 100:25 to 100:1 parts, preferably 100:20 to 100:5 parts. In certain preferred embodiments, the ratio of the β-diketone compound of formula (I) to at least one pyrethrin or pyrethroid is used at about 100:19 parts, 100:13 parts or 100:9 parts.

[0061]

[0072] In certain preferred embodiments, the amount of the combination to which the winged insect pests are exposed is such that the time to at least about 50% KD of the winged insect pest population is less than about 420 seconds, i.e., a time of 0 to about 420 seconds. Preferably it is a time of about 300 seconds or less, more preferably a time of about 240 seconds or less or 120 seconds or less. Similarly, the amount of the combination used is preferably such that the time to at least about 90% or more KD of the winged insect pest population is about 1,500 seconds or less, i.e., a time between 0 seconds and about 1,500 seconds, preferably about 1,200 seconds or less, preferably about 840 seconds or less, more preferably about 720 seconds or less. The time until 90% of the winged insect pest population reaches KD may be about 540 seconds or less or 420 seconds or less, preferably about 300 seconds or less, even more preferably about 240 seconds or less or 120 seconds or less. In some embodiments, 100% of the winged insect pest population can be knocked down in less than about 1,500, 1,200, 840, or 720 seconds, preferably less than 540 seconds or 420 seconds, preferably about 300 seconds or less, and even more preferably about 240 seconds or less or 120 seconds or less. These times to KD can often be achieved by using the above preferred amounts.

[0062]

[0073] In certain preferred embodiments, at least about 50% of the winged insect pest population dies in less than about 48 hours, i.e., between 0 and about 48 hours, preferably in less than about 40 hours, more preferably in less than about 32 hours or 24 hours. In some embodiments, at least about 70% or more of the winged insect pest population dies in less than about 48 hours, preferably in less than about 40 hours, more preferably in less than about 32 hours or 24 hours. In some embodiments, 100% of the winged insect pest population dies in less than about 48 hours, preferably in less than about 40 hours, more preferably in less than about 32 hours or 24 hours. These mortality rates can often be achieved by using the recommended amounts described above.

[0063]

[0074] In certain preferred embodiments, at least about 80% of the winged insect pest population is moribund or dead in less than about 48 hours, i.e., between 0 and about 48 hours, preferably in less than about 40 hours, more preferably in less than about 32 hours or 24 hours. In some embodiments, at least about 85% or 90% of the winged insect pest population is moribund or dead in less than about 48 hours, preferably in less than about 40 hours, more preferably in less than about 32 hours or 24 hours. In some embodiments, 100% of the winged insect pest population is moribund or dead in less than about 48 hours, preferably in less than about 40 hours, more preferably in less than about 32 hours or 24 hours. These moribund rates and mortality rates can often be achieved by using the recommended amounts described above.

[0064]

[0075] In certain preferred embodiments, as a result of exposure to the insecticide combinations disclosed herein, at least about 80% of the winged insect pest population that is KD or near death will subsequently die. Preferably, at least about 85%, 90%, or 95% of the KD or near - death insect population will subsequently die, and preferably 100% of the KD or near - death insect population will subsequently die. In other words, the rate at which KD and / or near - death flying insects turn into dead flying insects is at least about 80%, 85%, 90%, or 95%, and even 100%. An advantage of the present invention is that the rate at which flying insects recover from the KD and near - death states is low; in other words, the KD and near - death states turn into death at a high rate. This is often not achievable with pyrethrins or pyrethroids alone, and a higher proportion of the pest population may have the potential to recover from the KD and near - death states.

[0065]

[0076] As used herein, the term "winged insect" refers to an insect that includes wings at any stage of its life cycle. Preferably, the winged insect is also capable of flight, in which case the winged insect may be referred to as a flying winged insect.

[0066]

[0077] The winged insect pests to be controlled may be at any stage of the life cycle, such as eggs, larvae, pupae, adults, nymphs, etc. Since the combinations of the present invention have been found to be particularly effective against adults and larvae, in preferred embodiments, the winged insect pests are adults or larvae.

[0067]

[0078] Winged insects that can be controlled using the β - diketone compound of formula (I) or a combination of at least one pyrethroid or pyrethrin include the following: a. From Lepidoptera, for example, Adoxophyes orana, Agrotis ipsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Cacoecia murinana, Capua reticulana, Choristoneura fumiferana, Chilo partellus, Choristoneura occidentalis, Cirphis unipuncta, Cnaphalocrocis medinalis, Crocidolomia binotalis, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Feltia subterranea, Grapholitha funebrana, Grapholitha molesta, Heliocoverpa armigera, Heliocoverpa virescens, Heliocoverpa zea, Hellula undalis, Hibernia defoliaria, Hypliantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Manduca sexta, Malacosoma neustria, Mamestra brassicae, Mocis repanda, Operophthera brumata, Orgyia pseudotsugata, Ostrinia nubilalis, Pandemis heparana, Panolisflamnea, Pectinophora gossypiella, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Platynota stultana, Plutella xylostella, Prays citri, Prays oleae, Prodenia sunia, Prodenia ornithogalli, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sesamia inferens, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Syllepta derogata, Synanthedon myopaeforinis, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni, Tryporyza incertulas and Zeiraphera canadensis, and, furthermore, Galleria mellonella, Sitotroga cerealella, Ephestia cautella and Tineola bisselliella; b. From the order Coleoptera, for example, Anthonomus grandis, Anthonomus pomorum, Apion vorax, Atomaria linearis, Blastophagus piniperda, Cassida nebulosa, Cerotoma trifurcata, Ceuthorhynchus assimilis, Ceuthorhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Cryptolestes ferrugineus, Dendroctonus rufipennis, Diabrotica longicornis, Diabrotica punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Otiorhynchus sulcatus, Otiorhynchus ovatus, Phaedon cochleariae, Phyllopertha horticola, Phyllophaga sp., Phyllotreta chrysocephala, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Psylliodes napi, Scolytus intricatus and Sitona lineatus, and further, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Sitophilus granarius, Lasioderma serricorne, Oryzaephilus surinamensis, Rhyzopertha dominica, Sitophilus oryzae, Tribolium castaneum, Trogoderma granarium and Zabrotes subfasciatus;. c. From the order Diptera, for example, Anastrepha ludens, Ceratitis capitata, Contarinia sorghicola, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia coarctata, Delia radicum, Hydrellia griseola, Hyleniyia platura, Liriomyza sativae, Liriomyza trifolii, Mayetiola destructor, Orseolia oryzae, Oscinella frit, Pegomya hyoscyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi and Rhagoletis pomonella, and, in addition, Aedes aegypti, Aedes vexans, Aedes albopictus, Anopheles maculipennis, Chrysomya bezziana, Cochliomyia hominivorax, Chrysomya macellaria, Cordylobia anthropophaga, Culex pipiens, Culex quinquefasciatus, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haernatobia irritans, Haplodiplosis equestris, Hypoderma lineata, Lucilia cuprina, Lucilia sericata, Musca domestica, Muscina stabulans, Oestrus ovis, Tabanus bovinus and Simulium damnosum; d. From the order Thysanoptera, for example, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Haplothrips tritici, Heliothrips haemorrhoidalis, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci; e. from the order Hymenoptera, for example, Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Iridomyrmex humilis, Iridomyrmex purpureus, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri and Technomyrmex albipes; f. from the order Hemiptera, for example, Aphis, Bemisia, Phorodon, Aeneolamia, Empoasca, Perkinsiella, Pyrilla, Aonidiella, Coccus, Pseudococcus, Helopeltis, Lygus, Dysdercus, Oxycarenus, Nezara, Aleyrodes, Triatoma, Psylla, Myzus, Megoura, Phylloxera, Adelges, Nilaparvata, Nephotettix or Cimex spp.; g. from the order Heteroptera, for example, Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus ictericus, Leptoglossus phyllopus, Lygus hesperus, Lygus lineolaris, Lygus pratensis, Mormidea pictiventris, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor; h. From the order Homoptera, for example, Acyrthosiphon onobrychis, Acyrthosiphon pisum, Adelges laricis, Aonidiella aurantii, Aphidula nasturtii, Aphis fabae, Aphis gossypii, Aphis pomi, Bemisia tabaci, Brachycaudus cardui, Dalbulus maidis, Dreyfusia nordmannianae, Dysaphis radicola, Empoasca fabae, Eriosorna lanigerum, Laodelphax striatella, Macrosiphun euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzus persicae, Nephotettix cincticeps, Nilaparvata lugens, Perkinsiella saccharicida, Phorodon humuli, Cacopsylla mali, Psylla pyri, Cacopsylla pyricola, Rhopalosiphum maidis, Schizaphis graminum, Sitobion avenae, Sogatella furcifera, Toxoptera citricida, Trialeurodes abutilonea, Trialeurodes vaporariorum and Viteus vitifolaei; i. From the order Isoptera, for example, Kalotermes flavicollis, Coptotermes spp, Leucotermes flavipes, Macrotermes subhyalinus, Macrotermes darwiniensis, Mastotermes spp. Microtermes spp., Nasutitermes spp, for example, Nasutitermes walkeri, Odontotermes formosanus, Reticulitermes lucifugus and Termes natalensis; From the order Blattoidae, for example, Blatella germanica, Periplaneta spp., Supella longipalpa, Blatta orientalis, Shelfordella spp. and Drymaplaneta communis; From the order Orthoptera, for example, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus and Schistocerca gregaria, as well as Acheta domesticus, Blatta orientalis, Blattella germanica and Periplaneta americana; and, From the order Dermaptera, for example, Forficula spp.

[0068]

[0079] In a preferred embodiment, the winged insect pest is an insect of the order Diptera. In a preferred embodiment, the winged insect pest is a dangerous and / or nuisance winged insect pest and is generally considered to be a mosquito or a fly. In a preferred embodiment, the winged insect pest is of the genus Musca such as Musca domestica, the genus Aedes such as Aedes aegypti, Aedes vexans and Aedes albopictus, and the genus Culex such as Culex pipiens and Culex quinquefasciatus. The combination of the present invention is particularly effective against these winged insect pests.

[0069]

[0080] In certain embodiments, the winged insect pest is insecticide-resistant.

[0081] As used herein, the term "insecticide-resistant" means that the winged insect pest has acquired resistance to one or more insecticides previously used to control that pest. There may be winged insect pests with insecticide resistance within a population of pests. In preferred embodiments, the winged insect is resistant to one or more pyrethroids or pyrethrins. More preferably, the winged insect is permethrin-resistant and / or deltamethrin-resistant, which means that the winged insect pest has developed resistance to permethrin and / or deltamethrin, and more preferably is permethrin-resistant. For example, the known KS17 strain of Musca domestica, a species of the winged insect pest housefly, is known to exhibit essentially complete resistance to permethrin. Similarly, the known Puerto Rico strain of Aedes aegypti, a species of the winged insect pest mosquito, is known to exhibit resistance to permethrin.

[0070]

[0082] In certain embodiments, the winged insect pest is insecticide-susceptible.

[0083] As used herein, the term "insecticide-susceptible" means, in contrast to insecticide-resistance, that the winged insect pest has not acquired resistance to one or more insecticides previously used to control that pest. There may be winged insect pests susceptible to insecticides within a population of pests.

[0071]

[0084] It is advantageous to use the β-diketone compound of formula (I) in combination with one or more pyrethrins or pyrethroids. Without being bound by theory, the main mode of action of pyrethrins and pyrethroids is thought to act as sodium channel activators that prevent the closing of sodium channels, which can lead to paralysis and sometimes death in insects. On the other hand, the main mode of action of the β-diketone compound of formula (I) is different. It acts as a potassium channel activator that prevents the closing of potassium channels and is thought to often incapacitate insects, especially knockdown them, and usually lead to death within a few minutes. Furthermore, the mode of action of the β-diketone compound of formula (I) is thought to result from the core cyclohexene β-dione motif of the structural formula that defines the compounds of formula (I) herein. This core motif is hypothesized to provide a scaffold for the affinity binding to the potassium ion channels of insects. Furthermore, potassium ion channels are thought to play a particularly important role in the development and function of insect wings (see, for example, George, L.F. et al., G3, 2019, 9(4), 999-1008), and it is hypothesized that potassium ion channels are widely present in winged insects, including the developmental stages of the insect life cycle. Therefore, the β-diketone compound of formula (I) is particularly effective in controlling winged insects when combined with a second insecticide selected from pyrethrins or pyrethroids. By causing the β-diketone compound of formula (I) to act complementarily with one or more pyrethrins or pyrethroids against winged insect pests, it is possible to achieve effective control of winged insect pests while reducing the amounts of pyrethrins or pyrethroids and the β-diketone compound of formula (I) used to less than the effective amount, and even less than the added amount, including against insecticide-resistant winged insect pests. Composition of the present invention

[0085] The β-diketone compound of formula (I) and one or more pyrethrins or pyrethroids may be formulated separately for simultaneous or sequential application, or may be formulated together in a single composition.

[0072]

[0086] It is preferred to apply the β-diketone compound of formula (I) and one or more pyrethrins or pyrethroids together in a single composition and thus to formulate them together. Although the formulation of a single composition is described herein, generally the same also applies to separate compositions for use in simultaneous or sequential application.

[0073]

[0087] As described herein, the composition can be applied by means of dispersion in air, application to a surface, or application to an animal, for example, by dipping, spraying, pouring, washing, spraying or misting, perfusion, droplet application, or other aerial application methods. Thus, the composition can be formulated in any suitable form such as a spray, aerosol, oil, emulsion, wettable powder, flowable formulation, granule formulation, powder, dust, solution, suspension, emulsion, controlled release formulation, etc. by means such as dissolution, separation, suspension, mixing, impregnation, adsorption, precipitation, etc.

[0074]

[0088] The composition may optionally contain one or more additives or excipients such as, for example, carriers, stabilizers, emulsifiers, surfactants, propellants, antioxidants, ultraviolet absorbers, humectants, etc. Natural ingredients are preferred. Suitable additives and excipients are known to those skilled in the art.

[0075]

[0089] The selection of a suitable formulation can be made taking into account the combination, the winged insect pests and the control environment and can be determined by those skilled in the art. In a preferred embodiment, the composition is formulated as a liquid spray for use in a nebulizer or aerosol for indoor application.

[0076]

[0090] The β-diketone compound of formula (I) can exist as a substantially purified synthetic compound, a substantially purified isolated compound, or a crude extract, and thus the compositions of the present invention can include them. The use of a crude extract is preferred. When used as a crude extract, preferably, the β-diketone compound is present in a high proportion in the crude extract as described herein. The crude extract can be a phytochemical extract as described herein, in which case the compositions of the present invention can include at least one additional phytochemical extracted from a plant together with the β-diketone compound of formula (I). Additional phytochemicals other than the β-diketone compound of formula (I), pyrethroids, and pyrethrins can also be added to the compositions of the present invention, for example, when a source other than a plant extract is used as the source of the compound of formula (I) and no additional phytochemicals are present yet.

[0077]

[0091] The compositions can be formulated at respective concentrations of the β-diketone compound of formula (I) and one or more pyrethrins or pyrethroids suitable for the method of application, corresponding to the exposure of winged insect pests to less than their respective effective amounts. Generally speaking, the compositions can be formulated as concentrates for dilution prior to application. This can correspond, in certain embodiments, to compositions containing one or both of the β-diketone compound of formula (I) and one or more pyrethrins or pyrethroids in the range of 10 - 50,000 ppm, 100 - 10,000 ppm, 100 - 5,000 ppm, or 300 - 5,000 ppm, 500 - 5,000 ppm, or 800 - 2,500 ppm or 900 - 2,000 ppm. In other embodiments, the compositions can contain one or both of the β-diketone compound of formula (I) and one or more pyrethrins or pyrethroids in the range of 100 - 1,000 ppm, 200 - 800 ppm, 300 - 600 ppm, or 600 - 5,000 ppm, 1,000 - 2,500 ppm, or 20 - 100 ppm, 25 - 80 ppm, or 20 - 100 ppm or 50 - 100 ppm.

[0078]

[0092] The application rate of the composition in the environment can be adjusted as necessary to expose winged insect pests to less than their respective effective amounts, depending on the concentration of the β-diketone compound of formula (I) and one or more pyrethrins or pyrethroids. Generally speaking, the application rate to the agricultural environment can be an amount in any combination within the range of, for example, about 0.01 - 200 kg / ha, or 0.1 - 150 kg / ha, or 1 - 100 kg / ha for spray application. In certain preferred embodiments, the amount of the combination can be an amount within the range of about 50 - 200 kg / ha, or 75 - 150 kg / ha, or 90 - 130 kg / ha, or an amount of about 95 kg / ha or 130 kg / ha, for example, an amount within the range of about 90 kg / ha - 100 kg / ha, or about 125 - 135 kg / ha. The application rate in the household or industrial environment is 1 ng / m 3 ~1 g / m 3 、 or 1 μg / m 3 ~500 mg / m 3 in a combined amount within the range, or for example, for aerial application, 1 mg / m 3 ~100 mg / m 3 and can be any amount within the range.

[0079]

[0093] The β-diketone compound of formula (I) and one or more pyrethrins or pyrethroids can together contain any weight from about 0.00005% to about 90% of the single composition.

[0080]

[0094] As described herein, in a preferred embodiment, the amount of the β-diketone compound of formula (I) used in the combination is more than the amount of at least one pyrethrin or pyrethroid used in the combination, and the same applies to the composition. Depending on the specific winged insect pests, their susceptibility to the combination, the type of control desired, and the environment to which the combination is applied, the amounts of the β-diketone compound of formula (I) and at least one pyrethrin or pyrethroid in the composition can be determined as the amount per insect based on the predetermined application rates described herein.

[0081]

[0095] The combination of a β-diketone compound of formula (I) and one or more pyrethrins or pyrethroids can be combined with a synergist such as piperonyl butoxide (PBO).

[0082]

[0096] One or more other insecticides can also be included, for example, acetylcholinesterase (AChE) inhibitors, GABA-dependent chloride channel antagonists, nicotinic acetylcholine receptor agonists, allosteric acetylcholine receptor modulators, chloride channel activators, juvenile hormone mimics, feeding inhibitors for homopteran insects, mitochondrial ATP synthase inhibitors, nicotinic acetylcholine receptor channel inhibitors, chitin biosynthesis inhibitors, molting inhibitors, ecdysone receptor agonists or inhibitors, octopamine receptor agonists, mitochondrial complex I electron transport inhibitors, acetyl-CoA carboxylase inhibitors, voltage-dependent sodium channel blockers, and mitochondrial complex IV electron inhibitors. Insecticides of these categories are known to those skilled in the art and are commercially available. Kit

[0097] Also contemplated is a kit comprising a β-diketone compound of formula (I) as defined herein and at least a pyrethroid or pyrethrin, and instructions for exposing winged insect pests to their combination using less than an effective amount of one or both.

[0083]

[0098] The β-diketone compound of formula (I) and at least a pyrethroid or pyrethrin can be formulated together or separately as described herein.

[0099] The instructions may further include an application rate suitable for a particular winged insect pest or environment, preferably in accordance with the preferred embodiments described herein.

[0084]

[0100] The kit may further include an administration device.

[0101] As used herein, the terms "a" and "an" are used herein to refer to one or more of the grammatical objects of the article (i.e., at least one). For example, "an element" means one element or more than one element.

[0085]

[0102] Unless the context requires otherwise by express language or necessary implication, the term "comprise" or variations such as "comprises" or "comprising" used herein are used in an inclusive sense, i.e., used to identify the presence of the described features, but do not preclude the presence or addition of further features in various embodiments of the present invention.

[0086]

[0103] It should be understood that when prior art documents are referred to herein, such reference does not admit that such document constitutes a part of the common general knowledge of the art in Australia or other countries.

[0087]

[0104] To make the present invention more readily understood and capable of being practiced, specific preferred embodiments will be described below by way of non-limiting examples.

Example

[0088]

[0105] A typical procedure for the synthesis of the β-dione compound of formula (I) is as follows: 3-Methoxy-2,4,4-trimethylcyclohex-2-en-1,5-dione (1 molar equivalent) is dissolved in anhydrous diethyl ether and hexamethylphosphoramide (solvent ratio, 20:1 each) under a nitrogen atmosphere. The mixture is cooled to 0 °C, and lithium hydride (1.1 molar equivalents) (60% in mineral oil) is added little by little. After stirring the mixture for an additional 10 minutes, benzoyl cyanide [represented as R-CO-CN] (1.1 molar equivalents) is added. The mixture is warmed to room temperature over 12 hours, at which point the reaction is quenched with water and separated. The ether layer is dried (Na2SO4) and evaporated to give crude 1-benzoyl-3-methoxy-2,4,4-trimethylcyclohex-2-en-1,5-dione, which is purified by SiO2 column chromatography (hexane / ethyl acetate, gradient).

[0089]

[0106] Another typical procedure for synthesizing the β-dione compound of formula (I) is as follows: 3-Methoxy-2,4,4-trimethylcyclohex-2-en-1,5-dione (1 molar equivalent) and benzoyl cyanide are dissolved in anhydrous dichloromethane and cooled to 0 °C under a nitrogen atmosphere. Anhydrous powdered zinc chloride (1.1 molar equivalents) is added to the cooled solution, followed by slow addition of triethylamine (1.2 molar equivalents). The reaction mixture is stirred at room temperature for 5 - 6 hours and then poured into 2M hydrochloric acid. The mixture is separated, and the dichloromethane layer is washed with 5% sodium carbonate. Next, the aqueous carbonate phase is acidified with hydrochloric acid and extracted with methylene chloride and dried (Na2SO4). The solvent is removed, and the residue is subjected to SiO2 column chromatography (hexane / ethyl acetate) to give 1-benzoyl-3-methoxy-2,4,4-trimethylcyclohex-2-en-1,5-dione.

[0090]

[0107] The metal salt can be prepared by reacting the prepared compound with the corresponding metal hydroxide suspended in methanol or ethanol. The trialkylammonium salt can be prepared by reacting the prepared compound with a trialkylamine in a chlorinated solvent such as dichloromethane. The tetraalkylammonium salt can be prepared by adding a tetraalkylammonium halide salt to the metal salt in dichloromethane.

[0091]

[0108] Example 1

[0109] Topical dose mortality assay for the efficacy of tasmanone against Aedes aegypti

[0110] Qcide larval dose mortality assay

[0111] Table 1 shows the results of the toxicity of the Qcide formulation (540EW, 540 g / L of E. cloëziana oil, containing at least 75% by weight of tasmanone in "Qcide") against Aedes aegypti permethrin (SP)-sensitive Liverpool (LVP) strain and SP-resistant Puerto Rico (PRS) strain L3 larvae in a larval dose-response assay. The results represent n = 3 biological replicates. The lethal concentration (LC 50 ) of Qcide at 24, 48, and 72 hours after topical exposure is shown compared to permethrin (SP), an industrial synthetic pyrethroid, and β-triketone flavobason (comparative data integrated from previous studies). See Figures 1 and 2.

[0092]

Table 1

[0093]

[0112] The dose-mortality assay revealed that Qcide was toxic to the larvae of the SP-sensitive Aedes aegypti LVP and PRS strains at 24, 48, and 72 hours.

[0094]

[0113] For the LVP strain, Qcide showed toxicity in the μg range (LC 50 27 μg / mL at 24 hours), while the SP positive control showed toxicity in the ng range at all time points (LC 50showed toxicity (26 ng / mL). Compared to flavone as a positive control using comparative data from previous studies, Qcide showed higher toxicity than flavone (24-hour LC 50 41 μg / mL) at all time points for the LVP strain in the μg range.

[0095]

[0114] For the PRS strain, Qcide showed toxicity in the μg range (24-hour LC 50 18 μg / mL), while the SP positive control showed toxicity in the ng range (24-hour LC 50 0.7 μg / mL) at all time points. The larvae of the PRS strain showed approximately 25-fold greater resistance to SP compared to the LVP strain under the assay conditions. Compared to flavone as a positive control using comparative data from previous studies, Qcide showed higher toxicity than flavone (24-hour LC 50 39 μg / mL) at all time points for the PRS strain in the μg range.

[0096]

[0115] The dose-mortality data support the larvicidal activity of Qcide against SP-resistant mosquitoes and, to a lesser extent, the larvicidal activity of flavone against SP-resistant mosquitoes. This supports a different mode of action for Qcide (tazmanone) from that of SP and is hypothesized to be the same as the confirmed mode of action of flavone, a potassium channel activator.

[0097]

[0116] Qcide adult dose mortality assay

[0117] Table 2 shows the results of the toxicity of the 540EW Qcide formulation against 3- to 5-day-old adults of the Aedes aegypti LVP and PRS strains in a dose-response assay. The results represent n = 3 biological replicates. The lethal concentrations (LC 50 ) of Qcide at 24 and 48 hours after exposure are shown compared to SP. See Figures 3 and 4.

[0098]

Table 2

[0099]

[0118] The toxicity of Qcide against adult Aedes aegypti LVP and PRS strains sensitive to SP was revealed at 24 and 48 hours by a dose-mortality assay.

[0100]

[0119] For the LVP strain, Qcide showed toxicity in the mg range (LC 50 8.1 mg / mL) at 24 hours, while the SP positive control showed toxicity in the ng range at both time points (LD 50 543 ng / mL) at 24 hours.

[0101]

[0120] For the PRS strain, Qcide showed toxicity in the mg range (LC 50 8.5 mg / mL) at 24 hours, while the SP positive control showed toxicity in the μg range at both time points (LC 50 130 μg / mL) at 24 hours. Under the assay conditions, adult PRS strain mosquitoes showed approximately 240-fold greater resistance to SP compared to LVP.

[0102]

[0121] The dose-mortality data support the adult control activity of Qcide against SP-resistant mosquitoes and a mode of action different from that of SP.

[0122] Qcide larval death time assay

[0123] Table 3 shows the results of the toxicity of the 540EW Qcide formulation against Aedes aegypti LVP and PRS strain L3 larvae in a mortality time assay. The results represent n = 3 biological replicates. The lethal concentration (LC 90 ) and the lethal time (LT 50 ) after topical exposure to the dose are shown in comparison to SP and the industrial synthetic pyrethroid deltamethrin. See Figure 5.

[0103]

Table 3

[0104]

[0124] The rapid toxicity of Qcide to larvae of the SP-sensitive Aedes aegypti LVP and PRS strains was revealed by the time-mortality assay.

[0125] For the LVP strain, the Qcide activity was faster compared to the SP positive control (permethrin LC 90 dose with LT 50 5.5 hours and deltamethrin (LC 90 dose with LT 50 5.6 hours) (LC 90 dose with LT 50 2.1 hours).

[0105]

[0126] For the PRS strain, the activity of Qcide was faster compared to the SP positive control (permethrin LC 90 dose with LT 50 26.5 hours, deltamethrin (LC 90 dose with LT 50 11.7 hours) (LC 90 dose with LT 50 1.6 hours).

[0106]

[0127] The time-mortality data support the larvicidal activity of Qcide against SP-resistant mosquitoes and a mode of action different from that of SP.

[0128] Larval dose-mortality assay with combinations of Qcide

[0129] Table 4 shows the results of the toxicity of SP after co-administering the 500EW Qcide formulation (LC 10 dose) to Aedes aegypti LVP and PRS strain L3 larvae in the dose-mortality assay. The results represent n = 3 biological replicates. Toxicity is reported as the lethal concentration (LC 50 ) value with a 95% confidence interval. The synergy ratio (SR) and P value are shown. See Figures 6 and 7. Mortality of mosquitoes A and B after 24 hours and 48 hours for LVP is shown. The lower panel shows the Qcide positive control at LC 10 , LC 50 and LC 90 doses. See Figures 8 and 9. Mosquito mortality is shown for A and B of PRS at 24 hours and 48 hours. The lower panel shows...10 , LC 50 and LC 90 shows the Qcide positive control at the dosage.

[0107]

Table 4

[0108]

[0130] Table 5 shows the results of the toxicity of SP after co - administering the 540EW Qcide formulation (LC 20 dosage) to Aedes aegypti LVP and PRS strain L3 larvae. The results represent n = 3 biological replicates. Toxicity is reported as the lethal concentration (LC 50 ) value with a 95% confidence interval. The synergistic ratio (SR) and P - value are shown.

[0109]

Table 5

[0110]

[0131] LC 10 and LC 20 dosages of Qcide significantly increased the toxicity of permethrin against Aedes aegypti mosquitoes.

[0132] In the dose - mortality assay, it was revealed that Qcide combined with the SP positive control had statistically significant synergistic activity against Aedes aegypti LVP larvae at 24 hours (LC 10 and LC 20 dosages of Qcide were significant at p < 0.01). In particular, the LC 50 of SP alone was 20.5 ng / mL and 23.7 ng / mL, but when combined with the LC 10 and LC 20 dosages of Qcide, they were 16.0 ng / mL and 8.5 ng / mL respectively at 24 hours.

[0111]

[0133] LC 10 and LC 20The Qcide dosage also biologically significantly increased the toxicity of permethrin against Aedes aegypti mosquitoes.

[0134] In the dosage-mortality assay, a biologically significant synergistic activity of Qcide against Aedes aegypti PRS larvae in combination with the SP positive control became apparent at 24 hours (LC 10 and LC 20 dosage Qcide was biologically significant at p < 0.1). In particular, the LC 50 of SP alone was 2,100 ng / mL and 1,213 ng / mL, and the LC 10 and LC 20 dosages of Qcide, when combined, were 1,259 ng / mL and 567 ng / mL, respectively, at 24 hours.

[0112]

[0135] Example 2

[0136] Topical dose-mortality assay for the efficacy of tasmanone against Musca domestica

[0137] For both insecticide-resistant and -susceptible strains of houseflies, the LD 50 of either permethrin or pyrethroid insecticides was tested for sublethal dosages of flavoside and Qcide (industrial-grade substances) as topical synergists when applied simultaneously with the topical dosage. The classical synergist piperonyl butoxide (PBO) was the synergist against which both flavoside and Qcide were compared. The co-toxicity coefficient for the 24-hour mortality of each synergist was determined using the following formula.

[0113]

Number

[0114] Here, the observed mortality is the number of flies knocked down or killed in the combined treatment of the insecticide and the synergist; the predicted mortality is the total number of flies knocked down or killed in the treatment with the insecticide alone and the treatment with the synergist alone; a co-toxicity coefficient value of > 20 is considered a synergistic effect, a value of -20 ≤ but ≤ 20 is an additive mixture, and a value of < -20 is an antagonistic mixture; The synergistic ratio (SR) is calculated by dividing the percentage of knockdown or mortality of the treatment with only the insecticide by the treatment with the insecticide and the synergist. This value represents the rate of change in mortality due to the synergist.

[0115]

[0138] Materials and methods

[0139] In this study, two strains of the housefly (Musca domestica) were used. The insecticide-susceptible strain was reared at the USDA-ARS-CMAVE in Gainesville, Florida, and is called the "CAR21" strain. The resistant strain, known as the "KS17" strain, has various resistance mechanisms to both pyrethroids and organophosphates and shows extremely high resistance to pyrethroids. The KS17 strain was reared in the laboratory during the study period.

[0116]

[0140] The chemicals used in this study were permethrin (purity 99.5%, cis isomer 23.8%, trans isomer 75.8%, Chem Service, lot: 6343500), pyrethrum extract (total of pyrethrin I and II > 50%, lot BCCB9487), piperonyl butoxide (purity 90%, Acros Organics, lot: A0378711), flavoside technical (flavosone, batch FC1250017001BL, containing a minimum of 95 wt% flavosone) and Qcide (tazmanone, batch BGTQ1812, containing 80.7 wt% tazmanone). All insecticides and synergists were diluted with insecticide-grade acetone.

[0117]

[0141] Twenty 3- to 5-day-old female houseflies were sorted into each of 12 glass Petri dishes under CO2 anesthesia. The flies were allowed to recover from anesthesia before being used in the assay. For the CAR21 strain, the LD of permethrin and pyrethrin 50The dosage was 12 ng / fly for permethrin and 0.3% (v / v) pyrethrin. In the case of the KS17 strain, a dosage of 5,000 ng per fly of permethrin was used. This was because it was the upper limit of the amount that could be administered to the flies before the insecticide began to recrystallize on the dorsal thorax of the flies. This strain is known to have little or no mortality at this dosage. A dosage of 1% (v / v) pyrethrin was used for KS17. For both strains, the maximum sublethal dosages of flavoside (0.3% v / v), Qcide (1.25% v / v), and PBO (10 μg / fly) were determined. The dosages of Al or the synergist were prepared by serial dilution with acetone to a total volume of 500 μL.

[0118]

[0142] The flies were anesthetized with cold air (ice) and 0.5 μL drops of the synergist were applied to the dorsal thorax of each fly using a Hamilton PB-600 repetitive dispenser fitted with a 25 μL airtight syringe. Immediately after applying the synergist, the insecticide was sprayed in the same location as the droplet of the synergist as before and the two were mixed. Then, the flies were transferred to a 236.6 mL (8 ounce) flint glass bottle and fixed with a mesh screen. The flies were given a cotton ball soaked in a 20% sucrose solution on the mesh screen as a source of moisture and carbohydrates. The flies were placed in an environmental chamber maintained at 25 °C and atmospheric relative humidity.

[0119]

[0143] Knockdown was defined as flies showing extreme defects in coordinated movements including walking and flying compared to control flies from the same replicate. Otherwise, the knocked-down flies were able to regain their standing position and perform normal movements such as grooming when the bottle was gently tapped on the laboratory bench, if it was on the dorsal side of the fly.

[0120]

[0144] Mortality was evaluated at 24 hours and scored as flies that were unable to stand up on their dorsal side or that became completely immobile.

[0145] These experiments were repeated 4 times for each strain and each unique treatment or control.

[0121]

[0146] The differences between the insecticide and the insecticide + synergist, and the comparisons between the insecticide and PBO, and between the insecticide and flavoside or Qcide were analyzed in R version 4.1.1 using Fisher's exact test. In this analysis, the dead and surviving individuals for each treatment were collected. The Mansour co-toxicity index was also used to calculate the synergistic effect on 24-hour mortality.

[0122]

[0147] Results

[0148] Table 6 shows the results of the 24-hour mortality assays, co-toxicity coefficients (Co-Tox), and synergist ratios (SR; the value obtained by dividing the percent KD of the synergistic insecticide by the percent KD of the insecticide alone) of the synergists Qcide (Q), flavoside (Fla), and piperonyl butoxide (PBO) in combination with permethrin (Per) and pyrethrin (Py) in insecticide-susceptible (CAR21) and insecticide-resistant (KS17) strains of Drosophila. The bold Co-Tox values represent synergistic effects.

[0123]

Table 6

[0124]

[0149] Qcide showed a synergistic effect with permethrin and pyrethrin compared to flaveson on the insecticide-susceptible strain CAR21, and also showed a synergistic effect with permethrin and pyrethrin on the insecticide-resistant strain KS17.

[0125]

[0150] Thus, it was demonstrated that Qcide has the potential as a synergist with pyrethrin and permethrin for both susceptible and resistant Drosophila.

[0151] Example 3

[0152] Knockdown and kill assay of tasmanone against Musca domestica

[0153] A study was conducted to determine whether the knockdown and mortality performance of pyrethrin (+PBO) against Musca domestica could be improved by the addition of Qcide (containing at least 80% by weight of tasmanone). The products provided for the test are shown in Table 7.

[0126]

Table 7

[0127]

[0154] This study was conducted in a chamber with internal dimensions of 70 cm × 70 cm × 70 cm, which was composed of an aluminum frame with glass sides and top, a laboratory-grade stainless steel base, a hinged front door, and a small glass sliding door in the front door that allowed the entry of flies and aerosol sprays. The environmental temperature was maintained at 22 ± 2 °C.

[0128]

[0155] For each treatment, the chamber was cleaned using detergent and water. After that, the chamber was completely dried. Twenty mixed male and female adult Musca domestica houseflies, aged 2 - 5 days, were introduced into the chamber. The Preval spray system was attached to a solenoid spray system. The nozzle of the Preval spray system was directed slightly upward to aim at the center of the upper half of the rear wall of the chamber. Each treatment was repeated three times.

[0129]

[0156] The Preval spray system consisted of an aerosol can with a dip tube attached to a connected glass container. It was also possible to remove the glass container from the aerosol can, inject the candidate insecticide into the glass container, and then reattach the container. When the aerosol nozzle was pressed, the insecticide was sucked up into the dip tube and sprayed as an aerosol spray from the nozzle. The Preval spray system was installed in an automatic spray device set to the required spray time.

[0130]

[0157] Both Qcide and Product C are EW formulations and were diluted with water to the dilutions detailed in Table 8 for the treatments used in the study.

[0131]

Table 8

[0132]

[0158] The automatic spray system was activated with a spray time of 2.0 seconds. After spraying, the weight of the spray discharge was recorded.

[0159] Knockdown of the houseflies was recorded at various time intervals up to a maximum of 1,800 seconds (30 minutes). Houseflies were considered knocked down when coordinated movement on the back or side was no longer possible.

[0133]

[0160] After 1,800 seconds, the flies were collected and placed in clean plastic storage containers containing 10% sucrose pads to check for recovery. Mortality was observed 24 hours after treatment. Flies were considered dead if no obvious movement was seen in any appendage for 3 seconds (by observation).

[0134]

[0161] The control consisted of 20 houseflies treated in the same manner as the active treatment but without the active treatment in the chamber. For the active treatment, knockdown and mortality were recorded as described above.

[0135]

[0162] As a result, it took 540 seconds for Qcide at a concentration of 100 g / L to reach KD50. It did not reach KD90. The 24-hour mortality rate was 68.3%. Product C took 420 seconds to reach KD50 and 1,500 seconds to reach KD90. The 24-hour mortality rate was 96.7%. Product C50% took 540 seconds to reach KD50 and 1,500 seconds to reach KD90. The 24-hour mortality rate was 95.0%. For Product C25%, it did not reach KD50 and KD90. The 24-hour mortality rate was 25.5%. Product A took 240 seconds to reach KD50 and 720 seconds to reach KD90. The 24-hour mortality rate was 100%. Product A50% took 300 seconds to reach KD50 and 840 seconds to reach KD90. The 24-hour mortality rate was 96.7%. Product A25% took 420 seconds to reach KD50 and 1,200 seconds to reach KD90. The 24-hour mortality rate was 98.3%. Figures 10 and Table 9 show the results of KD50 and KD90 values and the 24-hour mortality rate.

[0136]

Table 9

[0137]

[0163] Product A (i.e., adding Qcide to Product C) improved KD50, KD90, and the 24-hour mortality rate. This also applies to the case of Product A50% (i.e., adding Qcide to Product C50%). For Product A25% (i.e., adding Qcide to Product C25%), KD50 and KD90 were not improved much, but the 24-hour mortality rate was significantly improved. The results demonstrate the advantage of adding Qcide below the labeled rate of pyrethrin / PBO and are promising results suggesting that Qcide has a synergistic effect with pyrethrin / PBO.

[0138]

[0164] Example 4

[0165] Efficacy of tasmanone in combination with pyrethrin against Musca domestica

[0166] Summary

[0167] To investigate the efficacy of the Qcide formulation (540 EW, 540 g / L E. cloeziana oil, containing approximately 80 wt% tasmanone in "Qcide") on knockdown and mortality of pyrethroid-susceptible housefly species M. domestica adult females when used in combination with pyrethrin (Pyrocide 50 formulation containing 50 g / L pyrethrin), a series of laboratory bioassays were conducted.

[0139]

[0168] Qcide and pyrethrin were tested alone and in combination. The houseflies were placed in mesh-covered plastic containers with a diameter of 8.5 cm that were arranged to allow spray application. The treatments were applied via a Potter spray tower. Knockdown and mortality were evaluated at 10 seconds, 2, 3, 4, 5, 10, 15, 20, 25, 30 minutes and 1, 24, 48, 72, 96 hours after spray application.

[0140]

[0169] Methods

[0170] Ten adult female houseflies were counted and placed in a storage container composed of a plastic container with a diameter of 8.5 cm with mesh attached to each opening to allow passage of the spray room. A plastic stand was used to lift the holding chamber from the base of the Potter tower spray platform. See Figure 11. The treatments were based on the relevant lethal concentration (LC) rates determined by using a preliminary test and Probit analysis using ToxRat Professional version 3.3 as shown in Table 10.

[0141]

Table 10

[0142]

[0171] The treatment was 100 cm 2It was applied through a Potter spray tower that had been pre-adjusted to supply a spray volume of 0.1 mL per point (100 L per hectare). After spraying, the flies were immediately transferred to an untreated collection container using CO₂ to make them easier to move. The collection container consisted of a plastic 1 / 2 pint cup and a mesh fleece fixed to the cup with a rubber band. After the flies were transferred, a cotton pad soaked in a 10% sucrose solution was provided. The treatment schedule is shown in Table 11.

[0143]

Table 11

[0144]

[0172] The treatment agent was diluted with deionized water and thoroughly mixed by vortex before spraying. Spraying was carried out using a Potter spray tower (Burkard Manufacturing Co. Limited, Hertfordshire, England) that had been pre-adjusted to achieve a scale spray of 100 L / ha. Each test unit was sprayed individually. Five replicate experiments were conducted for each treatment.

[0145]

[0173] Knockdown and mortality were evaluated at 10 seconds, 2, 3, 4, 5, 10, 15, 20, 25, 30 minutes and 1, 24, 48, 72, 96 hours after spraying. Knockdown was interpreted as a state where insects could not perform coordinated movements or correct their postures after being exposed to the insecticide. The dying state was interpreted as the insect lying on its back and twitching only one leg. Death was interpreted as a dead insect that did not move even when prodded or probed.

[0146]

[0174] During the experimental period, the temperature ranged from 21.0 °C to 25.6 °C (average 22.1 °C), and the relative humidity ranged from 44% to 52% (average 49%). See Appendix IV for all details of the environmental conditions.

[0147]

[0175] Results

[0176] Figure 12 shows the results of the average knockdown rate, moribund rate, and mortality rate of M. domestica after spray application for 24 hours and 96 hours. All combination treatments showed 100% effectiveness in the combination of knockdown, moribund state, and mortality rate both 24 hours and 96 hours after application, showing improved results compared to Qcide and pyrethrin alone at the same application rate. In all combination treatments, the mortality rate was also improved both 24 hours and 96 hours after application compared to using Qcide and pyrethrin alone at the same application rate.

[0148]

[0177] Table 12 shows the average knockdown rate, moribund rate, and mortality rate of M. domestica after spray application of only Qcide and pyrethrin treatments for 96 hours (mean ± SE, n = 5) (KD = knockdown, M = moribund, D = dead). Table 13 shows the average knockdown rate, moribund state, and mortality rate of M. domestica after spray application of a combination treatment of Qcide and pyrethrin for 96 hours (mean ± SE, n = 5) (KD = knockdown, M = moribund, D = dead, Q = Qcide, P = pyrethrin).

[0149]

Table 12

[0150]

Table 13

[0151]

[0178] Between 1 hour and 24 hours, all combination treatments changed the knockdown state and moribund state to complete death. A certain proportion of the flies knocked down by the pyrethrin treatment seemed to recover between 1 hour and 24 hours. The following combination treatments seem to be at least additive in the moribund state and mortality rate when Qcide and pyrethrin treatments are carried out alone at the same application rate (without antagonism): QcideLC 25 and pyrethrin LC 25 、QcideLC 25and pyrethrin LC 50 , Qcide LC 50 and pyrethrin LC 25 , Qcide LC 50 + pyrethrin LC 50 and Qcide LC 75 + pyrethrin LC 25 . The presence of synergistic effects / co-toxicity was calculated using the concentration addition (CA) method. All analyses were performed using R version 3.5.3 (R Development Core Team 2019). Qcide LC 25 + pyrethrin LC 25 (χ 2 = 21.868, p < 0.001), Qcide LC 25 + pyrethrin LC 50 (χ 2 = 15.145, p < 0.001) and Qcide LC 50 + pyrethrin LC 25 (χ 2 = 14.723, p < 0.001) showed synergistic effects.

[0152]

[0179] Conclusions

[0180] For all combinations of Qcide and pyrethrin, > 90% mortality was obtained 72 hours after spray application. When Qcide was combined with pyrethrin and used in the treatments of Qcide LC 25 + pyrethrin LC 25 , Qcide LC 25 + pyrethrin LC 50 and Qcide LC 50 + pyrethrin LC 25 , evidence of synergistic effects was shown.

Claims

1. Pest control formula (I) 【Chemistry 1】 (In the formula, X and Y are oxygen and sulfur-N-R, respectively. ４ Either selected from or one of C=X and C=Y is CH ２ And; A is (C=O)R １ , (C=S)R １ , OR ２ , SR ２ , (CR ３ NR ４ R ５ ), C(R ３ ) ２ OR ２ , NR ４ R ５ , (C=N-R ４ ), R １ , N=O, N(=O) ２ , NR ４ OR ２ , or SO ４ R ２ ; B is H, C １ -C １０ Alkyl, C ２ -C １０ It is an alkenyl, aryl, or heteroaryl; C, D, E, and F are, independently of each other, H, C １ -C １０ Alkyl, C ２ -C １０ Arylalkyl, C ３ -C ６ Cycloalkyl, C ２ -C １０ Alkenil, C ２ -C １０ Heteroarylalkyl, C ２ -C １０ Haloalkyl, C ２ -C １０ Dihaloalkyl, C ２ -C １０ Trihaloalkyl, C ２ -C １０ Haloalkoxy, OR ２ , SR ２ , (CR ３ NR ４ R ５ ), NR ４ R ５ (C = N - R ４ ) R １ , N=O, N(=O) ２ , NR ４ OR ２ and SO ４ R ２ Selected from; R １ is selected from H, C １ -C １０ alkyl, C ２ -C １０ arylalkyl, C ３ -C ６ cycloalkyl, C ２ -C １０ alkenyl, C ２ -C １０ heteroarylalkyl, C １ -C １０ haloalkyl, C １ -C １０ dihaloalkyl, C ２ -C １０ trihaloalkyl, C ２ -C １０ haloalkoxy, C １ -C １０ hydroxyalkyl, C １ -C １０ thioalkyl, C １ -C １０ nitroalkyl, OR ２ , SR ２ , (CR ３ NR ４ R ５ ), NR ４ R ５ , (C=N-R ４ )R ６ , N=O, N(=O) ２ , NR ４ OR ７ and SO ４ R ７ and is selected from; R ２ is selected from H, C １ -C １０ alkyl, C ２ -C １０ arylalkyl, C ３ -C ６ cycloalkyl, C ２ -C １０ alkenyl, C ２ -C １０ heteroarylalkyl, C ２ -C １０ haloalkyl, C ２ -C １０ dihaloalkyl, C ２ -C １０ trihaloalkyl, (CR ３ NR ４ R ５ ), NR ４ R ５ , (C=N-R ４ )R ６ , N=O, N(=O) ２ and NR ４ OR ７ ; R ３ H, C １ -C １０ Alkyl, C ２ -C １０ Arylalkyl, C ３ -C ６ Cycloalkyl, C ２ -C １０ Alkenil, C ２ -C １０ Heteroarylalkyl, C ２ -C １０ Haloalkyl, C ２ -C １０ Dihaloalkyl, C ２ -C １０ Trihaloalkyl, C ２ -C １０ Haloalkoxy, OR ７ , SR ７ , (CR ８ NR ４ R ５ ), NR ４ R ５ (C = N - R ４ ) R ６ , N=O, N(=O) ２ , NR ４ OR ７ and SO ４ R ７ Selected from; R ４ and R ５ H and C are independent of each other. １ -C １０ Alkyl, C ２ -C １０ Arylalkyl, C ３ -C ６ Cycloalkyl, C ２ -C １０ Alkenil, C ２ -C １０ Heteroarylalkyl, C ２ -C １０ Haloalkyl, C ２ -C １０ Dihaloalkyl, C ２ -C １０ Trihaloalkyl, OR ７ and SR ７ Selected from; R ６ H, C １ -C １０ Alkyl, C ２ -C １０ Arylalkyl, C ３ -C ６ Cycloalkyl, C ２ -C １０ Alkenil, C ２ -C １０ Heteroarylalkyl, C ２ -C １０ Haloalkyl, C ２ -C １０ Dihaloalkyl, C ２ -C １０ Trihaloalkyl, C ２ -C １０ Haloalkoxy, OR ７ , SR ７ , (CR ８ NR ９ R １０ ), NR ９ N １０ and NR ９ OR ７ Selected from; R ７ H, C １ -C １０ Alkyl, C ２ -C １０ Arylalkyl, C ３ -C ６ Cycloalkyl, C ２ -C １０ Alkenil, C ２ -C １０ Heteroarylalkyl, C ２ -C １０ Haloalkyl, C ２ -C １０ Dihaloalkyl, C ２ -C １０ Selected from trihaloalkyl groups; R ８ H, C １ -C １０ Alkyl, C ２ -C １０ Arylalkyl, C ３ -C ６ Cycloalkyl, C ２ -C １０ Alkenil, C ２ -C １０ Heteroarylalkyl, C ２ -C １０ Haloalkyl, C ２ -C １０ Dihaloalkyl, C ２ -C １０ Trihaloalkyl, OR １１ , SR １１ and NR ９ R １０ Selected from; R ９ and R １０ H and C are independent. １ -C １０ Alkyl, C ２ -C １０ Arylalkyl, C ３ -C ６ Cycloalkyl, C ２ -C １０ Alkenil, C ２ -C １０ Heteroarylalkyl, C ２ -C １０ Haloalkyl, C ２ -C １０ Dihaloalkyl, C ２ -C １０ Trihaloalkyl, OR １２ and SR １２ Selected from; R １１ and R １２ H and C are independent. １ -C １０ Alkyl, C ２ -C １０ Arylalkyl, C ３ -C ６ Cycloalkyl, C ２ -C １０ Alkenil, C ２ -C １０ Heteroarylalkyl, C ２ -C １０ Haloalkyl, C ２ -C １０ Dihaloalkyl and C ２ -C １０ Selected from trihaloalkyl groups; (and at least one second insecticide is selected from pyrethroids or pyrethrins.) A method for controlling winged insect pests, comprising the step of exposure to an effective amount of a combination of β-diketone compounds, Both the β-diketone compound of formula (I) and at least one second insecticide are used in amounts less than an effective amount; method.

2. The compound of formula (I) has a structural formula 【Chemistry 2】 The method according to claim 1, wherein the compound is selected from the compounds.

3. The method according to claim 1, wherein the compound of formula (I) is selected from tasmanone (1-isobutyroyl-4-methoxy-3,5,5-trimethylcyclohexa-3-ene-2,6-dione), agromerone (1-isobutyroyl-4-methoxy-5,5-dimethylcyclohexa-3-ene-2,6-dione), lateriticone (1-valeroyl-4-methoxy-3,5,5-trimethylcyclohexa-3-ene-2,6-dione), isolateriticone (1-isovaleroyl-4-methoxy-3,5,5-trimethylcyclohexa-3-ene-2,6-dione) and platiphyllo (6,6-dimethyl-2-acetyl-5-methoxycyclohexa-4-ene-1,3-dione).

4. The method according to claim 1, wherein the compound of formula (I) is selected from tasmanone (1-isobutyroyl-4-methoxy-3,5,5-trimethylcyclohexa-3-ene-2,6-dione).

5. The second insecticide is Acrinatrin, Allethrin, Bifenthrin, Bioallethrin, Bioallethrin-S-Cyclopentyl, Biorethmetrin, Cycloprotrin, Cyfluthrin, β-Cyfluthrin, Cyhalothrin, γ-Cyhalothrin, λ-Cyhalothrin, Cypermethrin, α-Cypermethrin, β-Cypermethrin, θ-Cypermethrin, ζ-Cypermethrin, Cyphenothrin, Deltamethrin, Dimefluthrin, Empenthrin, Esfenvalerate, Etofenprox, Fe The method according to claim 1, wherein the pyrethroid is selected from npropatrin, fenvalerate, flucitrinate, flumethrin, fluvalinate, tau-fluvalinate, halfenprox, imiprothrin, metofluthrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (chrysanthemum), resmethrin, RU15525, silafluofen, tefluthrin, tetramethrin, tralomethrin, transfluthrin, and ZX18901.

6. The method according to claim 1, wherein the second insecticide is selected from permethrin, deltamethrin, and cypermethrin.

7. The method according to claim 1, wherein the second insecticide is a pyrethrin selected from pyrethrin I, synerin I, jasmolin I, pyrethrin II, synerin II, and jasmolin II.

8. The method according to claim 1, wherein the winged insect pest is resistant to permethrin.

9. The method according to claim 1, wherein the winged insect pest is selected from the orders Lepidoptera, Coleoptera, Diptera, Thysanoptera, Hymenoptera, Hemiptera, Heteroptera, Homoptera, Isoptera, Blattoidae, Orthoptera, Phthiraptera, Siphonaptera, Thysanura, Dermaptera, and Psocoptera.

10. The method according to claim 1, wherein the winged insect pest is selected from the order Diptera.

11. Winged insect pests, Anastrepha, Ceratitis, Contarinia, Dacus, Dasineura, Delia, Hydrellia, Hyleniyia, Lir iomyza, Mayetiola, Orseolia, Oscinella, Pegomya, Phorbia, Rhagoletis, Aedes, Anopheles , Chrysomya, Cochliomyia, Cordylobia, Culex, Fannia, Gasterophilus, Glossina, Haernat obia, Haplodiplosis, Hypoderma, Lucilia, Musca, Muscina, Oestrus, Tabanus and Simulium, The method according to claim 1, selected from the genus.

12. The method according to claim 1, wherein the winged insect pest is selected from the genera Culex and Aedes.

13. The method according to claim 1, wherein both the β-diketone compound of formula (I) and at least one second insecticide are used in amounts less than the amount added.

14. The method according to claim 1, wherein winged insect pests are controlled by incapacitation, preferably by death.

15. A composition for controlling winged insect pests, comprising a β-diketone compound of formula (I) as described in claim 1 and at least one second insecticide selected from pyrethroids or pyrethrins, wherein both the β-diketone compound and at least one pyrethroid or pyrethrin are present in amounts less than an effective amount.

16. The composition according to claim 15, wherein both a β-diketone compound and at least one pyrethroid or pyrethrin are included in amounts less than the amount added.

17. The β-diketone compound of formula (I) is LC ５ ~LC ２５ It contains in an amount of at least one pyrethroid or pyrethrin for approximately LC ４０ ~Approximately LC ６０ It is contained in an amount of , or the β-diketone compound of formula (I) is LC １５ ~LC ６０ It contains in an amount and at least one pyrethroid or pyrethrin is LC １５ ~LC ６０ The composition according to claim 16, which is contained in the amount of [amount].

18. A kit for use in a method for controlling winged insect pests, comprising a β-diketone compound of formula (I) as described in claim 1, at least one second insecticide selected from pyrethroids or pyrethrins, and instructions for exposing winged insect pests to a combination of the β-diketone compound of formula (I) and at least one pyrethroid or pyrethrin using less than an effective amount of both the β-diketone compound and the pyrethroid or pyrethrin.

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