Reduced survival rate of unseen pests

Abstract

This disclosure relates to methods for controlling pests. More specifically, this disclosure relates to methods for reducing the viability of unemerged pests, such as eggs, by exposing them to an effective amount of a compound of formula (I) as defined herein. This disclosure also relates to methods for controlling pests by exposing unemerged pests to an effective amount of a compound of formula (I) as defined herein. Insecticide compositions are also described. JPEG2026527639000015.jpg4047

Description

[Technical Field]

[0001] Related applications

[0001] This application claims the interests of Australian Provisional Patent Application No. 2023902520, filed on 9 August 2023, the entire contents of which are incorporated herein by reference.

[0002]

[0002] This disclosure relates to methods for controlling pests. More specifically, this disclosure relates to methods for reducing the viability of unemerged pests, such as eggs, by exposing them to an effective amount of a compound of formula (I) as defined herein. This disclosure also relates to methods for controlling pests by exposing unemerged pests to an effective amount of a compound of formula (I) as defined herein. Insecticide compositions are also described. [Background technology]

[0003]

[0003] Effective pest control is essential across many industries, particularly in agriculture, in the production of food and livestock. For example, ineffective insect control and insect infestations can lead to the complete destruction of crops, catastrophic reduction of animal populations due to insect feeding, and the spread of diseases and infections, as well as contamination of food production lines, with associated health concerns for consumers, which are animals and humans. Household and industrial insect control is equally essential to mitigate the spread of insect-borne infections and diseases, as well as for good hygiene practices.

[0004]

[0004] Most pest control strategies target the control of post-emerging pests. For example, insects often reproduce throughout their life cycle, including post-emerging larval, nymphal, and adult forms, which are the targets of most insect control strategies. There are good reasons for this, including the fact that these forms, particularly the adult form, are considered to cause the most damage, pose the most danger, and require the most control. These forms are also often considered the easiest to control because they generally have the longest lifespan, exhibit the most obvious outbreaks, are the largest, are the most mobile (e.g., most susceptible to physical and mechanical control methods), and are the most susceptible (or often the only susceptible) to chemical control methods.

[0005]

[0005] There are relatively few pest control methods that target unemerged pests, such as eggs. Similarly, there is good reason for this, and generally the opposite is true: unemerged pests often cause little damage and pose little danger, but they are the shortest-lived, the smallest, immobile, difficult to detect, located in protected areas, the most difficult to control, and often less susceptible to chemical control methods.

[0006]

[0006] Susceptibility to chemical control methods is a key difference between unemerged and postemerged pests. Unemerged pests contain a sheath (e.g., a shell) that substantially provides a protective barrier for the contained unemerged pest morphs, which may be impermeable to many chemical control agents. Even when chemical control agents can penetrate this barrier, the contained insect morphs often do not have the same biological target sites that the chemical agent is effective against nymphs or adults, if the eggs are embryos, and / or not in the same abundance. Some unemerged morphs, including embryos, may also produce unique enzymes that break down chemical control agents. In specific examples, bed bug (Cimex lectularius) eggs have been shown to be less susceptible to pyrethroid insecticides than nymphs or adults through enhanced enzymatic degradation, eggshell permeability resistance, and lower biological target site sensitivity. In another example, long-eared beetle (Rhyzopertha dominica) eggs have been shown to be less susceptible to phosphine than nymphs and adults through a similar mechanism.

[0007]

[0007] This tends to necessitate the application of targeted chemical control agents (e.g., fixed-point application rather than broad-field spraying) and higher application rates in controlling unemerged pests, and even chemicals that can penetrate protective sheaths can make unemerged pest control economically and environmentally unfeasible. Ultimately, this leads to a focus on controlling other life cycle stages and pest morphologies, particularly nymphs and adults. There remain relatively few pest control agents that target unemerged pests.

[0008]

[0008] It is desirable to provide an improved pest control method to address at least some of the above problems, which may provide users with further pest management options. [Overview of the project] [Means for solving the problem]

[0009]

[0009] In one aspect, the present disclosure is a method for reducing the viability of unemerged pests, comprising exposing the unemerged pests to an effective amount of a compound of formula (I),

[0010]

Chemical Formula

[0011] (wherein, X and Y are each independently selected from oxygen, sulfur, and NR4, 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=NR4)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 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, ORG2, SR2, (CR3NR4R5), NR4R5, (C=NR4)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 10Haloalkoxy, C1~C 10 Hydroxyalkyl, C1-C 10 Thioalkyl, C1~C 10 Selected from nitroalkyl, OR2, SR2, (CR3NR4R5), NR4R5, (C=NR4)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=NR4)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=NR4)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 10Arylalkyl, 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 ), NR9R 10 Selected from , 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 and C2-C 10 Selected from trihaloalkyl groups, 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 NR9OR 10 Selected from, R9 and R 10 These are H, C1~C independently. 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 Selected from, R 11 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 and C2-C 10 trihaloalkyl, and R 12 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 and C2-C 10 trihaloalkyl). A method is provided that includes the step of exposing to

[0012] In another aspect, a method for controlling pests is provided that includes the step of exposing the pest to an effective amount of a compound of formula (I) described herein. In another aspect, there is provided the use of a compound of formula (I) described herein for reducing the viability of a non-emerged pest or for controlling a pest, which use comprises exposing the non-emerged pest to an effective amount of the compound of formula (I).

[0013] In another aspect, a kit is provided that comprises a compound of formula (I) described herein for use in reducing the viability of a non-emerged pest or for controlling a pest.

[0014] In a preferred embodiment of each aspect, the non-emerged pest is a pest egg. In a preferred embodiment of each aspect, the compound of formula (I) is a β-diketone compound of formula (I) as defined herein, preferably tasmanone. [Brief explanation of the drawing]

[0015] [Figure 1]

[0015] Figure 1 is a photograph of the ovicidal activity test against eggs of Cimex lectularius (Example 1), showing the appearance of dead eggs, hatched eggs, and dead nymphs. [Figure 2]

[0016] Figure 2 shows a graph of the mean percentage (mean ± standard error, n=5) of ovicidal and nymph mortality rates of bed bugs (Cimex lectularius) 14 days after treatment application in a dose-exploratory study of ovicidal activity against Cimex lectularius eggs (Example 1). [Figure 3]

[0017] Figure 3 is a graph showing the average percentage (mean ± standard error, n=5) of egg and nymph mortality rates of two-spotted spider mites and Tetranychus urticae five days after treatment application in a dose-exploratory study of ovicidal activity against Tetranychus urticae eggs (Example 3). [Figure 4]

[0018] Figure 4 shows a graph of the mean percentage (mean ± standard error, n=5) of ovicidal activity against Tetranychus urticae eggs and nymph mortality rates five days after treatment in the final dose exploration test (Example 3). [Modes for carrying out the invention]

[0016]

[0019] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art. Any methods and materials similar or equivalent to those described herein may be used in the embodiments of the practice or test described herein, but preferred methods and materials are described. For the purposes of this disclosure, several terms are defined throughout.

[0017]

[0020] As used herein, the terms “a” and “an” are used to refer to one or more (i.e., at least one) grammatical objects of articles. For example, “one element” means one element or more elements.

[0018]

[0021] As used herein, the term "and / or," for example, "A and / or B," shall be understood to mean either "A and B" or "A or B," and shall be construed as providing explicit support for both meanings or either meaning.

[0019]

[0022] As used herein, the term “approximately” means ±10% of the specified value unless otherwise stated.

[0023] Unless the context requires other meanings for the sake of explicit wording or necessary implications, when used herein, variations such as “comprise,” “comprises,” or “comprising” are used in a comprehensive sense, i.e., to identify the presence of the described features, but do not preclude the presence or addition of further features in the various embodiments disclosed.

[0020]

[0024] Where any prior art publication is referenced herein, such reference should not be understood as an endorsement that such publication forms part of the common knowledge in any country. Compound of formula (I)

[0025] The compound of formula (I) is defined as follows:

[0021] [ka]

[0022] During the ceremony, X and Y are each independently selected from oxygen, sulfur, and NR4, 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=NR4)R1, N=O, N(=O)2, NR4OR2, or SO4R, B is H, C1-C 10 alkyl, C2-C 10 alkenyl, aryl, or heteroaryl, C, D, E, and F 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 trihaloalkyl, C2-C 10 and are selected from haloalkoxy, OR2, SR2, (CR3NR4R5), NR4R5, (C=NR4)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 and are selected from nitroalkyl, OR2, SR2, (CR3NR4R5), NR4R5, (C=NR4)R6, N=O, N(=O)2, NR4OR7, and SO4R7, R2 is H, C1-C 10 alkyl, C2-C 10Arylalkyl, 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=NR4)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=NR4)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 ), NR9R10 Selected from , 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 and C2-C 10 Selected from trihaloalkyl groups, 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 NR9OR 10 Selected from, R9 and R 10 These are H, C1~C independently. 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 Selected from, R 11 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 10Selected from trihaloalkyl groups, R 12 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 Selected from trihaloalkyl groups.

[0023]

[0026] As used herein, "a" and "b" are integers. a ~C b " or "C a~b " refers to the number of carbon atoms in a particular group. That is, the group may contain "a" to "b" carbon atoms (including both ends). Therefore, for example, a "C1-C4 alkyl (C1 to C4 alkyl)" group (which may be written as "C1-C4 alkyl (C1-C4 alkyl)") includes alkyl groups having 1 to 4 carbon atoms, consisting of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, and 4 carbon atoms, such as CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, CH3CH2CH2CH2-, CH3CH2CH(CH3)-, and (CH3)3C-.

[0024]

[0027] As used herein, the term "alkyl" refers to a linear or branched saturated hydrocarbon group. Alkyl groups may have a specific number of carbon atoms, for example, C 1~C6 alkyl groups include alkyl groups having 1, 2, 3, 4, 5, or 6 carbon atoms in a linear or branched configuration. Suitable examples of 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.

[0025]

[0028] As used herein, the term "cycloalkyl" refers to saturated cyclic hydrocarbons. Cycloalkyls may have a specific number of carbon atoms; for example, C3-C6 cycloalkyls include cycloalkyls having 3, 4, 5, or 6 carbon atoms. Examples of preferred cycloalkyls include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0026]

[0029] As used herein, the term “alkenyl” refers to a linear or branched hydrocarbon group having one or more double bonds between carbon atoms. An alkenyl group may have a specific number of carbon atoms; for example, C2-C6 alkenyls include alkenyl groups having 2, 3, 4, 5, or 6 carbon atoms in a linear or branched configuration. Examples of preferred alkenyl groups include, but are not limited to, ethenyl, propenyl, isopropenyl, butenyl, butadienyl, pentenyl, pentadienyl, hexenyl, hexadienyl, heptenyl, octenyl, nonenyl, and decenyl.

[0027]

[0030] As used herein, the term “aryl” refers to a stable monocyclic, bicyclic, or tricyclic carbocyclic system having up to seven atoms in each ring, with at least one ring being aromatic. Examples of such aryl groups include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, indanyl, fluorenyl, phenantrenyl, biphenyl, and binaphthyl.

[0028]

[0031] As used herein, the term "heteroaryl" refers to a stable monocyclic, bicyclic, or tricyclic ring having up to seven atoms in each ring, where at least one ring is aromatic and at least one ring contains 1 to 4 heteroatoms selected from the group consisting of O, N, and S. Suitable heteroaryl groups include, but are not limited to, acridinyl, carbazolyl, synnolinyl, quinoxalinyl, quinazolinyl, pyrazolyl, indolyl, isoindolyl, 1H,3H-1-oxoisoindolyl, benzotriazolyl, furanyl, thienyl, thiophenyl, benzothienyl, benzofuranyl, benzodioxane, benzodioxin, quinolinyl, isoquinolinyl, oxazolyl, isoxazolyl, imidazolyl, pyrazinyl, pyridadinyl, 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-tetradinyl, and tetrazolyl. Certain heteroaryl groups have a 5-membered ring or a 6-membered ring, such as pyrazolyl, furanyl, thienyl, oxazolyl, indolyl, isoindolyl, 1H,3H-1-oxoisoindolyl, isoxazolyl, imidazolyl, pyrazinyl, pyridadinyl, pyridinyl, pyrimidinyl, pyrrolyl, thiazolyl, isothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, and 1,2,4-oxadiazolyl and 1,2,4-thiadiazolyl.

[0029]

[0032] As used herein, the term "haloalkyl" refers to an alkyl group in which one or more hydrogen atoms are substituted with halo atoms. Haloalkyl groups may have a certain number of halo substituents, such as dihaloalkyls (2) and trihaloalkyls (3). Suitable haloalkyl groups include 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, Examples include, but are not limited to, 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.

[0030]

[0033] The term "halo" refers to fluorine, chlorine, bromine, and / or iodine.

[0034] As used herein, the terms “hydroxyalkyl,” “thioalkyl,” and “nitroalkyl” refer to alkyl groups in which one or more hydrogen atoms are substituted with a hydroxyl group, a thiol group, or a nitro group, respectively.

[0031]

[0035] As used herein, the term "alkoxy" refers to an oxygen substituent substituted with an alkyl group. Suitable examples of 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).

[0032]

[0036] Compounds of formula (I) may exist in tautomeric forms containing the cyclohexene core motif, and many may exist as different geometric isomers and diastereomers. The compounds of formula (I) as defined herein are interpreted to include all tautomers, individual isomers, and mixtures of isomers. Separation of individual isomers or selective synthesis of individual isomers can be achieved by applying various methods known to those skilled in the art.

[0033]

[0037] The compound of formula (I) may exist as a solvate, for example, a hydrate, and / or as a salt. Suitable examples of salts include, but are not limited to, monovalent metal salts, such as sodium and potassium salts, divalent metal salts, such as calcium, magnesium, iron, and copper salts, and ammonium salts, such as isopropylammonium salt, trialkyl salts, and tetraalkylammonium salts. Examples of suitable salts include 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 agriculturally acceptable salts including 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, mucoic 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, EDTA, stearic acid, palmitic acid, oleic acid, lauric acid, pantothenic acid, tannic acid, ascorbic acid, and valeric acid. The compounds of this disclosure are construed to include all solvates and salts thereof.

[0034]

[0038] The compound of formula (I) was found to be effective against unemerged pests. It is thought that the compound of formula (I) can penetrate the protective sheath of unemerged pests.

[0039] In a preferred embodiment, in the compound of formula (I), X and Y are independently selected from oxygen and sulfur, respectively. A is (C=O)R1, (C=S)R1, (CR3NR4R5), NR4R5, (C=NR4)R1, or NR4OR2. B is H or C1~C 10 It is alkyl, C, D, E, and F are independent of H, C1-C 10 Selected from alkyl, OR2, and SR2, R1 is H, C1~C 10 Alkyl, C2~C 10 Alkenyl, C1~C 10Haloalkyl, C1~C 10 Dihaloalkyl, C2~C 10 Trihaloalkyl, C1-C 10 Hydroxyalkyl, C1-C 10 Thioalkyl and C1-C 10 Selected from nitroalkyl groups, R2 is H and C1~C 10 Selected from alkyl groups, R3 is H, C1~C 10 Alkyl, C2~C 10 Alkenyl, C2~C 10 Haloalkyl, C2~C 10 Dihaloalkyl, C2~C 10 Selected from trihaloalkyl groups, R4 and R5 are independently H, C1~C 10 Selected from alkyl and OR7, R7 is H and C1~C 10 Selected from alkyl groups.

[0035]

[0040] When X and Y are independently selected from oxygen and sulfur, respectively, the compound of formula (I) is classified as a β-diketone based on the core motif of cyclohexene β-dione in the structural formula thus formed, and this core motif defines the compound of formula (I). The term β-diketone is interpreted to include thioketones when X and Y can be selected from sulfur. In preferred embodiments, the compound of formula (I) is a β-diketone and is sometimes referred to as the "β-diketone compound of formula (I)".

[0036]

[0041] In a more preferred embodiment, in the β-diketone compound of formula (I), X and Y are independently selected from oxygen and sulfur, respectively. A is (C=O)R1, (C=S)R1, (CR3NR4R5), NR4R5, (C=NR4)R1, or NR4OR2. B is H, C, D, E, and F are independent of C1-C 10 Selected from alkyl and OR2, R1 is H, C1~C 10 Alkyl, C1-C 10 Haloalkyl, C1~C 10 Dihaloalkyl, C2~C 10 Trihaloalkyl, C1-C 10 Hydroxyalkyl, C1-C 10 Thioalkyl and C1-C 10 Selected from nitroalkyl groups, R2 is H, R3 is C1~C 10 Alkyl, C2~C 10 Haloalkyl, C2~C 10 Dihaloalkyl, C2~C 10 Selected from trihaloalkyl groups, R4 and R5 are independently C1~C 10 Selected from alkyl and OR7, R7 is H.

[0037]

[0042] Independently, each C1~C 10 Alkyl, C2~C 10 Alkenyl, C2~C 10 Haloalkyl, C2~C 10 Dihaloalkyl, C2~C 10 Trihaloalkyl, C2~C 10 Haloalkoxy, C1~C 10 Hydroxyalkyl, C1-C 10 Thioalkyl and C1-C 10 Nitroalkyls are preferably C1-C6 alkyl, C2-C6 alkenyl, C2-C6 haloalkyl, C2-C6 dihaloalkyl, C2-C6 trihaloalkyl, C2-C6 haloalkoxy, C1-C6 hydroxyalkyl, C1-C6 thioalkyl, and C1-C6 nitroalkyl.

[0038]

[0043] In a more preferred embodiment, the β-diketone compound of formula (I) is

[0039] [ka]

[0040] It is selected from the group consisting of the following.

[0044] In a more preferred embodiment, the β-diketone compound of formula (I) is selected from the group consisting of tasmanone (1-isobutroyl-4-methoxy-3,5,5-trimethylcyclohexa-3-ene-2,6-dione), agromerone (1-isobutroyl-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 platiphyllor (6,6-dimethyl-2-acetyl-5-methoxycyclohexa-4-ene-1,3-dione). Among the β-diketone compounds of formula (I), tasmanone in particular is considered to have the greatest activity against unemerged pests. In the most preferred embodiment, the β-diketone compound of formula (I) is tasmanone.

[0041]

[0045] The applicability of the compound of formula (I) to the methods disclosed herein arises from its mode of action. The main mode of action of the compound of formula (I) is by acting as a potassium channel activator that prevents the closure of potassium channels, and in many cases, it is thought to result in the incapacitation of unemerged pests, specifically the death of the unemerged pest morphology. Furthermore, the mode of action of the compound of formula (I) is thought to arise from the cyclohexene core motif of the structural formula that defines the compound of formula (I) described herein. This core motif is hypothesized to provide a scaffold for affinity binding to the potassium ion channels of unemerged pests. Moreover, the mode of action of the compound of formula (I) is considered to be most pronounced, i.e., to exhibit maximum biological activity, when the compound of formula (I) is the β-diketone compound of formula (I). This is thought to be due to the assumption that the cyclohexene β-dione core motif of these compounds provides a high binding affinity to the potassium ion channels of unemerged pests.

[0042]

[0046] The compounds of this disclosure can be prepared by methods similar to those known in the art. Exemplary methods are disclosed, for example, in EP-A-338992, EP-A-336898, U.S. Patent No. 4,202,840, U.S. Patent No. 4,869,748, EP-A-186118, EP-A-186119, EP-A-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, EP-A-249150, EP-A-137963, EP-A-394889, EP-A-506907, and EP-B-135191. An exemplary synthesis method is shown in the examples.

[0043]

[0047] Compounds of formula (I), particularly β-diketone compounds of formula (I), can also be obtained from natural sources, especially from volatile oil-containing plants, for example, by extraction.

[0048] The compound of formula (I) may be used directly in the methods disclosed herein as a substantially purified synthetic compound, a substantially purified isolated compound, a crude or extract form, or it may be formulated into a composition for use in the methods disclosed herein. "Substantially purified" means that the 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, and preferably 99.9% by weight. "Crude" form can be interpreted as any form in which the compound of formula (I) is present in an amount of less than about 97% by weight. plant extract

[0049] A "plant extract" is a substance extracted from a plant. Often, a plant extract containing the compound of formula (I) also contains at least one other compound extracted from the plant along with the compound of formula (I). Depending on the content of the compound of formula (I), the plant extract may be in a crude or substantially purified form.

[0044]

[0050] Volatile oil-containing plants capable of producing the compound of formula (I) and extracting the compound of formula (I), particularly the β-diketone compound of formula (I), may be from the Myrtaceae and Hypericaceae families, particularly from the genera Eucalyptus, Baeckea, and Melaleuca. Representative plant species include: (for tasmanone) Eucalyptus tenuiramis, Baeckea frutescens (also known as agromelon), Eucalyptus risdonii, and Eucalyptus cloeziana; (for lateriticone) Eucalyptus lateritica; and (for platiphyllo) Melaleuca cajuputi. Extraction methods are known to those skilled in the art and include, for example, steam distillation of plant biomass.

[0045]

[0051] In preferred embodiments for producing extracts containing tasmanone, the plants are the subject of Australian Plant Breeders' Rights Applications No. 2022 / 268, No. 2022 / 267, filed November 29, 2022, and No. 2022 / 266, filed November 26, 2022, selected from one or more Eucalyptus cloeziana varieties designated BGTECLD29, BGTECLD14, and BGTECLD30, respectively. Samples of BGTECLD29, BGTECLD14, and BGTECLD30 are held at James Cook University, Smithfield, Cairns QLD 4870, and Plant Biotech, 41 Menary Road, Coes Creek QLD 4560.

[0046]

[0052] Plant extracts often contain other components and are extracted from plants together with compounds of formula (I), so plant extracts are often compositions.

[0053] The plant extract may contain the compound of formula (I) in an amount of at least about 40% by weight, preferably at least about 45%, 50%, 55%, or 60% by weight. In some embodiments, the compound of formula (I) can be extracted from the plant in an amount of at least about 65%, 70%, 75%, 80%, 85%, 90%, and even 95% by weight relative to the plant extract.

[0047]

[0054] In many cases, plant extracts may be liquid (often oily), in which case the plant extract may contain the compound of formula (I) in amounts of at least about 50 vol% (500 g / L), preferably at least about 55 vol% (550 g / L), 60 vol% (600 g / L), 65 vol% (650 g / L), 70 vol% (700 g / L), 75 vol% (750 g / L), and preferably 80 vol% (800 g / L). In some embodiments, the compound of formula (I) can be extracted from plants in amounts of at least about 81 vol% (810 g / L), 82 vol% (820 g / L), 83 vol% (830 g / L), 84 vol% (840 g / L), and even 85 vol% (850 g / L).

[0048]

[0055] In preferred embodiments, the plant extract is a phytochemical extract. "Phytochemical extract" means a composition in which the plant extract contains at least one phytochemical other than any one of the compounds of formula (I), and which is present in addition, the phytochemical extracted from the plant together with the compound of formula (I). The preference for phytochemical extracts is that, although we do not wish to be bound by theory, the additional phytochemical may help control unemerged pests and reduce their viability by enhancing, even slightly, the activity of the compound of formula (I). For example, the at least one other phytochemical may be one or more of α- / β-phellandrene, cis- / trans-ment-2-en-1-ol, 1,8-cineole, eudesmol, eucalyptol, α-pinene, p-cymene, terpineol, terpinene, globulol, limonene, β-myrcene, citronellal, and linalool. pest

[0056] The pests covered by this disclosure are arthropods. The term “pest” refers to arthropods and is not intended to include mammals, marsupials, plants, or microorganisms. Most arthropods are oviparous. Oviparous arthropods represent preferred embodiments. In preferred embodiments, the pest is an insect (oviparous insect). In other preferred embodiments, the pest is an arachnid (oviparous spider).

[0049]

[0057] As used herein, “unemerged” pest refers to a pest at a stage in its life cycle that contains an unemerged pest morph within a protective sheath produced by the pest itself (which may be produced by the unemerged pest morph itself, an ancestor, a postemerged morph in a preceding life cycle stage, or otherwise). “Unemerged pest morph” refers to the pest itself within the protective sheath. Unemerged pests are distinctly different from “postemerged pests (morphs),” which refer to pests at a stage in their life cycle that are not within a protective sheath. Unemerged pest morphs are generally pests in a developmental stage of their life cycle that will transition to postemerged pest morphs. Many unemerged pests lack the ability to move independently (i.e., are sessile).

[0050]

[0058] Examples of unemerged pests include pest eggs and sheathed pupae. Pest eggs contain an embryo enclosed in an eggshell. In these embodiments, the embryo is the unemerged pest form, and the eggshell is a protective sheath. Examples of unemerged pupae include butterfly pupae, cocoons, and those having pupal exuviae. Cocoons and butterfly pupae contain a pupa within an outer covering, which often contains silk. In these embodiments, the pupa is the unemerged pest form, and the outer covering is a protective sheath. Other pupae may be enclosed in a pupal exuvia. In these embodiments, the pupa is the unemerged pest form, and the pupal exuvia is a protective sheath. Sheathed pupae can be naked pupae, pupae, or peripupa. In preferred embodiments, the unemerged pest is the pest egg. Compounds of formula (I), particularly the β-diketone compounds of formula (I), have been found to be especially effective against pest eggs.

[0051]

[0059] Insect pests can be selected from the following: a. From the order 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 little, 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, Ostrinianubilalis, Pandemis heparana, Panolis flamnea, 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, as well as Galleria mellonella, Sitotroga cerealella, Ephestia cautella and Tineola bisselliella, b. From the order Coleoptera, for example, Alphitobius diaperinus, 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 species, Phyllotreta chrysocephala, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Psylliodes napi, Scolytus intricatus and Sitona lineatus, as well as 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 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, as well as Aedes aegypti, Aedes vexans, Aedes albopictus, Anopheles maculipennis, Chrysomya bezziana, Cochliomyia hominivorax, Chrysomya macellaria, Cordylobia anthropophaga, Culex pipiens, Fannia canicularis, Gasterophilus intestinalis, Haernatobia irritans, Haplodiplosis equestris, Hypoderma lineata, Lucilia cuprina, Lucilia sericata, Musca domestica, Muscina stabulans, Oestrus ovis, Tabanus bovinus and Simulium damnosum, d. (Thysanoptera)から、For example、Frankliniella fusca、Frankliniella occidentalis、Frankliniella tritici、Haplothrips tritici、Heliothrips hemorrhoidalis、Scirtothrips citri、Rice thrips、Palm thrips and Tobacco thrips、 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 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, g. From the order Homoptera, for example, Acyrthosiphon onobrychis, Acyrthosiphon pisum, Adelges laricis, Aonidiella aurantii, Aphidula nasturtii, Aphis fabae, Aphis gossypii, Aphis pomi, Aulacorthum solani, Bemisia tabaci, Brachycaudus cardui, Brevicoryne brassicae, Dalbulus maidis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Empoasca fabae, Eriosorna lanigerum, Laodelphax striatella, Macrosiphum avenae, Macrosiphun euphorbiae, Macrosiphun rosae, Megoura viciae, Metopolophium dirhodum, Myzus persicae, Myzus cerasi, Nephotettix cincticeps, Nilaparvata lugens, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla pyri, Psylla pyricola, Rhopalosiphum maidis, Schizaphis graminum, Sitobion avenae, Sogatella furcifera, Toxoptera citricida, Trialeurodes abutilonea, Trialeurodes vaporariorum and Viteus vitifolaei, h. From the order Isoptera, for example, Kalotermes flavicollis, Coptotermes species, Leucotermes flavipes, Macrotermes subhyalinus, Macrotermes darwiniensis, Mastotermes species, Microtermes species, Nasutitermes species such as Nasutitermes walkeri, Odontotermes formosanus, Reticulitermes lucifugus and Termes natalensis, i. 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, Blattallella germanica and Periplaneta americana, j. From the order Phthiraptera, for example, Mallophaga such as Damalina, and Anoplura such as Linognathus and Haematopinus, and Pediculus species, k. From the order Hemiptera, for example, Aphis, Aleurocanthus, Bemisia, Phorodon, Aeneolamia, Empoasca, Perkinsiella, Pyrilla, Aonidiella, Coccus, Pseudococcus, He lopeltis, Lygus, Dysdercus, Oxycarenus, Nezara, Aleyrodes, Triatoma, Psylla, Myzus, Megoura, Phylloxera, Adelges, Nilaparvata, Nephotettix or Cimex species, l. From the order Siphonaptera, for example, species Ctenocephalides or Pulex, m. From the order Thysanura, for example, the Lepisina species, n. From the order Dermaptera, for example, the species Forficula, o. From the order Psocoptera, for example, the species Peripsocus.

[0052]

[0060] Arachnidae pests may be selected from, for example, spiders, pseudoscorpions, microscorpions, mites, and ticks. Preferably, the arachnidae pests are selected from mites, ticks, and spiders, and preferably from the following: a. Mites, for example, Aculops lycopersicae, Aculops pelekassi, Aculus Schlechtendali, Brevipalpus phoenicis, Brevipalpus californicus, Bryobia praetiosa, Bryobia rubrioculus, Dermanyssus gallinae, Eotetranychus carpini, Eotetranichus lewisi, Eutetranychus banksia, Eutetranychus orientalis, Eriophyes sheldoni, Eryophyes tiliae, Eriophyes inangulis, Eriophyes vitis, Oligonychus pratensis, Oligonychus coffeae, Oligonitis oryzae, Oligonychus milleri, Panonychus ulmi, Panonychus citri, Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Sarcoptes scabiei, Tarsonemus pallidus, Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus and Tetranychus urticae. b. Ticks, for example, Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus miccroplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobius megnini, Rhipicephalus apendiculatus, Rhipicephalus evertsi and Rhipicephalus microplus. c. Spiders, e.g., Lampona species (e.g., L. cylindrata, L. murina), Badumna species (e.g., B. insignis, B. longinqua), Steatoda grossa, Cheiracanthium species (e.g., C. punctorium, C. mildei, C. inclusum, C. lawrencei, C. japonicum, C. mildei), Parasteatoda tepidariorum, Kukulcania hibernalis, Eratigena species (e.g., E. agrestis, E. atrica), Tegenaria domestica, Pholcus phalangioides, Argiope keyserlingi, huntsman spiders (of the family Sparassidae), wolf spiders (of the family Lycosidae), Latrodectus species (e.g., L. hasselti, L. mactans, L. tredecimguttatus), Atrax robustus, Hadronyche species (e.g., H. formidabilis, H. cerberea, H. versuta, H. infensa, H. macquariensis), Loxosceles reclusa, jumping spiders (of the Salticidae family), and Araneus diadematus.

[0053]

[0061] Preferably, the pest is a parasitic pest of plants or animals. In preferred embodiments, the pest is selected from the order Siphonaptera, particularly Ctenocephalides or Pulex species; from Hemiptera or Homoptera, particularly Cimex, Bemisia, Aleurocanthus, Trialeurodes or Aleyrodes species; from the order Phthiraptera, particularly Pediculus species; from mites, particularly Tetranychus species; and from ticks, particularly Ixodes and Ornithodorus species.

[0054]

[0062] Pests may be insecticide-resistant or insecticide-sensitive. As used herein, the term “insecticide-resistant” means that a pest has developed resistance to one or more insecticides previously used to control it. “Insecticide-sensitive” means that a pest has not developed resistance to one or more other insecticides.

[0055]

[0063] Insecticide-resistant pests may exist within a pest population. Insecticide-resistant pests may be resistant to any one or more insecticides selected from the group consisting of sodium channel modulators, acetylcholinesterase (AchE) inhibitors, GABAergic chloride channel antagonists, nicotinergic acetylcholine receptor agonists, allosteric acetylcholine receptor modulators, juvenile hormone mimetic agents, homoptera feeding inhibitors, mitochondrial ATP synthase inhibitors, oxidative phosphorylation uncouplers, nicotinic acetylcholine receptor channel blockers, chitin biosynthesis inhibitors, molting inhibitors, ecdysone receptor agonists or disruptors, octopamine receptors, mitochondrial complex I electron transport inhibitors, acetyl-CoA carboxylase inhibitors, voltage-gated sodium channel blockers, mitochondrial complex IV electron transport inhibitors, mitochondrial complex IV electron transport inhibitors, ryanodine receptor modulators, and insect growth regulators. method

[0064] The present disclosure relates to reducing the viability of unemerged pests and / or controlling unemerged pests by exposing them to an effective amount of a compound of formula (I) described herein.

[0056]

[0065] As used herein, the term “reduced viability” refers to a reduction in the ability of a pre-emerging pest to fully emerge or to emerge with unsuppressed reproductive capacity. Reduced viability may be determined by comparison with pests not exposed to the compound of formula (I). Physical modifications that make post-emerging pests less attractive to mating partners are included in the components of suppressed reproductive capacity. Post-emerging pests exposed to the compound of formula (I) before emergence and dying before reaching reproductive maturity, or otherwise having suppressed reproductive capacity as a result of the exposure, are included in the components of suppressed reproductive capacity.

[0057]

[0066] As described above, the applicability of the compounds of formula (I), particularly the β-diketone compounds of formula (I), to the methods of this disclosure arises from their mode of action as potassium channel activators. Potassium ion channels are thought to play a particularly important role in the development of unemerged pest morphology, especially egg embryos, and it is assumed that the relative abundance of potassium ion channels in unemerged pest morphology, especially embryos, is similar to the abundance found in their nymphal and adult morphological counterparts.

[0058]

[0067] Even more surprisingly, it was found that the compounds of formula (I), particularly the β-diketone compounds of formula (I), can penetrate the protective sheath of unemerged pests, especially the eggshell, in amounts sufficient to be effective against them. It is thought that unemerged pest morphs, including the embryo, do not produce enzymes that can degrade the compounds of formula (I).

[0059]

[0068] Therefore, compounds of formula (I), particularly β-diketone compounds of formula (I), are especially effective in controlling pests when unemerged pests are exposed to them, and are particularly effective in reducing the viability of unemerged pests, especially pest eggs, when exposed to them. This is advantageous. Most pest control strategies target post-emerged pest forms (larvae, nymphs, and adults) because they are generally the easiest to control. This is partly because post-emerged forms are susceptible to chemical control methods, while unemerged forms are minimally or completely susceptible to certain chemicals. The efficacy of compounds of formula (I) in controlling unemerged pests provides another means of pest control.

[0060]

[0069] In a preferred embodiment, the unemerged pest morphs are killed or otherwise rendered incapacitated, preferably killed.

[0070] Unemerged pests with reduced viability can be similarly referred to as incapacitated unemerged pests. Incapacitation may be achieved by killing or otherwise rendering the unemerged pests in a dying state, or by reducing their ability to emerge with unsuppressed reproductive capacity. Therefore, methods that reduce the viability of unemerged pests can be similarly referred to as methods that incapacitate them.

[0061]

[0071] Unemerged pests can be incapacitated or controlled by applying an effective amount of the compound of formula (I) or a composition containing it to the unemerged pests or to an environment containing the unemerged pests, so as to expose the unemerged pests to the compound of formula (I).

[0062]

[0072] As used herein, the term “environment” means an environment in which an unemerged pest is present or may be present, to which the compound of formula (I) may be applied in order to expose the unemerged pest to the compound. An environment can be a domestic or industrial environment, which generally includes environments inhabited by humans and / or animals. A domestic environment is generally an environment used for leisure, such as a house, gymnasium, leisure center, other building, its rooms and furniture, sheds, cupboards or other storage spaces, tents, patios, verandas, etc., while an industrial environment is generally an environment used for industrial purposes, such as the manufacture, storage or sale of products, such as warehouses, manufacturing plants, retail stores, factories, other buildings, its rooms, furniture and equipment, etc. An environment can also be an agricultural environment, which is generally an industrial environment used for agricultural purposes, such as environments for crop cultivation, storage and / or transport of agricultural products, food processing, livestock facilities, etc., such as fields, greenhouses, silos, sheds, stables, etc.

[0063]

[0073] Pests generally reproduce through a life cycle in which pre-emerged and post-emerged pest forms are continuous. That is, post-emerged pests (e.g., adults) produce pre-emerged pests (e.g., through egg-laying), and these pre-emerged pests grow into post-emerged pests, and so on.

[0064]

[0074] As used herein, the term “control” in the context of pests means inhibiting any form of a pest, including the adult form, from being involved in an environment in a population size that would make it a pest in that environment. This is achieved by exposing unemerged pests to a compound of formula (I), which reduces the viability of the unemerged pests, resulting in a reduced or complete lack of ability to produce postemerged pest forms in the next stage of their life cycle, or a reduced or complete lack of ability to reproduce and produce subsequent generations of pests, ultimately leading to a reduction in the pest population. The compound of formula (I) may also be active against postemerged pest forms, and therefore control may also be achieved in part by reducing the postemerged pest population, but in the context of this disclosure, an incapacitating component for unemerged pests is required. Pest control does not necessarily require the complete eradication of all pests from the population in an environment, but can be achieved by limiting or reducing the number of active populations to a level where the pests are no longer harmful in that environment. What constitutes pest control in terms of the number of pest populations may vary among specific pests, populations, and environments, and can be determined by those skilled in the art.

[0065]

[0075] However, the complete, near-complete, or at least substantial elimination of pest populations from the environment is often desirable.

[0076] Therefore, in a preferred embodiment, the pests are controlled by reducing the number of pest populations in the environment by at least 50%, 55%, 60%, 65%, or 70%, more preferably at least 75%, 80%, 85%, 90%, or 95%, and more preferably up to 98%, 99%, or even 100%.

[0066]

[0077] Unemerged pests are often present in a population. For example, a single female adult pest may lay multiple eggs at once. Therefore, in a preferred embodiment, at least 50%, 55%, 60%, 65%, or 70%, more preferably at least 75%, 80%, 85%, 90%, or 95% of the unemerged pest population is rendered unviable, and more preferably up to 98%, 99%, or even 100%. Unemerged pests may exhibit physical signs of inactivation, such as discoloration, changes in shape, or changes in size, and therefore, unemerged pests can be identified by observing them for physical changes. Unemerged pests can also be identified as pests that remain unemerged even after the period in their life cycle when they would normally be emerging.

[0067]

[0078] The point in time at which pest control is determined after exposure to the compound of formula (I) may depend on the life cycle of the pest being controlled, particularly when eradication of the pest after emergence is desired. For example, the eggs of a given insect species may hatch, for instance, four days after oviposition. Therefore, if exposure occurs on day 1, the point at which control can be determined to have been achieved after exposure may be four days later, when the eggs are expected to hatch.

[0068]

[0079] Compounds of formula (I), particularly β-diketone compounds of formula (I), tend to be volatile and, therefore, when applied to an environment, generally maintain their activity in that environment only for a short period after application. This can be referred to as the "effective period." The effective period may depend on the specific compound of formula (I), the components of the composition containing it, the environment, the application rate, and the susceptibility of the unemerged pests, but generally it can be 1 to several hours after application, for example, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, or 22 hours after application, but is usually less than about 1 day (24 hours) after application. Therefore, if post-emerged pests that were exposed to compounds of formula (I) before emergence die before reaching reproductive maturity, or otherwise have their reproductive capacity suppressed, especially outside the effective period, this may be due to the unemerged pests being exposed to compounds of formula (I). Furthermore, some other chemical control agents are not lethal, but rather act as repellents and temporary incapacitators (knockdown agents), from which at least a portion of the pest population may recover. It is advantageous that the compound of formula (I) may be lethal.

[0069]

[0080] As used herein, the term “effective amount” in the context of the compound of formula (I) means an amount sufficient to reduce the viability of unemerged pests or to control pests by exposing them to it.

[0070]

[0081] The effective dose may be expressed in terms of LC (lethal concentration) or LD (lethal dose), i.e., the concentration or application rate effective in incapacitating (preferably killing) a certain percentage of unemerged pest populations, or in controlling pests by exposure to them. These are essentially the amounts of the compound to which unemerged pests should be exposed to increase the likelihood of their incapacitation, and are extrapolable to the amounts applied to an environment containing unemerged pests, ensuring that the unemerged pests in that environment are exposed to that amount.

[0071]

[0082] The amounts of LC and LD for any given pest may vary among pest species and can be determined by those skilled in the art through routine testing. However, generally speaking, the effective amount is at least LC 50 Amount, preferably at least LC 55 , LC 60 , LC 65 , LC 70 , LC 75 , LC 80 or LC 85 The effective amount may be a quantity (or equivalent LD50) of 50%, 55%, 60%, 65%, 70%, 75%, 80%, or 85%, respectively, which is a concentration that incapacitates unemerged pests or reduces the number of pest populations. In many cases, pest control requires the complete, near-complete, or at least substantial elimination of pest populations from the environment. Therefore, in a preferred embodiment, the effective amount is at least LC50. 90 Quantity, preferably LC 91 , LC 92 , LC 93 or LC 94 Quantity, more preferably at least LC 95 , LC 96 , LC 97 , LC 98 or LC 99 Quantity, or even LC 100 It can be a quantity (or an equivalent LD50).

[0072]

[0083] The physical amount of the compound of formula (I) constituting the effective amount may depend on the specific pest, its susceptibility to the compound, the level of infestation, and the type of control desired, and can be determined by those skilled in the art using the following guidelines. Generally speaking, the compound of formula (I) should be at least about 50 g / ha (0.005 g / m²). 2 ), 100g / ha (0.01g / m²) 2 ), 200g / ha (0.02g / m²) 2 ), 300g / ha (0.03g / m²) 2 ), 400g / ha (0.04g / m²) 2 ), 500g / ha (0.05g / m²) 2 ), 1,000g / ha (0.1g / m²) 2), 2,000g / ha (0.2g / m²) 2 ), 3,000g / ha (0.3g / m²) 2 ) or 4,000g / ha (0.4g / m²) 2 The amount of (I) can be applied to the environment as a lower limit. Preferably, the compound of formula (I) is at least about 50 g / ha (0.005 g / m²). 2 ), 100g / ha (0.01g / m²) 2 ), 200g / ha (0.02g / m²) 2 ), 300g / ha (0.03g / m²) 2 ) or 400g / ha (0.04g / m²) 2 The compound of formula (I) can be applied to the environment in amounts of up to or at least about 11,000 g / ha (1.1 g / m²). 2 ) or at most about 12,000 g / ha (1.2 g / m²) 2 It can be applied to the environment in amounts such as up to or at least about 15,000 g / ha (1.5 g / m²). 2 ), or at most or at least about 20,000 g / ha (2.0 g / m²) 2 This also includes cases where the compound of formula (I) is applied in amounts of approximately 40,000 g / ha (4.0 g / m²). 2 ), 35,000g / ha (3.5g / m 2 ), 30,000g / ha (3.0g / m²) 2 ), 29,000g / ha (2.9g / m 2 ), 28,000g / ha (2.8g / m²) 2 ), 27,000g / ha (2.7g / m²) 2 ), 26,000g / ha (2.6g / m²) 2 ), 25,000g / ha (2.6g / m 2 ) or 24,000 g / ha (2.4 g / m²) 2 The amount can be applied to the environment up to an upper limit of ). Any upper and lower limits can be combined without restriction. For example, the compound of formula (I) can be applied to the environment at approximately 50 g / ha (0.005 g / m²). 2 ) ~ approx. 30,000g / ha (3.0g / m 2 ), or approximately 6,000 g / ha (0.6 g / m²) 2) ~ approx. 24,000g / ha (2.4g / m 2 ), or approximately 200g / ha (0.02g / m²) 2 ) ~ approx. 24,000g / ha (2.4g / m 2 ), or approximately 100g / ha (0.01g / m²) 2 ) ~ approx. 12,000g / ha (1.2g / m 2 It can be applied to the environment in amounts such as ). These amounts and ranges are considered applicable to a wide range of pests. In a preferred embodiment, the compound of formula (I) is approximately 50 g / ha (0.005 g / m²). 2 ) ~ approx. 30,000g / ha (3.0g / m 2 ), or approximately 100g / ha (0.01g / m²) 2 ) ~ approx. 24,000g / ha (2.4g / m 2 ), or approximately 200g / ha (0.02g / m²) 2 ) ~ approx. 15,000g / ha (1.5g / m 2 ), or approximately 300g / ha (0.03g / m²). 2 ) ~ approx. 12,000g / ha (1.2g / m 2 It is applied to the environment in amounts of ). In some embodiments, for example in an agricultural environment, the compound of formula (I) is applied to the environment in amounts of about 50 g / ha (0.005 g / m²). 2 ) ~ approx. 4,000g / ha (0.4g / m 2 ), or approximately 100g / ha (0.01g / m²) 2 ) ~ approx. 3,000g / ha (0.3g / m 2 ), or approximately 200g / ha (0.02g / m²) 2 ) ~ approx. 2,000g / ha (0.2g / m 2 ), or approximately 300g / ha (0.03g / m²). 2 )~Approx. 1,000g / ha(0.1g / m 2 It is applied to the environment in the amount of ( ). combination

[0084] The compound of formula (I) may be applied alone (as a sole insecticide) or in combination with a second insecticide. “Second insecticide” means any insecticide compound other than those extracted from plants together with the compound of formula (I). “Combination” means that the compound of formula (I) and the second insecticide are used together, either separately or sequentially in a single composition or in separate compositions, such that the biological activity of the compound of formula (I) and the second insecticide occurs simultaneously or overlappingly.

[0073]

[0085] When the compound of formula (I) is used together with a second insecticide, one or both, preferably both, of the second insecticide and the compound of formula (I) may be used in amounts less than an effective amount. As used herein, the term “less than an effective amount” in the context of insecticides means an amount less than the amount that, when used alone, is effective in reducing the viability of unemerged pests or in controlling pests by exposure of unemerged pests to the insecticide. That is, less than an effective amount of insecticide is less than an effective amount of that insecticide. For example, if reducing the viability of unemerged pests, the effective amount of insecticide is less than an effective amount of LC 100 When it is a quantity, a quantity less than the effective amount is LC 100 Less than 100% (LC) <100 Quantity) and for example, LC 99 , LC 95 , LC 90 , LC 85 , LC 80 , 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 , LC 10 Or it may be the LC5 amount. Similarly, the effective amount of an insecticide is LC 50 In the case of a quantity, an amount less than the effective amount is LC 50 Less than 100% (LC) <50This is the quantity, and this is, for example, LC 45、 LC 40 , LC 35 , LC 30 , LC 25 , LC 20 , LC 15 , LC 10 Alternatively, it could be an LC5 quantity. The same principle is equally applicable to, for example, an LD quantity.

[0074]

[0086] When the compound of formula (I) is used together with a second insecticide, one or both, preferably both, of the second insecticide and the compound of formula (I) can be used in less than an additive amount. As used herein, “less than an additive amount” in the context of insecticides means an amount in which the combined effects of each insecticide, when used individually, are not effective in controlling pests. In other words, a combination of less than an additive amount of the compound of formula (I) and a second insecticide that is effective in controlling pests is a synergistic combination, i.e., super-additive. For example, if reducing the viability of unemerged pests, using the same example as above based on LC amounts, the effective amount of the combination is LC 100 In the case of quantities, amounts less than the sum of the compound of formula (I) and the second insecticide will result in the LC (Low Calculation Factor) when the effects of each are added together. 100 This is an amount less than LC5. In other words, and generally speaking, the percentage of pest populations incapacitated by each compound of formula (I) and the second insecticide is such that, when used alone, it does not reach the point of controlling the pest, but when used together, the pest is controlled. The same principle is equally applicable to LD5. For example, in a super-additive combination, the amount of compound of formula (I) used in the combination is LC5, LC5. 10 , LC 20 , LC 30 , LC 40 , LC 50 , LC 60 , LC 70 , LC 80 , LC 90 or LC 95 The amount of the second insecticide may be LC, respectively. 95 , LC 90 , LC80 , LC 70 , LC 60 , LC 50 , LC 40 , LC 30 , LC 20 , LC 10 Or it may be less than the amount of LC5. The same principle is equally applicable to the amount of LD.

[0075]

[0087] In a preferred combination, at least one second insecticide has a different mode of action than the compound of formula (I).

[0088] Many secondary insecticides are commonly known and commercially available in the art. Examples can be classified into the following modes of action: sodium channel modulators, acetylcholinesterase (AchE) inhibitors, GABAergic chloride channel antagonists, nicotinergic acetylcholine receptor agonists, allosteric acetylcholine receptor modulators, juvenile hormone mimetic agents, homoptera feeding inhibitors, mitochondrial ATP synthase inhibitors, oxidative phosphorylation uncouplers, nicotinic acetylcholine receptor channel blockers, chitin biosynthesis inhibitors, molting inhibitors, ecdysone receptor agonists or disruptors, octopamine receptors, mitochondrial complex I electron transport inhibitors, acetyl-CoA carboxylase inhibitors, voltage-gated sodium channel blockers, mitochondrial complex IV electron transport inhibitors, ryanodine receptor modulators, and insect growth regulators.

[0076]

[0089] Some specific exemplary second insecticides that are particularly applicable include thiodicarb, emamectin, flubendiamide, indoxacarb, chlorantraniliprole, spinosad, novalon, chlorfenapyr, lufenuron, cyantraniliprole, fenvalerate, diflubenzuron, triprene, methomyl, permethrin and cypermethrin, as well as synthetic pyrethroids and pyrethrins.

[0077]

[0090] The amount of the second insecticide used may be determined based on its label, including less than an effective amount and less than an additive amount, using guidelines such as those provided herein. In some combinations, the amount of the compound of formula (I) used in the combination is equal to or greater than the amount of at least one second insecticide used in the combination, or in other words, the amount of at least one second insecticide used in the combination is equal to or less than the amount of the compound of formula (I) used in the combination. composition

[0091] The compound of formula (I) can be used as is or in combination with other components in a composition. Plant extracts can constitute a composition containing phytochemical extracts as described herein.

[0078]

[0092] Compounds of formula (I) or plant extracts containing them can be formulated together with other ingredients. Since compounds of formula (I), particularly the β-diketone compounds of formula (I), tend to be liquid under atmospheric conditions, formulations can be formulated by any suitable method, preferably as liquid formulations. This may be by means of dissolution, emulsification, suspension, etc. Furthermore, impregnation into or capture within release forms such as gels, granules, or microcapsules is also intended.

[0079]

[0093] The formulation can be prepared as a concentrate or a diluted, ready-to-use preparation.

[0094] Other components include, but are not limited to, the second insecticide described herein, as well as adjuvants such as solvents, carriers, surfactants, defoamers, adhesion aids, stabilizers, thickeners, emulsifiers, wetting agents, synergists, humectants, dyes, and buffers. Many adjuvants are commonly known and commercially available in the art. Natural components are preferred.

[0080]

[0095] When using one or more second insecticides, it is preferable to formulate the compound of formula (I) and one or more second insecticides together in a single composition.

[0096] The selection of an appropriate formulation may be made considering the pest, the application environment, and any second insecticides included. A suitable formulation can be determined by those skilled in the art. Formulation methods and techniques are known to those skilled in the art.

[0081]

[0097] In a preferred embodiment, the compound of formula (I) is included as a plant extract and formulated together with other components.

[0098] Liquid compositions are preferred for broad-area application by spraying. Since compounds of formula (I) and plant extracts containing them tend to be oily, the compositions can be formulated as emulsions in water.

[0082]

[0099] The composition may be formulated with the compound of formula (I) and, if present, one or more second insecticides at concentrations appropriate to the method of application and the pests being controlled. In preferred embodiments, the composition is formulated with concentrations of the compound of formula (I) ranging from about 10 g / L to 400 g / L, 30 g / L to 240 g / L, or 60 g / L to 240 g / L. The concentration of the compound of formula (I) may also be expressed as volume percent, in which case the composition may be formulated with concentrations of the compound of formula (I) ranging from about 0.9 volume percent to 50 volume percent, 2.5 volume percent to 30 volume percent, or 5 volume percent to 30 volume percent. Using these concentrations, the effective amount of the compound of formula (I) described above is about 100 to 200 L / hectare (10 to 20 mL / m²). 2 This can be achieved with the application rate of ). kit

[0100] Compounds of formula (I) may also be provided in kits. The kits may include other components for formulating compositions comprising one or more second insecticides. The kits may include instructions for exposing unemerged pests to compounds of formula (I), and optionally instructions for formulating compositions containing compounds of formula (I). The instructions may include application rates and techniques suitable for specific pests, and optionally formulation instructions, preferably according to preferred embodiments described herein. Typical Embodiments

[0101] A preferred embodiment of the method described herein is a β-diketone compound of formula (I), preferably selected from tasmanone (1-isobutroyl-4-methoxy-3,5,5-trimethylcyclohexa-3-ene-2,6-dione), agromerone (1-isobutroyl-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), preferably tasmanone, and so on. a. The compound of formula (I) is provided as a plant extract, preferably a phytochemical extract, which preferably contains at least 80% by weight of the compound of formula (I). b. Unseen pests are pest eggs. c. The pests are parasitic insects of plants or animals, preferably selected from the order Siphonaptera, particularly Ctenocephalides or Pulex species, from Hemiptera, particularly Cimex species, from the order Phthiraptera, particularly Pediculus species, from mites, particularly Tetranychus species, and from ticks, particularly Ixodes and Ornithodorus species. d. Reducing the viability of unemerged pests and controlling them is achieved by killing the unemerged pest morph, or by killing the post-emerged pest morph as a result of exposure of the unemerged morph to the compound of formula (I). e. The compound of formula (I) is present at approximately 50 g / ha (0.005 g / m³). 2 ) ~ approx. 30,000g / ha (3.0g / m 2 ), or approximately 100g / ha (0.01g / m²) 2 ) ~ approx. 24,000g / ha (2.4g / m 2 ), or approximately 200g / ha (0.02g / m²) 2 ) ~ approx. 15,000g / ha (1.5g / m 2), or approximately 300g / ha (0.03g / m²). 2 ) ~ approx. 12,000g / ha (1.2g / m 2 It is applied to the environment in amounts of ). In some embodiments, the compound of formula (I) is approximately 50 g / ha (0.005 g / m²). 2 ) ~ approx. 4,000g / ha (0.4g / m 2 ), or approximately 100g / ha (0.01g / m²) 2 ) ~ approx. 3,000g / ha (0.3g / m 2 ), or approximately 200g / ha (0.02g / m²) 2 ) ~ approx. 2,000g / ha (0.2g / m 2 ), or approximately 300g / ha (0.03g / m²). 2 )~Approx. 1,000g / ha(0.1g / m 2 It is applied to the environment in the amount of, f. The compound of formula (I) is used in amounts less than the effective amount or less than the add-on amount. g. Compositions containing the compound of formula (I) in concentrations ranging from approximately 10 g / L to 400 g / L, 30 g / L to 240 g / L, or 60 g / L to 240 g / L are used. It is one or more of the above. [Examples]

[0083]

[0102] The compound of formula (I) can be prepared synthetically. In the first representative procedure of Scheme 1, 3-methoxy-2,4,4-trimethylcyclohexa-2-ene-1,5-dione (1 molar equivalent) is dissolved in anhydrous diethyl ether and hexamethyl phosphoramide (solvent ratio, 20:1) 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 10 minutes, the cyanide reagent R1-CO-CN (where R1 is as defined above) (1.1 molar equivalents) is added. The mixture is heated to room temperature over 12 hours, at which point the reaction is quenched with water and partitioned. The ether layer is dried (Na2SO4) and evaporated to obtain the crude compound, which is purified by SiO2 column chromatography (hexane / ethyl acetate, gradient).

[0084] [ka]

[0085]

[0103] In the second typical procedure, 3-methoxy-2,4,4-trimethylcyclohexa-2-ene-1,5-dione (1 molar equivalent) (commercially available) and the cyanide reagent R1-CO-CN (where R1 is as defined above) are dissolved in anhydrous dichloromethane and cooled to 0°C under a nitrogen atmosphere. To the cooled solution, anhydrous finely ground zinc chloride (1.1 molar equivalents) is added, followed by the 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 partitioned and the dichloromethane layer is washed with 5% sodium carbonate. The aqueous carbonate phase is then acidified with hydrochloric acid, extracted with methylene chloride, and dried (Na2SO4). The solvent is removed and the residue is subjected to SiO2 column chromatography.

[0086]

[0104] Metal salts can be prepared by reacting the prepared compound with the corresponding metal hydroxide suspended in methanol or ethanol. Trialkylammonium salts can be prepared by reacting the prepared compound with a trialkylamine in a chlorinated solvent such as dichloromethane. Tetraalkylammonium salts can be prepared by adding a tetraalkylammonium halide to a metal salt in dichloromethane.

[0087] Example 1 Ovicidal activity of Cimex lectularius eggs overview

[0105] A series of laboratory biological studies were conducted to determine the ovicidal activity of a 540 g / L EW formulation of Eucalyptus cloeziana extract oil containing 80.66 wt% tasmanone against bed bugs (Cimex lectularius) based on inhibition of egg hatching / mortality during the egg or nymph stage.

[0088]

[0106] Adult bed bugs were placed on filter paper in a holding container and left until a sufficient number of eggs were laid, after which the adults were removed. Next, the filter paper containing the eggs was placed in a test plot consisting of a transparent plastic container (12 cm in diameter). The treatment was carried out over 100 cm. 2 The solution was applied as a localized spray via a pre-calibrated Potter tower designed to deliver a spray volume of 1 g per unit. The lids of the test plots were left uncovered for 1 hour after spraying to allow any generated vapors to dissipate. Evaluations were performed approximately 3, 7, and 14 days after treatment application. Five replicate experiments were conducted for each treatment, with approximately 15 eggs included per replicate.

[0089]

[0107] Spray application of Qcide 540 EW resulted in a high combination of nymphal and ovicidal activity at doses exceeding 6000 mg ai / L. Mortality remained low in the water-controlled study (0% mortality on day 14). methodology

[0108] Adult bed bugs, Cimex lectularius, an insecticide-susceptible strain, were placed on filter paper in a holding container and left for approximately two days to allow egg-laying. After two days, the adults were removed, and the number of eggs accumulated on the filter paper was counted. The filter paper was divided using scissors so that each repeatable experiment contained approximately 15 eggs. The filter paper containing the eggs was placed in individual test plots, each consisting of a transparent plastic container (12 cm in diameter) with a pinhole in the lid for ventilation. The number of eggs contained was recorded on the lid of each test plot.

[0090]

[0109] Two treatment schedules were performed: an initial dose-finding test and a final dose-finding test. Both used five replicates for a series of treatment volumes of Qcide 540 EW, with the latter being refined based on the results of the former (Table 1). Treatment volumes were prepared by dilution with deionized water without additional adjuvants / wetting agents. Test solutions were prepared in plastic beakers and mixed by hand using a stirring rod.

[0091] [Table 1]

[0092]

[0110] In the test plot containing eggs, 100 cm 2 The solution was sprayed individually using a pre-calibrated Potter Tower (Burkard, United Kingdom) designed to deliver a spray volume of 1 g of solution per unit. After treatment, the lids of the plots were left open for 1 hour to allow any vapors to dissipate. After 1 hour, the lids were replaced. During the experiment, the temperature ranged from 25.0°C to 27.4°C for the initial dose-finding tests and from 25.2°C to 29.3°C for the final dose-finding tests. Evaluations were performed approximately 3, 7, and 14 days after treatment application. The proportion of viable and dead eggs / nymphs present was assessed (Figure 2). result

[0111] The results are presented in graphs and tables. Mean percentage values ​​and standard errors were calculated. Probit analysis was performed using ToxRat Professional version 3.3. The results of the experiment are summarized in Table 2. Probit analysis was performed on the ovicidal and nymph mortality results together to obtain the overall mortality rate relative to the treatment rate.

[0093]

[0112] In the initial dose-finding trial treatment schedule, mortality effects were recorded at doses of 3000 mg ai / L and 30000 mg ai / L, with ovicidal mortality rates of 30% and 97.3%, and nymph mortality rates of 1.5% and 2.7%, respectively (Table 2, Figure 2).

[0094]

[0113] In the final dose-finding trial treatment schedule, doses of 1500 mg ai / L, 3000 mg ai / L, 6000 mg ai / L, 12000 mg ai / L, and 24000 mg ai / L resulted in ovicidal mortality rates of 1.3%, 0%, 12.9%, 26.2%, and 32.5% at day 14, respectively. The nymph mortality rates from hatched eggs at doses of 1500 mg ai / L, 3000 mg ai / L, 6000 mg ai / L, 12000 mg ai / L, and 24000 mg ai / L were observed to be 1.3%, 11.3%, 52.8%, 72.2%, and 67.5% at day 14 after spray application (Table 3). Mortality rates remained low in the water-controlled trial. Egg exposure to tasmanone was thought to contribute to the nymph mortality rate on day 14.

[0095] [Table 2]

[0096] [Table 3]

[0097] Example 2 Ovicidal activity of Tetranychus kanzawai against eggs

[0114] Ten adult female Tetranychus kanzawai mites were released onto separate bean leaves and allowed to lay eggs. The following day, the number of eggs laid was counted, and the leaves were sprayed with 8 mL of a diluted solution of a 200 g / L EC preparation of Eucalyptus cloeziana extract oil containing at least 75 wt% tasmanone (Qcide 200 EC) at an appropriate concentration (Table 4). After spraying, the treated leaves were incubated at 25°C and 70% RH. The number of hatched eggs was counted on the fifth day after treatment (Table 4).

[0098] [Table 4]

[0099] Example 3 Ovicidal activity of Tetranychus urticae against eggs overview

[0115] A series of laboratory biological studies were conducted to determine the ovicidal activity of a 540 g / L EW formulation of Eucalyptus cloeziana extract oil containing 80.66 wt% tasmanone (Qcide 540 EW) against the two-spotted spider mite (TSM), Tetranychus urticae, based on inhibition of egg hatching / mortality during the egg or nymph stage.

[0100]

[0116] Each test plot contained a transparent plastic sauce pot with 1% pre-set agar, on which pieces of green bean leaves were placed. Approximately 15 adult TSM mites were introduced into each plot and left for 24 hours to allow the mites to lay eggs. After 24 hours, the adult mites were removed and the number of eggs was counted. Each plot contained approximately 15 eggs. The treatment was carried out at 500 L / Ha (100 cm²). 2 The treatment was applied as a localized spray via a pre-calibrated Potter Tower (Burkard, United Kingdom) designed to deliver a spray volume equal to 0.5 g of solution per unit. The lids of the test plots were left uncovered for 1 hour after spray application to allow any generated vapors to dissipate. Evaluations were performed on day 1 and day 5 after treatment application. Five replicate experiments were conducted for each treatment.

[0101]

[0117] When Qcide 540 EW was sprayed onto TSM eggs at doses of 375 mg ai / L, 750 mg ai / L, 1500 mg ai / L, 2250 mg ai / L, and 3000 mg ai / L, ovicidal mortality rates of 3.2%, 33.2%, 74.6%, 86.8%, and 91.7% were obtained on day 5, respectively. Mortality rates remained low in the water-controlled study (ovicidal mortality rate <2% on day 5). methodology

[0118] The treatment was performed by dilution with deionized water without the addition of additional adjuvants / wetting agents. The test solutions were prepared in plastic beakers and mixed by hand using a stirring rod. A series of serial dilutions of Qcide 540 EW in deionized water were prepared. Five selected test doses were determined based on initial dose-finding tests, and the results are shown in Figure 3 and Table 5.

[0102]

[0119] In the test plot containing eggs, 500 L / Ha (100 cm³) 2 Each sample was sprayed using a pre-calibrated Potter Tower (Burkard, United Kingdom) designed to deliver a spray volume and coverage equal to 0.5 g of solution per sample. After treatment, the sample lids were left open for 1 hour to allow any vapors to dissipate, then the lids were replaced after 1 hour, and the test samples were placed in a temperature and humidity controlled cabinet.

[0103]

[0120] Bean leaf fragments, approximately 30 mm in diameter, were placed with their abaxial side facing upwards on a 1% agar bed in a 55 mm diameter sauce pot. Twenty adult mites, a mix of males and females, were manually transferred from the preserved culture using a painter's brush. These sections containing the adult mites were kept in a temperature and humidity controlled cabinet.

[0104]

[0121] After 24 hours, the number of eggs accumulated on each leaf was counted (approximately 15 eggs per plot), and the number of eggs was recorded on the lid of each plot. If too many eggs were laid, the excess eggs were removed from the plot (using a paintbrush or by removing a portion of the leaf). Adult mites were removed from the plots before treatment to prevent further egg-laying.

[0105]

[0122] Evaluations were performed using a binocular microscope on day 1 and day 5 after treatment application. The ratio of viable and dead eggs / larvae was assessed. Five replicate experiments were conducted for each treatment (a total of 6 conditions), resulting in a total of 30 tests.

[0106]

[0123] During the experiment, the temperature ranged from 25.7°C to 27.1°C, and the relative humidity ranged from 45% to 58%.

[0124] For statistical analysis, mean percentage values and standard errors were calculated. The probit analysis was performed using ToxRat Professional version 3.3. The results of egg killing and nymph mortality were combined to perform a probit analysis to obtain the total mortality against the treatment rate. Results

[0125] The results are summarized in Tables 6 and 7, and Figure 4. Spraying applications of Qcide 540 EW at dosages of 375 mg ai / L, 750 mg ai / L, 1500 mg ai / L, 2250 mg ai / L, and 3000 mg ai / L against TSM eggs resulted in egg killing mortalities of 3.2%, 33.2%, 74.6%, 86.8%, and 91.7% on the 5th day, respectively. The mortalities of nymphs from hatched eggs at dosages of 375 mg ai / L, 750 mg ai / L, 1500 mg ai / L, 2250 mg ai / L, and 3000 mg ai / L were observed to be 0%, 0%, 7.1%, 11%, and 6% on the 5th day after spraying application, respectively. The mortalities remained low in the water control test, with an egg killing mortality of 2% and a nymph mortality of 1.9%. Exposure of eggs to tasmamon was considered to contribute to nymph mortality.

[0107]

Table 5

Claims

1. A method for reducing the survival ability of unemerged pests, wherein the unemerged pests are subjected to an effective amount of the compound of formula (I). 【Chemistry 1】 (In the formula, X and Y are, independently, oxygen, sulfur, and NR 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 )[[ID=十七]] ２ , OR ２ , NR ４ R ５ , (C=NR ４ ), R １ , N=O, N(=O) ２ , NR ４ , OR ２ or SO ４ R ２ and It should be noted that in the original text, there is an incorrect "十七" in the line break "[[ID=十七]] ２ ", which is likely a misrepresentation. I have translated it as is based on the rules, but this might need to be double-checked in the original context. 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 independent of H and 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=NR ４ ) R １ , N=O, N(=O) ２ , NR ４ OR ２ and SO ４ R ２ Selected from, R １ is 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 ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ 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 = NR ４ ), R ６ , N = O, N(=O) ２ and NR ４ OR ７ and is selected from 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=NR ４ ) R ６ , N=O, N(=O) ２ , NR ４ OR ７ and SO ４ R ７ Selected from, R ４ and R ５ These are H and C, independently. 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 R 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 and 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 OR １０ Selected from, R ９ and R １０ These are H and C, independently. 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 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 and C ２ ~C １０ Selected from trihaloalkyl groups, R １２ 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 and C ２ ~C １０ (Selected from trihaloalkyl groups) The above method, comprising the step of exposure to.

2. X and Y are independently selected from oxygen and sulfur, A is (C=O)R １ (C=S)R １ , (CR ３ NR ４ R ５ ), NR ４ R ５ (C=NR ４ ) R １ or NR ４ OR ２ And, B is H or C １ ~C １０ It is alkyl, C, D, E, and F are independent of H and C. １ ~C １０ Alkyl, OR ２ and SR ２ Selected from, R １ H, C １ ~C １０ Alkyl, C ２ ~C １０ Alkenil, C １ ~C １０ Haloalkyl, C １ ~C １０ Dihaloalkyl, C ２ ~C １０ Trihaloalkyl, C １ ~C １０ Hydroxyalkyl, C １ ~C １０ Thioalkyl and C １ ~C １０ Selected from nitroalkyl groups, R ２ H and C １ ~C １０ Selected from alkyl groups, R ３ H, C １ ~C １０ Alkyl, C ２ ~C １０ Alkenil, C ２ ~C １０ Haloalkyl, C ２ ~C １０ Dihaloalkyl, C ２ ~C １０ Selected from trihaloalkyl groups, R ４ and R ５ These are H and C, independently. １ ~C １０ Alkyl and OR ７ Selected from, R ７ H and C １ ~C １０ Selected from alkyl groups, The method according to claim 1.

3. X and Y are independently selected from oxygen and sulfur, A is (C=O)R １ (C=S)R １ , (CR ３ NR ４ R ５ ), NR ４ R ５ (C=NR ４ ) R １ or NR ４ OR ２ And, B is H, C, D, E, and F are independent of C １ ~C １０ Alkyl and OR ２ Selected from, R １ H, C １ ~C １０ Alkyl, C １ ~C １０ Haloalkyl, C １ ~C １０ Dihaloalkyl, C ２ ~C １０ Trihaloalkyl, C １ ~C １０ Hydroxyalkyl, C １ ~C １０ Thioalkyl and C １ ~C １０ Selected from nitroalkyl groups, R ２ H is, R ３ C １ ~C １０ Alkyl, C ２ ~C １０ Haloalkyl, C ２ ~C １０ Dihaloalkyl, C ２ ~C １０ Selected from trihaloalkyl groups, R ４ and R ５ Independently, C １ ~C １０ Alkyl and OR ７ Selected from, R ７ H is The method according to claim 1 or 2.

4. The compound of formula (I) 【Chemistry 2】 A method according to any one of claims 1 to 3, selected from the group consisting of the following.

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

6. The method according to any one of claims 1 to 5, wherein the compound of formula (I) is tasmanone.

7. The method according to any one of claims 1 to 6, wherein the unappeared pest is the egg of the pest.

8. A method for controlling pests, comprising the step of exposing unseen pests to an effective amount of the compound of formula (I) described in any one of claims 1 to 6.

9. The method according to any one of claims 1 to 8, wherein the compound of formula (I) is provided in a plant extract.

10. The method according to claim 9, wherein the plant extract is a phytochemical component extract.

11. The method according to claim 9 or 10, wherein the extract is derived from a plant of the species Eucalyptus.

12. The method according to any one of claims 9 to 11, wherein the plant extract contains the compound of formula (I) in an amount of about 50% to about 95% by weight.

13. The method according to any one of claims 1 to 12, wherein the pest is selected from the orders Siphonaptera, Hemaptera, Phthiraptera, mites, and ticks.

14. The method according to any one of claims 1 to 13, wherein the pest is selected from the group consisting of the species Ctenocephalides, Pulex, Cimex, Bemisia, Aleurocanthus, Trialeurodes, Aleyrodes, Pediculus, Tetranychus, Ixodes, and Ornithodorus.

15. An effective amount of the compound of formula (I) is applied to an environment containing unemerged pests at a rate of approximately 50 g / ha (0.005 g / m²). ２ ) ~ approx. 40,000g / ha (4.0g / m ２ The method according to any one of claims 1 to 14, wherein the amount is )

16. The method according to any one of claims 1 to 15, wherein the compound of formula (I) is applied to the environment as a composition containing about 10 g / L to 400 g / L.

17. The method according to any one of claims 1 to 16, wherein the compound of formula (I) is used in combination with at least one second insecticide.

18. Use of a compound of formula (I) according to any one of claims 1 to 6 for reducing the viability of unemerged pests or for controlling pests, wherein the use involves exposing unemerged pests to an effective amount of the compound of formula (I).

19. A kit for use in reducing the viability of unemerged pests or controlling pests, comprising a compound of formula (I) as described in any one of claims 1 to 6, and optionally another component.

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