Pesticidal methods and compositions

Abstract

The present disclosure relates generally to methods and uses for controlling pests. More particularly, the present disclosure relates to methods and uses for controlling pests in a covered environment, comprising exposing said pests to an effective amount of a vapour form of a compound of formula (I) as defined herein. Also described are pesticidal compositions, kits comprising a compound of formula (I) and a diffuser, diffusers and refill vessels for diffusers.

Description

PESTICIDAL METHODS AND COMPOSITIONS RELATED APPLICATION

[0001] This application claims the benefit of Australian provisional patent application number 2023902139, filed 3 July 2023, the entire contents of which is incorporated herein by reference. FIELD OF THE DISCLOSURE

[0002] The present disclosure relates generally to methods and uses for controlling pests. More particularly, the present disclosure relates to methods and uses for controlling pests in a covered environment, comprising exposing said pests to an effective amount of a vapour form of a compound of formula (I) as defined herein. Also described are pesticidal compositions, kits comprising a compound of formula (I) and a diffuser, diffusers and refill vessels for diffusers. BACKGROUND OF THE DISCLOSURE

[0003] Effective pest control is important across many industries, not least of all in agriculture in the production of food and livestock. For instance, insect infestation arising from ineffective insect control can result in complete destruction of a stored crop harvest, or contamination of the harvest and food production lines, with the associated health concerns for animal and human consumers, including through the spread of disease and infection. Arthropod vector-borne diseases can also spread rapidly through animal populations, especially those relying on animal houses, resulting in losses and potentially decimation of the animal population. Domestic and industrial insect control is similarly important to mitigate the spread of insect-borne infection and diseases and for good hygiene practices.

[0004] Arthropod vectors, including the mosquito vectors of dengue, malaria and filariasis, and fly species such as sand and filth flies that transmit diseases such as leishmaniasis, enteric and helminth infections, remain significant public health pests worldwide.

[0005] With the rising threat from pesticide resistant vectors and global environmental change there is an increasing need to incorporate more pest controlinterventions to reduce the spread of, or eliminate, these diseases, to protect harvests, avoid contamination of food production lines, and for good hygiene practices. There is also a need to improve current pest control tools and advance the development of pest control products based on new paradigms, including those that function through alternative mechanisms of action.

[0006] Resistance development to pyrethroids is a particular ongoing concern. The implications are a decrease in the effectiveness of pyrethroids in pest control, requiring greater quantities of pyrethroids to be used for comparable control with a net increase in risk of pest resurgence, product cost and possible damage risks to individuals, commodities and the environment.

[0007] It would be desirable to provide improved pest control methods to address at least one of the problems above and / or which may provide further pest management options for users. SUMMARY OF THE DISCLOSURE

[0008] In one aspect, the present disclosure provides a method for controlling pests in a covered environment, comprising exposing said pests in said covered environment to an effective amount of a vapour form of a compound of formula (I): 2 O R6R5wherein R1is selected from –C(=O)R7, -OR8, -SR8, -C1-10hydroxyalkyl, -NR9R10, -C(=N- R9)R7, -C(=N-OH)R7, -NO, -NO2, -N(OR8)R7and –OSO3R8; R2 is selected from hydrogen, -C1-10alkyl, -C2-10alkenyl, aryl and heteroaryl; R3, R4, R5 and R6 are each independently selected from hydrogen, -C1-10alkyl, -C3-6cycloalkyl, -C2-10alkenyl, -C1-10haloalkyl, -C1-10dihaloalkyl, -C1-10trihaloalkyl, -OR8, -SR8, -NR9R10, -C(=N-R9)R7, -NO, -NO2, -NR9OR8, -OSO3R8, -C1- 10alkylaryl and –C(=O)R7;R7is selected from hydrogen, -C1-10alkyl, -C2-10alkylaryl, C3-6cycloalkyl, -C2-10alkenyl, -C1-10alkylheteroaryl, -C1-10haloalkyl, -C1-10dihaloalkyl, -C1-10trihaloalkyl, -C1-10haloalkoxy, -C1-10hydroxyalkyl, -C1-10thioalkyl, -C1-10nitroalkyl, -C1-3alkylOC1-3alkyl, - C1-3alkylOC1-3haloalkyl, -C1-3alkylOC1-3dihaloalkyl, -C1-3alkylOC1-3trihaloalkyl, -OR8, - SR8and –NR9R10; R8 is selected from hydrogen, -C1-10alkyl, -C2-10alkylaryl, -C3-6cycloalkyl, -C2- 10alkenyl, -C1-10alkylheteroaryl, -C1-10haloalkyl, -C1-10dihaloalkyl, -C1-10trihaloalkyl, -C1-10haloalkoxy, -C1-10hydroxyalkyl, -C1-10thioalkyl and -C1-10nitroalkyl; and R9and R10are independently selected from hydrogen, -C1-10alkyl, -C2-10alkylaryl, -C3-6cycloalkyl, -C2-10alkenyl, -C1-10alkylheteroaryl, -C1-10haloalkyl, -C1-10dihaloalkyl, - C1-10trihaloalkyl.

[0009] In another aspect, there is provided the use of a compound of formula (I) as defined herein, for controlling pests in a covered environment, wherein said pests are exposed to an effective amount of a vapour form of said compound of formula (I) in said covered environment.

[0010] In another aspect, there is provided a diffuser containing a compound of formula (I) as defined herein.

[0011] In another aspect, there is provided a refill vessel containing a compound of formula (I) as defined herein, for fitting to a diffuser.

[0012] In another aspect, there is provided a kit comprising a compound of formula (I) as defined herein, and a volatilization aid. DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 provides a bar chart showing the average percent mortality of Myzus persicae when exposed to chlorpyrifos and flavesone vapour for 24 hours. Error bars show the standard error.

[0014] Figure 2 provides photographs showing the laboratory bioassay set-up used to investigate the vapour activity of chlorpyrifos and flavesone.

[0015] Figure 3 provides photographs showing aphid cups at 24 hours exposure to vapour of a) flavesone (5 g a.i. / L), b) flavesone (50 g a.i. / L), c) chlorpyrifos (25 g a.i. / L).

[0016] Figure 4 shows the Peet-Grady style chamber used to assess the spatial activity of flavesone to Aedes aegypti.

[0017] Figure 5 shows the spatial assay set up in PeetGrady style chamber showing a table with a mark for the location of the active ingredient (AI) source, a small fan below the table, a humidifier (towards the back wall), and a series of testing cups at three horizontal distances and at (a) 70 cm vertical distance below and (b) approx. 30 cm vertical distance above the AI source.

[0018] Figure 6 provides a bar chart showing mortality of 4-5-day-old adults of Aedes aegypti (LVP strain) at three horizontal distances (25, 50, and 100 cm) and at ~30 cm vertical distance (suspended cups) from the FLC (flavesone) source at 10-minutes intervals up to 1hr post-exposure. Results represent n=3 technical replicate, n=1 biological replicate.

[0019] Figure 7 provides a bar chart showing mortality of 4-5-day-old adults of Aedes aegypti (LVP strain) at three horizontal distances (25, 50, and 100 cm) and at ~ 30 cm vertical distance (suspended cups) from the FLC source at 1, 24, 48, 72, and 96 hrs post- exposure. Results represent n=3 technical replicate, n=1 biological replicate. The legend corresponds to the bars to the right of each number on the time axis.

[0020] Figure 8 provides a bar chart showing mortality of 4-5-day-old adults of Aedes aegypti (LVP strain) at three horizontal distances (25, 50, and 100 cm) and at 70 cm vertical distance (cups on the floor) from the FLC source at 10-minutes intervals up to 1hr post- exposure. Results represent n=3 technical replicate, n=1 biological replicate.

[0021] Figure 9 provides a bar chart showing mortality of 4-5-day-old adults of Aedes aegypti (LVP strain) at three horizontal distances (25, 50, and 100 cm) and at 70 cm vertical distance (cups on the floor) from the FLC source at 1, 24, 48, 72, and 96 hrs post- exposure. Results represent n=3 technical replicate, n= 1 biological replicate. The legend corresponds to the bars to the right of each number on the time axis.

[0022] Figure 10 shows the glass vial containing test sample and a wick used in the electric emanator.

[0023] Figure 11 shows the spatial set up in Peet-Gradystyle chamber showing the location of the test sample and disposed towards three corners of the chamber a testing cup and disposed towards the fourth corner a fan.DETAILED DESCRIPTION

[0024] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art of the disclosure. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, preferred methods and materials are described. For the purposes of the present disclosure, a number of terms are defined throughout.

[0025] As used herein, the terms "a" and "an" are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. By way of example, “an element” means one element or more than one element.

[0026] As used herein, the term “and / or”, e.g., “A and / or B” shall be understood to mean either "A and B" or "A or B" and shall be taken to provide explicit support for both meanings or for either meaning.

[0027] As used herein, the term “about”, unless stated to the contrary, refers to ±10% of the designated value.

[0028] Except where the context requires otherwise due to express language or necessary implication, as used herein the term “comprise” or variations such as “comprises” or “comprising” is used in an inclusive sense, i.e., to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the disclosure.

[0029] It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in any country. Compounds of Formula (I)

[0030] The present disclosure contemplates methods and compositions for controlling pests by exposing the pests to a compound of formula (I) in a vapour form.

[0031] A compound of formula (I) is defined as follows:2O R6R5wherein R1 is selected from –C(=O)R7, -OR8, -SR8, -C1-10hydroxyalkyl, -NR9R10, -C(=N- R9)R7, -C(=N-OH)R7, -NO, -NO2, -N(OR8)R7 and –OSO3R8; R2is selected from hydrogen, -C1-10alkyl, -C2-10alkenyl, aryl and heteroaryl; R3, R4, R5 and R6 are each independently selected from hydrogen, -C1-10alkyl, -C3- 6cycloalkyl, -C2-10alkenyl, -C1-10haloalkyl, -C1-10dihaloalkyl, -C1-10trihaloalkyl, -OR8, -SR8, -NR9R10, -C(=N-R9)R7, -NO, -NO2, -NR9OR8, -OSO3R8, -C1-10alkylaryl and –C(=O)R7; R7 is selected from hydrogen, -C1-10alkyl, -C2-10alkylaryl, C3-6cycloalkyl, -C2-10alkenyl, -C1-10alkylheteroaryl, -C1-10haloalkyl, -C1-10dihaloalkyl, -C1-10trihaloalkyl, -C1-10haloalkoxy, -C1-10hydroxyalkyl, -C1-10thioalkyl, -C1-10nitroalkyl, -C1-3alkylOC1-3alkyl, - C1-3alkylOC1-3haloalkyl, -C1-3alkylOC1-3dihaloalkyl, -C1-3alkylOC1-3trihaloalkyl, -OR8, - SR8 and –NR9R10; R8is selected from hydrogen, -C1-10alkyl, -C2-10alkylaryl, -C3-6cycloalkyl, -C2-10alkenyl, -C1-10alkylheteroaryl, -C1-10haloalkyl, -C1-10dihaloalkyl, -C1-10trihaloalkyl, -C1- 10haloalkoxy, -C1-10hydroxyalkyl, -C1-10thioalkyl and -C1-10nitroalkyl; and R9and R10are independently selected from hydrogen, -C1-10alkyl, -C2-10alkylaryl, -C3-6cycloalkyl, -C2-10alkenyl, -C1-10alkylheteroaryl, -C1-10haloalkyl, -C1-10dihaloalkyl, - C1-10trihaloalkyl.

[0032] As used herein, “Cato Cb” or “Ca-b” in which “a” and “b” are integers refer to the number of carbon atoms in the specified group. That is, the group can contain from “a” to “b”, inclusive, carbon atoms. Thus, for example, a “C1 to C4 alkyl” (which may be denoted “C1-C4 alkyl”) group includes alkyl groups having from 1 to 4 carbons, consisting of 1 carbon atom, 2 carbon atoms, 3 carbon atoms and 4 carbon atoms, e.g., CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, CH3CH2CH2CH2-, CH3CH2CH(CH3)- and (CH3)3C-.

[0033] As used herein, the term "alkyl" refers to straight chain or branched saturated hydrocarbon group and having from 1 to 10 carbon atoms. An alkyl group may have a specified number of carbon atoms, for example, C1-C6 alkyl includes alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms in a linear or branched arrangement. Examples of suitable alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i- butyl, t-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 4-methylbutyl, n-hexyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 5-methylpentyl, 2-ethylbutyl, 3-ethylbutyl, heptyl, octyl, nonyl and decyl.

[0034] As used herein, the term "cycloalkyl" refers to a saturated cyclic hydrocarbon. A cycloalkyl group may have a specified number of carbon atoms, for example, C3-C6 cycloalkyl includes cycloalkyl groups having 3, 4, 5 or 6 carbon atoms. Examples of suitable cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0035] As used herein, the term "alkenyl" refers to a straight-chain or branched hydrocarbon group having one or more double bonds between carbon atoms and having from 2 to 10 carbon atoms. An alkenyl group may have a specified number of carbon atoms, for example, C2-C6 alkenyl includes alkenyl groups having 2, 3, 4, 5 or 6 carbon atoms in a linear or branched arrangement. Examples of suitable alkenyl groups include, but are not limited to, ethenyl, propenyl, isopropenyl, butenyl, butadienyl, pentenyl, pentadienyl, hexenyl, hexadienyl, heptenyl, octenyl, nonenyl and decenyl.

[0036] As used herein, the term "aryl" refers to a stable, monocyclic, bicyclic or tricyclic carbon ring system of up to 7 atoms in each ring, wherein at least one ring is aromatic. Examples of such aryl groups include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, indanyl, fluorenyl, phenanthrenyl, biphenyl and binaphthyl.

[0037] As used herein, the term "heteroaryl" refers to a stable monocyclic, bicyclic or tricyclic ring of up to 7 atoms in each ring, wherein at least one ring is aromatic, and at least one ring contains from 1 to 4 heteroatoms selected from the group consisting of O, N and S. Examples of suitable heteroaryl groups include, but are not limited to, acridinyl, carbazolyl, cinnolinyl, quinoxalinyl, quinazolinyl, pyrazolyl, indolyl, isoindolyl, 1H,3H-1-oxoisoindolyl, benzotriazolyl, furanyl, thienyl, thiophenyl, benzothienyl, benzofuranyl, benzodioxane, benzodioxin, quinolinyl, isoquinolinyl, oxazolyl, isoxazolyl, imidazolyl, pyrazinyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl,tetrahydroquinolinyl, thiazolyl, isothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,4- oxadiazolyl, 1,2,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,4,5-tetrazinyl and tetrazolyl. Particular heteroaryl groups have 5- or 6-membered rings, such as pyrazolyl, furanyl, thienyl, oxazolyl, indolyl, isoindolyl, 1H,3H-1-oxoisoindolyl, isoxazolyl, imidazolyl, pyrazinyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl, thiazolyl, isothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl and 1,2,4-oxadiazolyl and 1,2,4-thiadiazolyl.

[0038] As used herein, the term “haloalkyl” refers to an alkyl group in which one or more hydrogen atoms is substituted with a halo atom. A haloalkyl group may have a specified number of halo substitutions, for example, dihaloalkyl (two) and trihaloalkyl (three). Examples of suitable haloalkyl groups include, but are not limited to, fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1,1- difluoroethyl, 2,2-fluoroethyl, 1,1,2-trifluoroethyl, 2,2,2-trifluoroethyl, 3-fluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, 4-fluorobutyl, 4,4-difluorobutyl, 4,4,4- trifluorobutyl, 5-fluoropentyl, 5,5-difluoropentyl, 5,5,5-trifluoropentyl, 6-fluorohexyl, 6,6-difluorohexyl or 6,6,6-trifluorohexyl, chloromethyl, dichloromethyl, trichloromethyl, 1-chloroethyl, 2-chloroethyl, 1,1-dichloroethyl, 2,2-chloroethyl, 1,1,2- trichloroethyl, 2,2,2-trichloroethyl, 3-chloropropyl, 3,3-dichloropropyl, 3,3,3- trichloropropyl, 4-chlorobutyl, 4,4-dichlorobutyl, 4,4,4-trichlorobutyl, 5-chloropentyl, 5,5-dichloropentyl, 5,5,5-trichloropentyl, 6-chlorohexyl, 6,6-dichlorohexyl or 6,6,6- trichlorohexyl, bromomethyl, dibromomethyl, tribromomethyl, 1-bromoethyl, 2- bromoethyl, 1,1-dibromoethyl, 2,2-dibromoethyl, 1,1,2-tribromoethyl, 2,2,2- tribromoethyl, 3-bromopropyl, 3,3-dibromopropyl, 3,3,3-tribromopropyl, 4-bromobutyl, 4,4-dibromobutyl, 4,4,4-tribromobutyl, 5-bromopentyl, 5,5-dibromopentyl, 5,5,5- tribromopentyl, 6-bromohexyl, 6,6-dibromohexyl or 6,6,6-tribromohexyl and the like.

[0039] The term "halo" refers to fluorine, chlorine, bromine and / or iodine.

[0040] As used herein, the term “hydroxyalkyl”, “thioalkyl” and “nitroalkyl” each refer to an alkyl group in which one or more hydrogen atoms is substituted with a hydroxyl group, a thiol group or a nitro group, respectively.

[0041] As used herein, the term “alkoxy” refers to an oxygen substituent that is substituted with an alkyl group. Examples of suitable alkoxy groups include, but are not limited to, -OCH3, -OCH2CH3, -O(CH2)2CH3, -OCH(CH3)2, -O(CH2)3CH3, - OCH2CH(CH3)2, -OC(CH3)3, -O(CH2)4CH3and -O(CH2)5(CH3).

[0042] As used herein, the term “oxo” (which may be denoted “=O”) means an oxygen that is double bonded to a carbon atom.

[0043] A compound of formula (I) as classified as a β-triketone with reference to the core cyclohexen β-trione motif of the structural formula which defines a compound of formula (I). As such, reference to a compound of formula (I) may equally be expressed as a “β-triketone compound of formula (I)”. Notwithstanding, compounds of formula (I) may exist in tautomeric forms involving the core cyclohexen β-trione motif. Many compounds of formula (I) are also capable of existing in differing geometric isomers and diastereomers. The compounds of formula (I) as defined herein are taken to include all tautomers, individual isomers and mixtures of isomers. Separation of individual isomers or selective synthesis of individual isomers is accomplished by application of various methods which are known to practitioners in the art.

[0044] Compounds of formula (I) may exist as solvates, for example, hydrates, and / or as salts. Examples of suitable 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 isopropyl ammonium, trialkyl and tetraalkylammonium salts. Examples of suitable salts also include agriculturally acceptable salts including salts of agriculturally acceptable inorganic acids such as hydrochloric, sulphuric, phosphoric, nitric, carbonic, boric, sulfamic, and hydrobromic acids, or salts of agriculturally acceptable organic acids such as acetic, propionic, butyric, tartaric, maleic, hydroxymaleic, fumaric, maleic, citric, lactic, mucic, gluconic, benzoic, succinic, oxalic, phenylacetic, methanesulphonic, toluenesulphonic, benezenesulphonic, salicyclic, sulphanilic, aspartic, glutamic, edetic, stearic, palmitic, oleic, lauric, pantothenic, tannic, ascorbic and valeric acids. The compounds of formula (I) of the present disclosure are taken to include all solvates and salts thereof.

[0045] In preferred embodiments: R1 is selected from -C(=O)R7, -OR8, -SR8, -C1-10hydroxyalkyl, -NR9R10 and - OSO3R8; R2 is selected from hydrogen and -C1-10alkyl; R3, R4, R5 and R6 are each independently selected from hydrogen, -C1-10alkyl, - C2-10alkenyl, -C1-10haloalkyl, -C1-10dihaloalkyl, -C1-10trihaloalkyl, -OR8, -SR8, -NO2, and -OSO3R8;R7is selected from -C1-10alkyl, -C2-10alkenyl, -C1-10haloalkyl, -C1-10dihaloalkyl, - C1-10trihaloalkyl, -C1-10haloalkoxy, -C1-10hydroxyalkyl, -C1-10thioalkyl, -C1-10nitroalkyl, - C1-3alkylOC1-3alkyl, -C1-3alkylOC1-3haloalkyl, -C1-3alkylOC1-3dihaloalkyl, -C1- 3alkylOC1-3trihaloalkyl, -OR8, -SR8 and –NR9R10; R8is selected from -C1-10alkyl, -C2-10alkenyl, -C1-10haloalkyl, -C1-10dihaloalkyl, - C1-10trihaloalkyl, -C1-10haloalkoxy, -C1-10hydroxyalkyl, -C1-10thioalkyl and -C1- 10nitroalkyl; and R9and R10are independently selected from -C1-10alkyl, -C2-10alkenyl, -C1-10haloalkyl, -C1-10dihaloalkyl and -C1-10trihaloalkyl.

[0046] In preferred embodiments, the compound of formula (I) is a compound of formula (II) as follows: 11O) wherein R11 is selected from –CR12R13R14 or –NR15R16; one of R12and R13is hydrogen and the other is hydroxyl or –OCR17R18R19or R12and R13 together form an oxo group (=O) or a =N-OH group; R14 is –CH(CH3)CR20R21R22, -CH2CH(CH3)CR20R21R22 or – CH(CH3)CH2CR20R21R22; R15and R16are independently selected from hydrogen and C1-10alkyl; R17, R18 and R19 are independently selected from hydrogen or halo; and R20, R21and R22are independently selected from hydrogen, hydroxyl, halo, NO2and –OCR17R18R19; or a tautomer thereof.

[0047] In more preferred embodiments, the compound of formula (I) is a compound of formula (III) as follows:R25R26O) wherein one of R23 and R24 is hydrogen and the other is hydroxyl or –OCR27R28R29 or R23 and R24 together form an oxo group (=O); R25is –CR30R31R32, -CH2CR30R31R32or –CH(CH3)CR30R31R32; R26is H or –CH3; wherein where R26is H, R25is –CH(CH3)CR30R31R32; R27, R28 and R29 are independently selected from hydrogen or halo; and R30, R31and R32are independently selected from hydrogen, hydroxyl, halo, NO2and –OCR27R28R29; or a tautomer thereof.

[0048] In more preferred embodiments, the compound of formula (I) is selected from the group consisting of compounds of structural formula as follows: CH2F O CBr3O 2OCH3OO O CH2F O CBr3O OCH3O O N OOCH2FO CBr3O 2OCH3O O

[0049] In more preferred embodiments, the compound of formula (I) is selected from the group consisting of flavesone (1-isobutyroyl-3,3,5,5-tetramethyleyclohexan-2,4,6- trione), leptospermone (1-valeroyl-3,3,5,5 tetramethylcyclohexan-2,4,6-trione), isolpetospermone (1-isovaleroyl 3,3,5,5-tetramethylcyclohexan-2,4,6-trione), papuanone (1-pentoyl-3,3,5,5-tetramethylcyclohexan 102,4,6-trione), grandiflorone (1- (2-phenylethyl)-3,3,5,5-tetramethylcyclohexan-2,4,6-trione) and jensenone (1-valeroyl- 3,5-dicarbonylcyclohexan-2,4,6-trione), and more preferably flavesone, leptospermone and isolpetospermone. In most preferred embodiments, the compound of formula (I) isflavesone. Of the compounds of formula (I), and in particular flavesone, these compounds have been found to possess the most useful combination of properties including volatility and efficacy in pest control when used in vapour form.

[0050] The compounds of formula (I) may be obtained by synthetic methods, including methods analogous to those known in the art. Exemplary analogous methods are disclosed for example in EP-A-338992, EP-A-336898, U.S. Pat. No.4,202,840, U.S. Pat. No. 4,869,748, EP-A-186118, EP-A-186119, EP-A-186120, U.S. Pat. No. 4,695,673, U.S. Pat. No. 4,780,127, U.S. Pat. No. 4,921,526, U.S. Pat. No. 5,006,150, U.S. Pat. No.5,545,607, U.S. Pat. No.5,925,795, U.S. Pat. No.5,990,046, U.S. Pat. No. 6,218,579, EP-A-249150, EP-A-137963, EP-A-394889, EP-A-506907 and EP-B- 135191. Exemplary synthetic methods are given in the Examples.

[0051] The compounds of formula (I) may also be obtained from natural sources, and particularly from volatile oil-bearing plants, for example by extraction. Volatile oil- bearing plants which may produce a compound of formula (I) may be from the family Myrtaceae and Hypericaceae, and particularly of the genus Eucalyptus, Hypericum, Corymbia and Melaleuca. Representative plant species include Leptospermum polygalifolium (flavesone, isoleptospermone) Hypericum japonicum (flavesone), Leptospermum scoparium (flavesone, leptospermone, isolpetospermone, grandiflorone), Callistemon citrinus (leptospermone), Eucalyptus papuana (papuanone), Corymbia dallachiana (papuanone), Leptospermum morrisonii (grandiflorone), Eucalyptus bensonii (jensenone), Eucalyptus niegacornuta (jensenone), Eucalyptus cornuta (jensenone) and Eucalyptus jensenii (jensenone). Extraction methods are known to those of skill in the art and include for example for example steam distillation of plant biomass.

[0052] The compounds of formula (I) may be used as obtained, either directly in the methods of the disclosure or formulated into a suitable composition for use in the methods of the disclosure, as substantially purified synthetic compound, substantially purified isolated compound, or in crude extract. Preferably, the compound of formula (I) is substantially purified, being present in at least about 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, and preferably at least about 95 wt%.

[0053] The applicability of a compound of formula (I) to pest control arises from its mode of action. The primary mode of action of compounds of formula (I) is believed tobe by acting as a potassium channel activator to prevent the closure of potassium channels, often leading to pest incapacitation and specifically knockdown, at times within the space of a few minutes, followed by death. It is further believed that the mode of action of compounds of formula (I) arises from the core cyclohexen β-dione motif of the structural formula which defines a compound of formula (I) as described herein. It is postulated that this core motif provides the scaffold for affinity binding with pest potassium ion channels.

[0054] Compounds of formula (I) are used in the vapour form. As used herein, the term “vapour form” refers to a substance in the gas phase at a temperature lower than its critical point, which is condensable to a liquid or solid form by increasing its pressure without reducing temperature. That is, a vapour form is distinct from a liquid or solid form including fine or micronized droplet or particulate liquids and solids as may be found in many airborne pesticide application methods including sprays, aerosols, fogs and mists.

[0055] The present inventors have found that compounds of formula (I) are volatile under the typical pressure and temperature conditions of covered environments (about 1 atm and temperature of about -15oC or greater, often about 20oC), and possess the physicochemical properties including thermal stability, flash point and volatility, under the typical pressure and temperature conditions of covered environments, for vapourisation in said covered environments in controllable amounts providing for the control of a wide range of pests in said environments by exposure thereto.

[0056] Compound molecular weight is often an indicator of volatility. Generally speaking, a compound with a molecular weight of 450 g / mol or less may be volatile and / or possess vapourisation potential. In preferred embodiments, the compound of formula (I) has a molecular weight of 310 g / mol or less so as to qualify it as an “aroma compound”, which generally increase in volatility or vapourisability under the typical pressure and temperature conditions of covered environments as the molecular weight decreases. Preferably, the compound of formula (I) has a molecular weight in the range of about 140 g / mol to 310 g / mol, preferably 140 g / mol to 300, 290 or 280 g / mol.Methods and Uses of the Disclosure

[0057] The present disclosure is predicated on the discovery that pests inhabiting covered environments are susceptible to the vapour form of compounds of formula (I) when exposed thereto.

[0058] Without wishing to be limited by theory, it is believed that the pests inhabiting covered environments are susceptible to the vapour form of compounds of formula (I) when exposed thereto by a combination of effects through contact with the compound and by inhalation and / or inspiration of the compound in air. It is thought that pest susceptibility through the combined effects of contact and inhalation is increased relative to exposure by contact alone, which is the exposure mode of liquid and solid forms including fine or micronized droplet or particulate liquids and solids as may be found in many airborne pesticide application methods including sprays, aerosols, fogs, and mists. For this reason, it is thought that compounds of formula (I) in the vapour form are particularly effective in pest control as compared to liquid and solid forms.

[0059] As used herein, the term “controlling” refers to inhibiting the pest from participating in activities in an environment in population numbers causing it to be a pest in that environment. Control may be by way of expelling pests from that environment and / or incapacitating pests. Expelling pests encompasses reducing or inhibiting infestation and repelling pests from an environment. Incapacitating pests encompasses knockdown (KD), killing, or otherwise causing a moribund state.

[0060] Control of pests does not necessarily require completely expelling pests from an environment or incapacitation of all pests in an environment. Reducing active population numbers may be sufficient to cause a pest to cease being pestilent, and for it to thus be controlled, even if some of a population remains present and active. What constitutes control of a pest may differ between the particular pest, its population numbers and the environment, and is determinable by one of skill in the art.

[0061] Often complete or near complete expulsion or incapacitation of pests from / in an environment is desirable. Accordingly, in preferred embodiments, at least 50%, 55%, 60%, 65% or 70% of individuals in a pest population are expelled or incapacitated. More preferably, at least 75%, 80%, 85%, 90% or 95% of individuals in a pest population are expelled or incapacitated, and even as much as 100%.

[0062] In preferred embodiments, the pests are controlled by being incapacitated. Preferably, the pests are incapacitated by knockdown and / or death, preferably death.

[0063] As used herein, the term “environment” refers to an environment that hosts pests, to which a compound of formula (I) may be applied to expose the pests thereto to control them. Environments may generally be regarded as either covered or uncovered environments. Environments are generally air-filled.

[0064] As used herein, a “covered environment” refers to an area which is covered overhead, or in other words, in the skywards direction. Examples include a building, room of a building, shed, hut, honai, shack, cabin, cellar, crawl space, cupboard, pantry, wardrobe, tent, umbrella, patio, verandah, porch, balcony, warehouse, animal house, aviary, greenhouse, silo, factory, tarped stockpile, bunker, bag, vehicle, duct, etc. Preferably the covered environment is enclosed, meaning covered overhead and on all sides e.g., with walls (doors, windows and other access points, ventilation etc. notwithstanding). Enclosed environments are generally protected from inclement weather and allow for airflow to be substantially controlled. Many enclosed environments are dwellings being household or industrial environments that are generally inhabited by humans and / or animals. A household environment is one generally used for leisure, such as houses, gymnasiums, leisure centres and the like, whereas an industrial environment is one generally used for industrial purposes such as manufacture, storage or vending of products, such as warehouses, manufacturing plants, retail outlets and the like. In certain environments the covered environment is an environment associated with agricultural purposes, which are generally industrial environments and include, for example, environments for covered crop cultivation, storage and / or cartage of agricultural goods, food processing, animal housing and the like.

[0065] As used herein, the term “effective amount” in context of the β-triketone compound of formula (I) or pesticidal composition containing it, is meant an amount that is sufficient to control pests by exposure thereto.

[0066] An effective amount of a pesticide or pesticidal composition may be represented by an LC or an LD amount; that is a concentration or dosage, respectively, that is effective for killing or knockdown (knockdown may be termed a KD amount expressed as a concentration and can be taken to apply to otherwise moribund states) of a percentage of individuals in a pest population sufficient for it to cease being a pest. LC,LD and / or KD amounts for any given pest is determinable by one of skill in the art through routine trials. They essentially come to an amount of compound to which a pest should be exposed in order to have the desired effect, and are extrapolatable to amounts to be applied to an environment containing pests to ensure that the pests in that environment are exposed to that amount. Depending on, for example, the particular pest, the environment and the population numbers, this will generally be, for example, an LC50, LC55, LC60, LC65, LC70, LC75, LC80, LC85, LC90 and LC95 amount (or equally an LD or KD amount), being the concentration that kills 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%, respectably, of individuals of a pest population. This may also be an LC100 amount (or LD100 or KD100 amount) when control of the pests requires killing (or knockdown, or otherwise moribund) of every individual in the pest population.

[0067] In pest control, it is often preferred to eradicate all or most of a pest population from an environment. In which case, in preferred embodiments, the effective amount of the compound of formula (I) when used alone (meaning, not in combination with another pesticide) is at least an LC90amount which may be an LC90, LC91, LC92, LC93, LC94, LC95, LC96, LC97, LC98, LC99 or LC100 amount, preferably at least an LC95 amount and more preferably at least an LC99 amount including an LC100 amount (and as equally applicable to LD or KD amounts). A similar principle may be applied to expelling pests from an environment; that is, that an amount is used that results in at least 90% of an exposed pest population being expelled, which may be 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or 100%, preferably at least 95% and more preferably at least 99% or even 100%.

[0068] The physical amount of the compound of formula (I) that constitutes an effective amount is dependent on the particular pest, its susceptibility to the compound, level of infestation, and the type of control desired, and is determinable by one of skill in the art. Generally speaking, in a covered environment, the compound of formula (I) may be applied in a vapour form in an amount based on the volume of space defining the environment (i.e., generally determined to be the airspace covered by the overhead cover). This may be within the range of 1 ng / m3to 1 g / m3or 1 µg / m3to 500 mg / m3or from 1 mg / m3to 250 mg / m3. The amount to be applied may also be expressed as a volume per volume of space defining the environment, and may be within the range of 1 pL / m3to 1 mL / m3or 1 nL / m3to 0.5 mL / m3or anywhere from 1 µL / m3to 0.25 mL / m3. Theseranges are believed to be applicable to a broad range of pests. In preferred embodiments applicable to many insect pests, especially flying insects, the compound of formula (I) is applied to a covered environment in a vapour form in an amount of 10 µL / m3to 0.25 mL / m3, preferably 50 µL / m3to 0.2 mL / m3, and more preferably 0.1 mL / m3.

[0069] The effective amount of the compound of formula (I) may be applied to a covered environment over a period of time, or in other words, in an amount per unit time based on the volume of space defining the environment. This may be within the range of 0.5 ng / m3 / hr to 500 mg / m3 / hr or 0.5 µg / m3 / hr to 250 mg / m3 / hr or from 0.5 mg / m3 / hr to 125 mg / m3 / hr. Or expressed as a volume, this may be 0.5 pL / m3 / hr to 500 µL / m3 / hr or 0.5 nL / m3 / hr to 250 µL / m3 / hr or anywhere from 0.5 µL / m3 / hr to 250 µL / m3 / hr. In preferred embodiments applicable to many insect pests, especially flying insects, the compound of formula (I) is applied to a covered environment in a vapour form at a rate of 5 µL / m3 / hr to 125 µL / m3 / hr, preferably 25 µL / m3 / hr to 200 µL / m3 / hr, and more preferably 50 µL / m3 / hr.

[0070] The amount to be applied to an environment and the time taken may be controlled by the starting amount and by controlling the volatility of the compound of formula (I). For instance, a greater airborne concentration may be achieved in a shorter time by increasing the volatility i.e., increasing the rate of conversion from liquid or solid to vapour. Controlling the volatility is generally achievable by controlling the temperature of the compound of formula (I) (which may be done by controlling the temperature of the environment) and / or the surface area of the amount of the compound of formula (I) that is exposed to the environment and / or by agitation. A decreased temperature reduces volatility, as does a reduced surface area and reduced agitation, while an increased temperature increases volatility as does an increased surface area and increased agitation.

[0071] Controlling the volatility is achievable by the use of aids, which may operate on a principle of controlling temperature and / or surface area and / or agitation. Aids are generally known as diffusers or emanators, herein collectively called “diffusers”. Example of diffusers that control surface area are those that include wicking means such as reeds, fabric, paper and the like which are designed to be in contact with the compound of formula (I). Wicking means generally operate by drawing compound of formula (I) into the wicking material thus increasing the surface area for release of vapour. A diffuserthat contains a wicking means may be referred to as a “wicking diffuser”. Examples of diffusers that control temperature are those that include a heat source such as a flame or electric element which heat compound of formula (I) to increase the rate of conversion from a liquid or solid to a vapour form. A diffuser that contains a heat source may be referred to as a “temperature diffuser”. Examples of diffusers that control agitation include a mechanical agitator such an ultrasonic sound wave emanator which through mechanical force applied to the compound of formula (I) cause vapour to be released. A diffuser that contains a mechanical agitator may be referred to as a “mechanical diffuser”. Wicking, temperature and mechanical diffusers are not necessarily mutually exclusive; a diffuser may be a wicking and temperature diffuser, a wicking and mechanical diffuser, a temperature and mechanical diffuser, or a wicking, temperature and mechanical diffuser. Examples of diffusers include those that operate on battery power or are designed to plug-in to mains electricity sockets and may be referred to as an “electric diffuser”. Electric diffusers often generate heat to increase the volatility of the compound of formula (I) cause vapour to be released. In an electric diffuser, the compound of formula (I) may be present in a liquid form or impregnated to a release form such as a gel. Contemplated as a diffuser is also simply heating an open crucible containing compound of formula (I) e.g., by a flame such as may be provided by a tea candle. Many diffusers are available commercially.

[0072] Many diffusers comprise vessels for containing the compound of formula (I) to be released in vapour form. Often, particularly in the case of electric diffusers, the vessel is designed to be removed once emptied and re-filled or replaced with a charged vessel for refitting to the diffuser. These vessels may be referred to as a “refill vessel”.

[0073] For compounds of formula (I), to achieve an application rate of 50 µL / m3 / hr in a typical covered environment with conditions of about 1 atm and 20oC, generally requires the use of a diffuser. Accordingly, in preferred embodiments, the compound of formula (I) is applied to the environment using a diffuser. In preferred embodiments, the diffuser is a temperature and / or a mechanical diffuser. Preferably, the diffuser is an electric diffuser.

[0074] The compound of formula (I) may be applied to an environment with the use of a dispersing aid to assist the vapour form to disperse in the covered environment fasterand / or more broadly. A dispersing aid may be as simple as an apparatus designed to increase air movement e.g., a fan. Some diffusers may include integrated dispensing aids.

[0075] The amount to be applied to an environment and the time taken may also be determined by the number of release points (that is, the point of release of the volatile form into an environment) of a compound of formula (I) e.g., diffusers used. Generally speaking, the greater the number of release points, the higher the rate of release to the environment. It has been found to advantage that effective pest control is achievable using a single release point per at least about 6 m3, 7 m3, 8 m3, 9 m3or 10 m3, of the volume of space defining the environment, preferably at least about 8 m3of the volume of space defining the environment, preferably in the range of 8 to 10 m3of the volume of space defining the environment, even of about 90 m3, 95 m3or 100 m3, for instance 15 m3, 25 m3, 35 m3, 45 m3, 55 m3, 65 m3, 75 m3, 85 m3, 90 m3, 95 m3or 100 m3, of the volume of space defining the environment, and even of about 225 m3or 250 m3, for instance 125 m3, 150 m3, 175 m3, 200 m3, 225 m3or 250 m3, of the volume of space defining the environment.

[0076] With applicable application amounts and rates, in preferred embodiments, the compound of formula (I) when applied to a covered environment reaches at least 50%, preferably 55%, preferably 60%, preferably 70% and more preferably 75%, effectiveness in the control of pests within 24 hours, preferably 12 hours, preferably 6 hours, preferably 4 hours, preferably 2 hours, preferably 1 hour, preferably 50 minutes, preferably 40 minutes, preferably 30 minutes and most preferably 20 minutes, of application to the environment. In some embodiments, the compound of formula (I) may reach 80%, 85% or even 90% effectiveness within 4 hours, 2 hours, 1 hour, 50 minutes, 40 minutes, 30 minutes or even 20 minutes, of application to the environment.

[0077] In preferred embodiments, the compound of formula (I) when applied to a covered environment is effective (i.e., reaches full effectiveness) in the control of pests within 4 hours, preferably 2 hours, preferably 1 hour, preferably 50 minutes, preferably 40 minutes, preferably 30 minutes and most preferably 20 minutes, of application to the environment.

[0078] Preferably, when pest incapacitation represents the desired control, at least 20%, preferably, 25%, preferably 30% and preferably 35% are incapacitated within 4 hours, preferably 2 hours, preferably 1 hour, preferably 50 minutes, preferably 40minutes, preferably 30 minutes and most preferably 20 minutes, of application to the environment.

[0079] Pests located above the release point of a vapour form of a compound of formula (I) (that is, above the horizontal plane intersecting the point of release of the volatile form of a compound of formula (I) into an environment), for example airborne pests, may be particularly susceptible. This is because vapours released from a source typically emanate upwards and outwards from the release point creating, at least initially, highest vapour concentrations above the horizontal plane intersecting the release point. However, it is also a benefit of the disclosure that the vapour form of a compound of formula (I) is effective in the control of pests located below the release point, for example ground-dwelling pests. Preferably, when pest incapacitation represents the desired control, at least 40%, preferably, 45%, preferably 50% and preferably 55% of pests above the release point are incapacitated within 4 hours, preferably 2 hours, preferably 1 hour, preferably 50 minutes, preferably 40 minutes, preferably 30 minutes and most preferably 20 minutes, of application to the environment.

[0080] The compound of formula (I) may also be provided in a kit along with a diffuser, and optionally along with one or more of a dispersing aid, and instructions for exposing pests to the compound of formula (I). The instructions may contain application rates suitable for specific pests, preferably concordant with the preferred embodiments as herein described.

[0081] Preferred embodiments of the methods and uses are outlined as follows: a. When the compound of formula (I) is applied alone to an enclosed environment, at least 75%, 80%, 85%, 90%, 95% or even 100%, of individuals of a pest population are expelled or incapacitated, preferably incapacitated, and preferably by death; b. The compound of formula (I) when used alone is applied in an amount of 10 µL / m3to 0.25 mL / m3, preferably 50 µL / m3to 0.2 mL / m3, and more preferably 0.1 mL / m3, in an amount per unit time based on the volume of space defining the environment within the range of 05 µL / m3 / hr to 125 µL / m3 / hr, preferably 25 µL / m3 / hr to 200 µL / m3 / hr, and more preferably 50 µL / m3 / hr, using a single release point per 8-10 m3of the volume of space defining the environment; andc. The compound of formula (I) when used alone reaches 80%, 85%, 90% or even 100% effectiveness within 4 hours, 2 hours, 1 hour, 50 minutes, 40 minutes, 30 minutes or even 20 minutes, of application to the environment.

[0082] In most preferred embodiments, all of a.-c. apply. Pests

[0083] The pests to which the present disclosure relates are generally insect and arachnid pests. The term “pest” is not intended to encompass mammals, marsupials, bacteria and the like, or plants. In preferred embodiments, the pest is an insect. In other preferred embodiments, the pest is an arachnid.

[0084] The pest when controlled may be in any stage of its life cycle, for example, an egg, larvae, pupa, adult or nymph. Preferably the pest is an adult or nymph.

[0085] The insect pests which the compound of formula (I) may be used to control include as follows: a. from the order of the lepidopterans (Lepidoptera), for example, Adoxophyes orana, Agrotis ipsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Cacoecia murinana, Capua reticulana, Choristoneura fumiferana, Chilo partellus, Choristoneura occidentalis, Cirphis unipuncta, Cnaphalocrocis medinalis, Crocidolomia binotalis, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Feltia subterranea, Grapholitha funebrana, Grapholitha molesta, Heliocoverpa armigera, Heliocoverpa virescens, Heliocoverpa zea, Hellula undalis, Hibernia defoliaria, Hypliantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Manduca sexta, Malacosoma neustria, Mamestra brassicae, Mocis repanda, Operophthera brumata, Orgyia pseudotsugata, Ostrinia nubilalis, Pandemis heparana, Panolis flamnea, Pectinophora gossypiella, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Platynota stultana, Plutella xylostella, Prays citri, Praysoleae, 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, also Galleria mellonella, Sitotroga cerealella, Ephestia cautella and Tineola bisselliella; b. from the order of the beetles (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, Dendroctonus rufipennis, Diabrotica longicornis, Diabrotica punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Otiorhynchus sulcatus, Otiorhynchus ovatus, Phaedon cochleariae, Phyllopertha horticola, Phyllophaga sp., Phyllotreta chrysocephala, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Psylliodes napi, Scolytus intricatus and Sitona lineatus, also Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Cryptolestes ferrugineus, Sitophilus granarius, Sitophilus zeamais, Lasioderma serricorne, Oryzaephilus surinamensis, Rhyzopertha dominica, Sitophilus oryzae, Tribolium castaneum, Tribolium confusum, Trogoderma granarium and Zabrotes subfasciatus; c. from the order of the dipterans (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, also Aedes aegypti, Aedes vexans, Aedes albopictus, Anopheles maculipennis, Anopheles stephensi, Anopheles gambiae, Chrysomya bezziana, Cochliomyia hominivorax, Chrysomya macellaria, Cordylobia anthropophaga, Culex pipiens, Culex quinquefasciatus, Culex sitiens, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haernatobia irritans, Haplodiplosis equestris, Hypoderma lineata, Lucilia cuprina, Lucilia sericata, Musca domestica, Muscina stabulans, Oestrus ovis, Tabanus bovinus and Simulium damnosum; d. from the order of the thrips (Thysanoptera), for example, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Haplothrips tritici, Heliothrips haemorrhoidalis, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci; e. from the order of the hymenopterans (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 of the heteropteranis (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 of the homopterarts (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, Macrosiphon 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 of the termites (Isoptera), for example, Kalotermes flavicollis, Coptotermes spp, Leucotermes flavipes, Macrotermes subhyalinus, Macrotermes darwiniensis, Mastotermes spp. Microtermes spp., Nasutitermes spp such as Nasutitermes walkeri, Odontotermes formosanus, Reticulitermes lucifugus and Termes natalensis; i. from the order of the orthopterans (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, also Acheta domesticus, Blatta orientalis, Blattella germanica and Periplaneta americana; j. from the order of the phthirapterans (Phthiraptera), for example, Mallophaga, such as Damalina spp., and Anoplura such as Linognathus and Haematopinus spp.; k. from the order of the hemipterans (Hemiptera), for example, Aphis, Bemisia, Phorodon, Aeneolamia, Empoasca, Perkinsiella, Pyrilla, Aonidiella, Coccus, Pseudococcus, Helopeltis, Lygus, Dysdercus, Oxycarenus, Nezara, Aleyrodes, Triatoma, Psylla, Myzus, Megoura, Phylloxera, Adelges, Nilaparvata, Nephotettix or Cimex spp. such as Cimex lectularius and Cimex hemipterus; l. from the order of the siphonapterans (Siphonaptera), for example, Ctenocephalides or Pulex spp.; m. from the order of the thysanurans (Thysanura), for example, Lepisina spp.; n. from the order of the dermapterans (Dermaptera), for example, Forficula spp.; and o. from the order of the psocopterans (Psocoptera), for example, Peripsocus spp.

[0086] The arachnid pest which the compound of formula (I) may be used to control include spiders, scorpions, pseudoscorpions, microscopions and mites and ticks, especially mites, ticks and spiders as follows: a. Mites such as 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 such as 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 such as 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, Hunstman 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 family Salticidae) and Araneus diadematus.

[0087] Representative pests include insects from the order of the Homoptera or Hemiptera and particularly Myzus species, insects from the order of the Coleoptera and particularly Oryzaephilus, Rhyzopertha, Sitophilus, Tribolium, Cryptolestes, andAlphitobius species, insects from the order of the Orthoptera and particularly Blattella and Periplaneta species, and insect from the order of Diptera, particularly flying insects, particularly Musca species, Aedes species, Anopheles species, and Culex species.

[0088] In certain preferred embodiments, the pest is a flying insect. As used herein, the term “flying insect” refers to an insect which has wings and is capable of self- sustained flight in air. Flying insects are preferred because they may often be found above the release point of a vapour of a compound of formula (I). As above, vapours released from a source typically emanate upwards and outwards from the release point creating, at least initially, high vapour concentrations above the horizontal plane intersecting the release point, which is where flying insects may commonly be found. Further, it is thought that potassium ion channels play a particularly important role in the development and function of insect wings, and it is postulated that there is a prevalence of potassium ion channels in flying insects. Accordingly, compounds of formula (I) are particularly effective in the control of flying insects when applied to a covered environment in a vapour form.

[0089] In preferred embodiments, the flying insect pest is from the order of Diptera which contains particularly dangerous and / or nuisance flying insect pests. Preferably, the pest is a mosquito or fly. Preferably, the flying insect pest is selected from the group consisting of a Musca species such as Musca domestica, Aedes species such as Aedes aegypti, Aedes vexans and Aedes albopictus, Anopheles species such as Anopheles maculipennis, Anopheles stephensi and Anopheles gambiae, and Culex species such as Culex pipiens and Culex quinquefasciatus.

[0090] In certain preferred embodiments, the pest is a grain storage pest. Grain storage pests are preferred because they may often be found embedded within a grain stockpile. As compared with liquid applications such as spray applications, vapours are capable of penetrating grain stockpiles where embedded grain storage pests become exposed to the vapour. Preferably, the grain storage pest is selected from the group consisting of a Oryzaephilus species such as Oryzaephilus surinamensis, Rhyzopertha species such as Rhyzopertha dominica, Sitophilus species such as Sitophilus granarius, Sitophilus zeamais and Sitophilus oryzae, Tribolium species such as Tribolium castaneum and Tribolium confusum, and Cryptolestes species such as Cryptolestes ferrugineus.

[0091] In certain preferred embodiments, the pest is a parasitic pest to humans or animals. Parasitic pests are preferred for a similar reason as flying insect pests: because they tend to cling to animals, humans or their surroundings, they may often be found above the release point of a vapour of a compound of formula (I). The parasitic pest may be an insect, mite or tick. The parasitic pest may be an insect such as a Cimex species insect such as Cimex lectularius and Cimex hemipterus.

[0092] In certain preferred embodiments, the pest is a dwelling pest, being a pest that inhabits environments that are generally inhabited by humans and / or animals. Dwelling pests are preferred because they may often be found hidden in cracks and crevices, and in other hidden areas of dwellings. As compared with liquid applications such as spray applications, vapours are capable of penetrating into hidden areas where dwelling pests become exposed to the vapour. The dwelling pest may be an insect or spider. The dwelling pest may be an insect selected from the group consisting of a Blattella and Periplaneta species such as Blatta orientalis, Blattella germanica and Periplaneta americana.

[0093] The compound of formula (I) may be used to control pesticide-resistant pests. As used herein, the term “pesticide-resistant” is meant that the pest has developed resistance to one or more pesticides that has previously been used to control it. The pesticide-resistant pest may be present in a population of pests.

[0094] In examples, the pest may be resistant to any one or more of the second pesticides as described below.

[0095] In particularly applicable embodiments, the pest is resistant to one or more pyrethroids or pyrethrins. More preferably, the pest is permethrin-resistant and / or deltamethrin-resistant, meaning that the pest has developed resistance to permethrin and / or deltamethrin. For example, the known KS17 strain of the winged insect pest house fly species Musca domestica is known to demonstrate essentially complete resistance to permethrin. Similarly, the known Puerto Rico strain of the winged insect pest mosquito species Aedes aegypti is known to demonstrate resistance to permethrin. Pesticide Combinations

[0096] The compound of formula (I) may be applied alone (as the only pesticide) or in combination with a second pesticide.

[0097] As used herein, the term “combination” refers to the compound of formula (I) and the second other pesticide being used together, whether in a single composition or separate compositions or sequentially in separate compositions, such that the biological activity of both overlaps or occurs at the same time. In preferred embodiments, when a combination is used, the compound of formula (I) and the second pesticide are used together in a single composition as described herein.

[0098] A second pesticide may be used in a vapour form or otherwise, though is preferably used in a vapour form. This may be by virtue of the second pesticide itself being volatile and / or by virtue of the second pesticide being capable of forming an azeotrope with the compound of formula (I).

[0099] The volatility of a second pesticide may be less than, the same, or greater than the volatility of a compound of formula (I), though like for the compound of formula (I), in preferred embodiments a second pesticide is volatile under the typical pressure and temperature conditions of covered environments (about 1 atm and temperature of about - 15oC or greater, often about 20oC), and possess the physicochemical properties including thermal stability, flash point and volatility, under the typical pressure and temperature conditions of covered environments, for vapourisation in said covered environments in controllable amounts. Preferably, the volatility of a second pesticide is about the same or similar to the volatility of a compound of formula (I), being within about 25%, whether greater or less.

[0100] When used with a second pesticide, the compound of formula (I) and the second pesticide may be applied each in a sub-effective amount.

[0101] As used herein, the term “sub-effective amount” in context of a pesticide is meant an amount that is less than that which, when used alone, is effective for controlling the pest. That is, a sub-effective amount is less than an effective amount.

[0102] For example, in the case of incapacitating a pest, and using the same example as above based on an LC amount, when the effective amount of a pesticide is an LC100 amount, a sub-effective amount is less than an LC100amount (an LC<100amount), which may be for example an LC99, LC95, LC90, LC85, LC80, LC75, LC70, LC65, LC60, LC55, LC50, LC45, LC40, LC35, LC30, LC25, LC20, LC15, LC10 or LC5 amount. Similarly, when the effective amount of a pesticide is an LC50amount, a sub-effective amount is less than an LC50amount (an LC<50amount) which may be for example and LC45,LC40, LC35, LC30,LC25, LC20, LC15, LC10or LC5amount. The same principle is equally applicable to LD or KD amounts. A similar principle may be applied to expelling pests from an environment; that is, when the effective amount results in 100% of a pest population being expelled, a sub-effective amount, when used alone, results in less than 100% expulsion of the pest population.

[0103] When used with another pesticide, the compound of formula (I) and the second pesticide are preferably applied each in a sub-additive amount.

[0104] As used herein, a “sub-additive amount” in terms of a pesticide in a pesticide combination is meant an amount that, when the effects of each when used alone are added together, would not be effective for controlling the pests. In other words, a combination effective for controlling pests that comprises a sub-additive amount of a β-triketone compound of formula (I) and a second pesticide, is a synergistic combination; that is, super-additive.

[0105] For example, in the case of incapacitating a pest, and using the same example as above based on an LC amount, when the effective amount of a combination is an LC100amount, a sub-additive amount of each of the compound of formula (I) and the second pesticide is an amount that, when the effects of each of which when used alone are added together, is less than an LC100amount. In other words, and generally speaking, the percentage of a pest population that each of the compound of formula (I) and the second pesticide kills, when used alone, does not amount to control of the pest. The same principle is equally applicable to LD or KD amounts. A similar principle may be applied to expelling pests from an environment; that is, when the effective amount of the combination in controlling the pests results in 100% of an pest population being expelled, a sub-additive amount of each of the compound of formula (I) and the second pesticide is an amount that, when the percentage population expelled by each when used alone is added together, results in less than 100% expulsion of the pest population.

[0106] For example, the amount of the compound of formula (I) used in the combination may be an LC5, LC10, LC20, LC30, LC40, LC50, LC60, LC70, LC80, LC90or LC95 amount, while the amount of the second pesticide is less than an LC95, LC90, LC80, LC70, LC60, LC50, LC40, LC30, LC20, LC10 or LC5 amount, respectably. The same principle is equally applicable to LD or KD amounts, and a similar principle in terms of pest population proportions may be applied to expelling pests from an environment.

[0107] In preferred combinations, at least one second pesticide has a different mode of action from the compound of formula (I).

[0108] In examples, the second pesticide may be an insecticide selected from one or more of the group consisting of: a. sodium channel modulators such as a pyrethrin, pyrethroid, DDT and methoxychlor. Pyrethrins include compounds identical to a known natural pyrethrin produced by the plant species Chrysanthemum cinerariaefolium or C. coccineum, including pyrethrin I, cinerin I, jasmolin I, pyrethrin II, cinerin II and jasmolin II. Pyrethroids include acrinathrin, allethrin, bifenthrin, bioallethrin, bioallethrin-S-cyclopentyl, bioresmethrin, cycloprothrin, cyfluthrin, β-cyfluthrin, cyhalothrin, γ-cyhalothrin, λ-cyhalothrin, cypermethrin, α-cypermethrin, β-cypermethrin, θ-cypermethrin, ζ- cypermethrin, cyphenothrin, deltamethrin, dimefluthrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, tau-fluvalinate, halfenprox, imiprothrin, metofluthrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, RU15525, silafluofen, tefluthrin, tetramethrin, tralomethrin, transfluthrin and ZX18901. b. an acetylcholinesterase (AChE) inhibitor such as a carbamate or an organophosphate. Carbamates include alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb and xylylcarb. Organophosphates include acephate, azamethiphos, azinphos, azinphos-methyl, azinphos-ethyl, cadusafos, chlorethoxyfos, chlorfenvinfos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos, dicrotophos, dimethoate, dimethylvinphos, disulfoton, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, isofenphos, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton- methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone,phosmet, phosphamidon, phoxim, pirimiphos, pirimiphos-methyl, profenfos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, triclorfon and vamidothion. c. a GABA-gated chloride channel antagonist such as an organochloride or a fiprole. Organochlorides include chlordane, endosulfan and α-enosulfun. Suitable fiproles include ethiprole, fipronil, pyrafluprole, and pyriprole. d. a nicotinergic acetylcholine receptor agonist such as nicotine or a chloronicotinyl compound. Chloronicotinyl compounds include acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiocloprid and thiamethoxam. e. an allosteric acetylcholine receptor modulator such a spinetoram or spinosad. f. a chloride channel actuator such as abamectin, emamectin benzoate, lepimectin or milbemectin. g. a juvenile hormone mimic such as hydroprene, kinoprene, methoprene, S- methoprene, fenoxycarb or pyriproxyfen. h. a homopteran feeding blocker such as pymetrozine or flonicamid. i. a mitochondrial ATP synthase inhibitor such as diafenthiuron or tetradifan. j. an uncoupler of oxidative phosphorylation such as chlorfenapyr or DNOC. k. a nicotinic acetylcholine receptor channel blocker such as bensultap, cartap hydrochloride, thiocyclam or thiosultap-sodium. l. an inhibitor of chitin biosynthesis such as a benzoylurea or buprofezin. Benzoylureas include bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron or triflumuron. m. a moulting disruptor such as cyromazine. n. an ecdysone receptor agonist or disruptor such as a diacylhydrazine. Diacylhydrazines include chromafenozide, halofenozide, methoxyfenozide or tebufenozide. o. an octopamine receptor agonist such as amitraz. p. a mitochondrial complex I electron transport inhibitor such as hydramethylnon, acequinocyl and fluacrypryrim.q. an acetyl CoA carboxylase inhibitor such as a tetronic acid derivative or a tetramic acid derivative. Tetronic acid derivatives include spirodiclofen and spiromesfen and a suitable tetramic acid derivative is spirotetramat. r. a voltage-dependent sodium channel blocker such as indoxacarb or metaflumizone. s. a mitochondrial complex IV electron inhibitor such as a phosphine or cyanide. Phosphines include zinc phosphide, aluminium phosphide, calcium phosphide or phosphine. t. a mitochondrial complex IV electron transport inhibitor such as cyenopyrafen. u. a ryanodine receptor modulator such as chloranthraniliprole, cyantraniliprole and flubendiamide.

[0109] In preferred combinations, the second pesticide is a sodium channel modulator, more particularly a pyrethrin and / or a pyrethroid, even more particularly pyrethrin I, pyrethrin II, permethrin, bifenthrin, cyfluthrin, cypermethrin, deltamethrin, metofluthrin and / or transfluthrin, most especially pyrethrin I, pyrethrin II, metofluthrin, transfluthrin and / or prallethrin.

[0110] In examples, the second pesticide may be an aracnicide selected from one or more of the group consisting of abamectin, acequinocyl, acrinathrin, aldicarb, alpha- cypermethrin, amidithion, amiton, amitraz, aramite, arsenous oxide, azinphos-ethyl, azinphos-methyl, azobenzene, azocyclotin, azothoate, benomyl, benzoximate, benzylbenzoate, bifenazate, bifenthrin, binapacryl, bromocyclen, bromophos, bromophos-ethyl, bromopropylate, butocarboxim, camphechlor, carbanolate, carbaryl, carbofuran, carbophenothion, carvacrol, chinomethionat, chlorbenside, chlordimeform, chlorfenapyr, chlorfenethol, chlorfenson, chlorfensulphide, chlorfenvinphos, chlorobenzilate, chloromebuform, chloromethiuron, chloropropylate, chlorpyrifos, chlorthiophos, clofentezine, closantel, coumaphos, crotamiton, crotoxyphos, cyanthoate, cycloprate, cyenopyrafren, cyflumetofen, cyhalothrin, cyhexatin, cypermethrin, cyromazine, DDT, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton- S, demeton-S-methyl, diafenthiuron, dialifos, diazinon, dichlofluanid, dichlorvos, dicofol, dieldrin, dienochlor, diflovidazin, dimefox, dimethoate, dinex, dinobuton, dinocap, dinocton, dinopenton, dinosulfon, dinoterbon, dioxathion, diphenyl sulfone, disulfoton, DNOC, endosulfan, endothion, ethion, ethoate-methyl, etoxazole, fenazaflor,fenazaquin, fenbutatin oxide, fenothiocarb, fenpropathrin, fenpyroximate, fenson, fentrifanil, fenvalerate, fipronil, fluacrypyrim, fluazuron, flubenzimine, flucycloxuron, flucythrinate, fluenetil, flufenoxuron, flumethrin, fluorbenside, fluvalinate, formetanate, formothion, formparanate, genit, halfenprox, heptenophos, hexachlorophene, hexythiazox, isocarbophos, lindane, malathion, mecarbam, methacrifos, methamidophos, methiocarb, metolcarb, mevinphos, milbemectin, mipafox, monocrotophos, naled, nifluridide, omethoate, oxamyl, oxydeprofos, oxydisulfoton, parathion, permethrin, phenkapton, phorate, phosalone, phosmet, phoxim, pirimiphos-methyl, propargite, propetamphos, propoxur, prothidathion, prothoate, pyridaben, pyrimidifen, quinalphos, quintiofos, schradan, sophamide, spirodiclofen, sulfluramid, sulfotep, sulfur, tau- fluvalinate, tebufenpyrad, TEPP, tetrachlorvinphos, tetradifon, tetrasul, thiocarboxime, thiofanox, thiometon, thioquinox, thuringiensin, triarathene, triazophos, trichlorfon and vamidothion.

[0111] The at least one second pesticide may be obtained commercially.

[0112] In preferred embodiments, the second pesticide is administered to the environment also in a vapour form, and accordingly will generally comprise a compound that is vapourisable either independently, azeotropically or in formulation with a compound of formula (I). This applies at least to the preferred second pesticide being a pyrethrin and / or a pyrethroid, even more particularly pyrethrin I, pyrethrin II, permethrin, bifenthrin, cyfluthrin, cypermethrin, deltamethrin and / or transfluthrin, most especially pyrethrin I, pyrethrin II, metofluthrin, transfluthrin and / or prallethrin.

[0113] In some combinations, the amount of the compound of formula (I) used in the combination is the same or greater than the amount of the at least one second pesticide used in the combination, or in other words, the amount of the at least one second pesticide used in the combination is the same or less than the amount of the compound of formula (I) used in the combination.

[0114] An at least one second pesticide may also be provided in the kit as described above. Compositions of the Disclosure

[0115] The compounds of formula (I) may be used neat or it may be formulated in a suitable composition along with other ingredients.

[0116] In a composition, a preferred other ingredient is a solvent. A solvent may be volatile. In preferred embodiments a solvent is volatile under the typical pressure and temperature conditions of covered environments (about 1 atm and temperature of about - 15oC or greater, often about 20oC), and possess the physicochemical properties including thermal stability, flash point and volatility, under the typical pressure and temperature conditions of covered environments, for vapourisation in said covered environments in controllable amounts. Also contemplated is a solvent which has no or low volatility but which is capable of releasing a compounds of formula (I) and second pesticide if included, in a vapour form. Preferably, the volatility of a solvent is about the same or similar to the volatility of a compound of formula (I), being within about 20%, whether greater or less. A solvent may assist the release of a compound of formula (I) and second pesticide if included, in vapour form, through interacting effects such as azeotrope effects. Preferred solvents are volatile solvents that are non-toxic (to humans and animals) and non-flammable, and may be comprised of synthetic and / or natural compounds such as terpenes and / or lactates.

[0117] When one or more second pesticides are used, it is preferred that the compound of formula (I) and the one or more second pesticides are applied together in a single composition, and thus formulated together.

[0118] As described herein, the compound of formula (I) is applied in a vapour form. The composition may thus be formulated in any suitable way, though will generally a liquid formulation, by means of dissolving, emulsifying, suspending, or other. Impregnation to a release form, such as a gel, a matrix, solid particles or granules is also contemplated.

[0119] When formulated together, especially in a liquid or other form from which the vapour form may be released, the compound of formula (I) and a second pesticides may be included in amounts depending on the relative volatility and the desired ratio of compound of formula (I) and second pesticide present in the vapour form. For example, if the volatility of a compound of formula (I) and a second pesticide is approximately the same under the same conditions, and a ratio of compound of formula (I) to second pesticide of about 1:1 is desired, then the compound of formula (I) and a second pesticide may be included in a composition in approximately equal amounts. Similarly, if the volatility of a compound of formula (I) is half that of a second pesticide under the sameconditions, and a ratio of compound of formula (I) to second pesticide of about 1:1 is desired, then the compound of formula (I) may be included in a composition in approximately double the amount of the second pesticide. In another example, if the volatility of a compound of formula (I) and a second pesticide is approximately the same under the same conditions, and a ratio of compound of formula (I) to second pesticide of about 1:2 is desired, then the compound of formula (I) may be included in a composition in approximately half the amount of the second pesticide. And so on. The above examples assume no interacting effects which may modify vapourisation, such as azeotrope effects, though these interacting effects are determinable by routine experimentation and if present may be factored-in to the relative amounts included in a composition.

[0120] The composition may contain one or more additives or excipients as required, for example a solvent, carrier, stabilizer, propellant, emulsifier, synergist (such as piperonyl butoxide) or other. Natural ingredients are preferred. Suitable additives are known to those of skill in the art.

[0121] Appropriate formulation selection may be made with consideration of the pest and environment of control, any second pesticide included, and is determinable by one of skill in the art. In preferred embodiments, the composition is formulated as a liquid.

[0122] The compounds of formula (I) may be present as, and thus the compositions of the present disclosure may contain, substantially purified synthetic compound, substantially purified isolated compound, or crude extract. The use of a substantially purified synthetic compound is preferred.

[0123] The composition may be formulated with a concentration of the compound of formula (I) and one or more second pesticides, if present, appropriate for the method of application and pest to be controlled. The composition may be formulated as a concentrate for dilution before application. This may amount to, in certain embodiments, compositions comprising in the range of 10 to 50,000 ppm, 100 to 10,000 ppm, 100 to 5000 ppm, or 300 to 5000 ppm, 500 to 5000 ppm, or 800 ppm to 2,500 ppm or 900 ppm to 2,000 ppm, of the compound of formula (I).EXAMPLES

[0124] A compound of formula (I) may be prepared synthetically as described in WO 2002 / 089587. For example, 1,3,5-trihydroxybenzene may be reacted with RCN in the presence of zinc chloride as shown in scheme 1: O ROH Scheme 1

[0125] Anhydrous methyl iodide (6 Eq) is slowly added to the 1-acyl-2,4,6- trihydroxybenzene (1 eq) and sodium ethoxide (6 eq) in anhydrous methanol as shown in scheme 2 to afford the 1-acyl-3,3,5,5-tetramethyl-2,4,6-cyclohexatrione (US 4,202,840). O R OScheme 2

[0126] Metal salts can be prepared by the reaction of the prepared compounds with corresponding metal hydroxides suspended in methanol or ethanol. Trialkylammonium salts can be prepared by the reaction of the prepared compounds with trialkylamines in a chlorinated solvent such as dichloromethane. Tetraalkylammonium salts can be prepared by adding a halogenated tetraalkylammonium salt to a metal salt in dichloromethane. Example 1

[0127] Assessing the vapour activity of flavesone against Myzus persicae

[0128] The green peach aphid (Myzus persicae) is an important pest of a variety of crops, particularly due to the aphid’s ability to transmit plant viruses. Control of this pest relies heavily on the application of broad-spectrum pesticides. However, resistanin M. persicae to multiple chemical classes, including pyrethroids, organophosphates, carbamates and neonicotinoids is commonplace.

[0129] The efficacy of flavesone 500EW vapour activity against M. persicae was investigated.

[0130] The technical details of flavesone 500EW are as follows: Formulation type: Oil in water emulsion; Flavesone content: 475 525 g / L; Appearance: White fineemulsion; Density: 1.045 – 1.055 g / mL @ 20oC; pH: 4-6; Viscosity: 200 – 400 cP @ 25oC; Emulsion stability: Maximum 2.0 mL cream after 30 minutes.

[0131] A series of pilot experiments were undertaken to optimise the methodology and determine the appropriate rate of a standard volatile insecticide, Chlorpyrifos (product Lorsban 500EC), to elicit aphid mortality via vapour activity. The label rate of Lorsban 500EC registered against M. persicae on tomatoes (100 mL / 100 L water), equivalent to 0.5 g a.i. / L., was used as a guide. Through the pilot experiments, three rates of Chlorpyrifos were determined to be appropriate (see Table 1). The rates of flavesone (product flavesone 500EW) selected for this trial were equivalent to 5x, 10x, 25x, 50x, and 100x the field rate of Chlorpyrifos (see Table 1).

[0132] Insecticide solutions were prepared at each test concentration via serial dilution, and 5 mL of each solution (or a control of water) was pipetted into a designated 250 mL glass jar (6.6 cm diameter x 10.4 cm). Six replicate jars were used for each treatment, except for Chlorpyrifos at 25 g a.i. / L which had four. Two 90 mm Whatman No.1 filter papers were placed against the internal sides of each jar, with the lower end resting in the insecticide solution so that the solution would wick upwards to saturate the filter paper. This was undertaken to increase the surface area for evaporation of the test solutions.

[0133] A colony of M. persicae were established from long-term laboratory cultures of a known insecticide-susceptible population. The colony was maintained on canola (Brassica napus) within an exclusion cage in a controlled temperature room at 24°C with a photoperiod of 16:8 LD. This colony was used for all trials detailed in this example.

[0134] Ten 2-4 day old aphid nymphs were introduced onto a radish (Raphanus sativa, cv. Cherry belle) cotyledon which rested on 10% agar solution within a small plastic cup (3.6 cm diameter x 4 cm). Each cup was then covered with fine mesh fabric using a rubber band to prevent the movement of aphids. A single cup was introduced into each jar containing insecticide solution by placing the cup on a platform fashioned from a 3.5 cm diameter petri dish (to prevent the cup having direct contact with the insecticide). See Figure 2 for photos of the experimental set-up. Jars were then sealed with a lid and placed in a controlled temperature cabinet maintained at 30°C ± 1°C. The humidity within the jars was measured to be >97% for the duration of the experiment.

[0135] After 24 hours, individual aphids were scored as alive (vibrant and moving freely), dead (not moving over a 5 second period) or knocked down (inhibited movement). Knocked-down individuals were pooled with dead individuals for analysis as knocked down arthropods invariably die and therefore do not contribute to the next generation.

[0136] An overall treatment effect was tested using a Fisher’s exact test. Pairwise Fisher’s exact tests at the 95% confidence level (with Bonferroni’s correction of within family p-values) were also performed to compare each treatment. Fisher’s exact tests are appropriate for binomial event data (i.e., dead vs. alive), while Bonferroni correction was used to correct for type II error due to repeated tests. All analyses within this report were conducted using R (R Core Team, 2018).

[0137] A high level of vapour toxicity was detected in this trial, and there was a significant overall treatment effect on M. persicae mortality after 24 hours exposure to insecticide vapour (Fisher’s exact test, P <0.001). Table 1 shows a summary of the treatment rates and the resulting mean mortality. While mortality was low (7%) for the water control, Flavesone at 5 g a.i. / L and higher resulted in 100% mortality after 24 hours (Figure 1). Pairwise comparisons showed that all rates of flavesone tested caused significant mortality compared with the water control (denoted by an asterisk in Table 1). As expected, Chlorpyrifos also caused considerable aphid mortality, which was significantly different to the water control at each rate tested (Table 1 & Figure 1).

[0138] When Flavesone was tested at equivalent rates to Chlorpyrifos, Flavesone resulted in significantly higher M. persicae mortality (Fisher’s exact test, P <0.001 at 2.5 g a.i. / L, and P <0.0001 at 5 g a.i. / L). No phytotoxic effects were observed on the radish cotyledons exposed to insecticide vapour of Flavesone or Chlorpyrifos at the rates tested (see Figure 2 for photographs).Table 1. Summary of treatments and resulting mean M. persicae mortality at 24 hours of insecticide vapour exposure. Treatments statistically different to the water control under Fisher’s exact test with Bonferroni correction are indicated with an asterisk (*). y at %)Example 2

[0139] Assessing the vapour activity of flavesone against mosquitoes

[0140] A forced exposure assay was conducted in a Peet-Grady style chamber (2.4 m (L) X 1.8 m (W) X 2m (H)) to assess the spatial activity of the active ingredient (AI) flavesone to mosquitoes (Figure 4).

[0141] The assay was performed using 3- to 5-day old adult Aedes aegypti male and female LVP strain (SP susceptible) mosquitoes and Technical Grade Flavocide (FLC), heated to 100°C using a ceramic emanator device (wax candle warmer).

[0142] The technical details of FLC are as follows: Flavesone content: Min. 95%; Physical state: Liquid; Density: 1.085 g / mL @ 20◦C; pH: 3.76 at 27.3oC.

[0143] Mosquitoes were anesthetised, placed in cups (5 mosquitoes / cup), and the cups covered with mesh before being transferred to the testing chamber. To assess the dimensions of the vapour plume, efficacy was evaluated at 25 cm, 50 cm and 100 cm horizontal distance from the AI source, and at two vertical heights (ground level on thefloor of the test chamber and suspended 100 cm from the ground (Figure 5a), at a height level with the emanator device (Figure 5b).

[0144] The assay involved a maximum of three technical replicates / distance / height (i.e., a total of 15 mosquitoes / distance / height), corresponding to Zones 1, 2, 3 (Figure 4). Test article (2 mL) was dispensed to the dish of the emanator device, and the device was placed on a small platform at 100 cm from the ground. The device was heated continuously by tea light. The temperature of AI was recorded at one hour via thermometer and the remaining volume of AI was determined at the end of the experimental period. A small fan located beneath the platform and directed towards the ceiling was used to disperse AI throughout the test space.

[0145] Mosquitoes were introduced and exposed in cups for a period of one hour. Cups were removed immediately at the end of the exposure period and scored for mortality at 10 min intervals for 60 mins post-exposure, before being transferred to clean cups and placed in an insectary under controlled conditions of 27-28°C and 80% RH. Mortality was recorded at 24-96 hours post-exposure.

[0146] For controls, cups were placed first in the untreated test arena, removed after 1 hr and mortality assessed at 1 hour and at 24-96 hrs. Test articles were assessed only following establishment of 0% mortality in controls at 1 hr and the experiment was considered valid only if controls exhibited <10% mortality at 24-96 hrs. The results are reported as percent mortality at 1, 24-96 hrs post-exposure for each distance and height.

[0147] Evidence of AI spatial activity against mosquitoes was provided following 1- hour exposure. Evidence of AI spatial activity was provided over a 100 cm radial area, and at ~30 cm vertical distance above and 70 cm below AI source. Rapid mortality of AI- treated adult mosquitoes was observed starting at 20 minutes post-exposure. Up to 80% mortality of AI-treated mosquitoes was observed at 1hr post-exposure, 30 cm above AI source. See Figures 6-9.

[0148] At 2 hrs time point, a 50% reduction in volume of FLC was observed when heated to 100oC.Example 3

[0149] Assessing the vapour activity of flavesone + pyrethrins against mosquitoes

[0150] A laboratory study was conducted in a Peet-Grady chamber to investigate the spatial activity of flavesone in combination with pyrethrins against mosquitoes when applied as a vapour by an electric emanator.

[0151] The assay was performed using 3- to 8-day old female adult Culex quinquefasciatus mosquitoes and test samples Technical Concentrate Flavocide (TC, 96% flavesone), and a flavesone + pyrethrins (CAS No. 8003-34-7) (Combination) test sample. The combination treatment test sample comprised 2% flavesone and 2% pyrethrins.

[0152] The Peet-Grady chamber used was a 1.8 X 1.8 X 1.8 metre spray chamber composed of stainless steel walls and glass viewing panes with a plastic composite substrate. A sheet of clear polythene sheeting was used to line the floor to collect product residues and limit contamination of the chamber. The temperature of the test chamber was controlled at 24±2 °C. The electric emanator was an off-the-shelf commercial product emitting vapour from a glass vial containing test sample and a wick (Figure 10). The emanator was placed in the centre of the test chamber on the floor.

[0153] Healthy mosquitoes were aspirated from a cohort grouped mixed-sex stock cage and held in a collection receptacle at 5 °C for 5-10 minutes to facilitate sexing and counting. Ten (10) adult female mosquitoes were counted into a test container (cylindrical capsule fitted either end with a 1 mm mesh screen both side aspects, with a small hole drilled into the side). Mosquitoes were given approximately 1 hour to recover post counting before being exposed to the Peet-Grady chamber where they were allowed to acclimatize for 15 minutes. Three (3) test containers were positioned within the test chamber suspended from the celling frame at 40 cm from the test chamber corners and 1.5 metres from ground level (Figures 11). For tests using a fan, the air in the test chamber was circulated with a 30-cm diameter fan providing a wind speed of 4.5 m / s to 5.0 m / s. Once insects were acclimatised, test samples were then allowed to emanate into the test chamber (the electric emanator was switched on).

[0154] After approximately 4 hours of exposure, mosquitoes were removed from the test chamber and transferred into clean holding receptacles; a clear plastic ½ pint container fitted with a breathable gauze cover as a lid, secured with an elastic band, witha cotton wool pad semi-saturated with 10% sucrose solution placed on top the gauze, accessible for nutrition and hydration purposes. All mosquitoes were then taken to a climate cabinet where they were held until the end of the 24-hour duration of the experimental period.

[0155] Assessments of mosquitoes for knockdown, moribund and death were made at 1, 2, 4 and 24-hours post treatment application using the following criteria: Knockdown refers to a state in which a mosquito is rendered incapable of coordinated movement or unable to right itself. Moribund refers to mosquitoes on their backs with only a single appendage twitching. Mortality refers to dead mosquito, one that does not move, even when poked or probed. The number of mosquitoes in each assessment category were added together for a total count and converted to a percentage. Percentages were averaged across all replicates.

[0156] The quantity of test sample prior to and after testing was recorded.

[0157] After conducting a test, the chamber ventilation was switched on for a minimum of 1 hour before any new replicate test was undertaken. The internal surfaces of the chamber were washed with a high strength detergent solution following each replicate to remove any insecticide residues.

[0158] Untreated control replicates were tested using the same handling procedure and environmental conditions as treated replicates, with the exception that they were not placed within the test chamber and not treated with the test samples.

[0159] The results are presented in Table 2.Table 2. Summary of treatments and resulting mean C. quinquefasciatus knockdown and mortality at 1, 2, 4 and 24 hours of insecticide vapour exposure. C = combination treatment; F = fan; Control applies ± fan; KD = knockdown; M = moribund; D = dead. F 0 0

[0160] The TC test sample resulted in complete knock down in 4 hours which converted to complete death at 24 hours. The combination treatment without fan resulted in high levels of knockdown in four hours which converted to a higher level of death at 24 hours. The combination treatment with fan resulted in complete knockdown in four hours and a high level of death at 24 hours.

[0161] The combination treatments comprised 2% + 2% flavesone + pyrethrins as compared to the 96% flavesone TC test sample. Considering the significantly lower concentrations of active ingredient in the combination treatments, these results are convincing evidence of a strong combined effect in vapour form.

Claims

The claims defining the invention are as follows:

1. A method for controlling pests in a covered environment, comprising exposing said pests in said covered environment to an effective amount of a vapour form of a compound of formula (I): 2 O R6R5wherein R1is selected from –C(=O)R7, -OR8, -SR8, -C1-10hydroxyalkyl, -NR9R10, -C(=N- R9)R7, -C(=N-OH)R7, -NO, -NO2, -N(OR8)R7and –OSO3R8; R2 is selected from hydrogen, -C1-10alkyl, -C2-10alkenyl, aryl and heteroaryl; R3, R4, R5and R6are each independently selected from hydrogen, -C1-10alkyl, -C3-6cycloalkyl, -C2-10alkenyl, -C1-10haloalkyl, -C1-10dihaloalkyl, -C1-10trihaloalkyl, -OR8, -SR8, -NR9R10, -C(=N-R9)R7, -NO, -NO2, -NR9OR8, -OSO3R8, -C1- 10alkylaryl and –C(=O)R7; R7is selected from hydrogen, -C1-10alkyl, -C2-10alkylaryl, C3-6cycloalkyl, -C2-10alkenyl, -C1-10alkylheteroaryl, -C1-10haloalkyl, -C1-10dihaloalkyl, -C1-10trihaloalkyl, -C1- 10haloalkoxy, -C1-10hydroxyalkyl, -C1-10thioalkyl, -C1-10nitroalkyl, -C1-3alkylOC1-3alkyl, - C1-3alkylOC1-3haloalkyl, -C1-3alkylOC1-3dihaloalkyl, -C1-3alkylOC1-3trihaloalkyl, -OR8, - SR8and –NR9R10; R8 is selected from hydrogen, -C1-10alkyl, -C2-10alkylaryl, -C3-6cycloalkyl, -C2-10alkenyl, -C1-10alkylheteroaryl, -C1-10haloalkyl, -C1-10dihaloalkyl, -C1-10trihaloalkyl, -C1-10haloalkoxy, -C1-10hydroxyalkyl, -C1-10thioalkyl and -C1-10nitroalkyl; and R9 and R10 are independently selected from hydrogen, -C1-10alkyl, -C2-10alkylaryl, -C3-6cycloalkyl, -C2-10alkenyl, -C1-10alkylheteroaryl, -C1-10haloalkyl, -C1-10dihaloalkyl, - C1-10trihaloalkyl.

2. The method according to claim 1, wherein the compound of formula (I) is a compound of formula (II):11O) wherein R11 is selected from –CR12R13R14 or –NR15R16; one of R12 and R13 is hydrogen and the other is hydroxyl or –OCR17R18R19 or R12 and R13together form an oxo group (=O) or a =N-OH group; R14 is –CH(CH3)CR20R21R22, -CH2CH(CH3)CR20R21R22 or – CH(CH3)CH2CR20R21R22; R15and R16are independently selected from hydrogen and C1-10alkyl; R17, R18and R19are independently selected from hydrogen or halo; and R20, R21 and R22 are independently selected from hydrogen, hydroxyl, halo, NO2 and –OCR17R18R19.

3. The method according to claim 1, wherein the compound of formula (I) is a compound of formula (III): R25R26O) wherein one of R23 and R24 is hydrogen and the other is hydroxyl or –OCR27R28R29 or R23 and R24 together form an oxo group (=O); R25is –CR30R31R32, -CH2CR30R31R32or –CH(CH3)CR30R31R32; R26 is H or –CH3; wherein where R26 is H, R25 is –CH(CH3)CR30R31R32; R27, R28 and R29 are independently selected from hydrogen or halo; andR30, R31and R32are independently selected from hydrogen, hydroxyl, halo, NO2and –OCR27R28R29.

4. The method according to claim 1, wherein the compound of formula (I) is selected from the group consisting of: 2F O CBr3O OCH3O O N O O CH2F OCBr3O OCH3O O N O O CH2F O CBr3O2OCH3O O.

5. The method according to any one of claims 1 to 4, wherein the compound of formula (I) is selected from the group consisting of flavesone, leptospermone, isolpetospermone, papuanone, grandiflorone and jensenone.

6. The method according to claim 5, wherein the compound of formula (I) is flavesone.

7. The method according to any one of claims 1 to 6, wherein the compound of formula (I) is applied to the covered environment at a rate of 0.5 ng / hr to 500 mg / hr or 0.5 µg / hr to 250 mg / hr or from 0.5 mg / hr to 125 mg / hr or 0.5 pL / hr to 500 µL / hr or 0.5 nL / hr to 250 µL / hr or 0.5 µL / hr to 250 µL / hr, per m3of space defining the environment.

8. The method according to any one of claims 1 to 7, wherein the compound of formula (I) is applied to the covered environment using a single release point per at least about 6 m3of the volume of space defining the environment.

9. The method according to any one of claims 1 to 8, wherein the compound of formula (I) is applied to the covered environment using a diffuser.

10. The method according to any one of claims 1 to 9, wherein the diffuser is temperature and / or a mechanical diffuser.

11. The method according to any one of claims 1 to 10, wherein the diffuser is an electric diffuser.

12. The method according to claim any one of claims 1 to 11, wherein the compound of formula (I) is applied to the covered environment using a dispersing aid.

13. The method according to any one of claims 1 to 12, wherein the compound of formula (I) is used in combination with at least one second pesticide.

14. The method according to claim 13, wherein the at least one second pesticide is selected from the group consisting of a sodium channel modulator, an acetylcholinesterase (AChE) inhibitor, a GABA-gated chloride channel antagonist, a nicotinergic acetylcholine receptor agonist, an allosteric acetylcholine receptor modulator, a chloride channel actuator, a juvenile hormone mimic, a homopteran feeding blocker, a mitochondrial ATP synthase inhibitor, an uncoupler of oxidative phosphorylation, a nicotinic acetylcholine receptor channel blocker, an inhibitor of chitin biosynthesis, a moulting disruptor, an ecdysone receptor agonist or disruptor, an octapamine receptor agonist, a mitochondrial complex I electron transport inhibitor, an acetyl CoA carboxylase inhibitor, a voltage-dependent sodium channel blocker, a mitochondrial complex IV electron inhibitor, a mitochondrial complex IV electron transport inhibitor or a ryanodine receptor modulator.

15. The method according to claim 14, wherein the at least one second pesticide is a sodium channel modulator, preferably a pyrethroid and / or pyrethrin, more preferably pyrethrin I, pyrethrin II, metofluthrin, transfluthrin and / or prallethrin.

16. The method according to any one of claims 13 to 15, wherein the compound of formula (I), the at least one second pesticide, or both the compound of formula (I) and the at least one second pesticide, are used in a sub-effective amount.

17. The method according to any one of claims 13 to 16, wherein the compound of formula (I), the at least one second pesticide, or both the compound of formula (I) and the at least one second pesticide, are used in a sub-additive amount.

18. The method according to any one of claims 1 to 17, wherein the pest is a flying insect.

19. The method according to claim 18, wherein the pest is an insect of the order Diptera.

20. The method according to claim 19, wherein the insect is a Musca species, Aedes species, Anopheles species, or a Culex species.

21. The method according to claim 20, wherein the insect is selected from the group consisting of Musca domestica, Aedes aegypti, Aedes vexans, Aedes albopictus, Anopheles maculipennis, Anopheles gambiae, Culex pipiens and Culex qunquefasciatus.

22. The method according to any of claims 1 to 21, wherein the pests are pesticide resistant pests.

23. The method according to any one of claims 1 to 22, wherein controlling pests comprises expelling and / or incapacitating pests.

24. The method according to claim 23, wherein controlling pests comprises expelling and / or incapacitating at least 75%, 80%, 85%, 90% or 95% of individuals in a pest population.

25. The method according to claim 23 or 24, wherein the pests are controlled within 1 hour, preferably 50 minutes, preferably 40 minutes, preferably 30 minutes and most preferably 20 minutes of application to the environment26. The method according to any one of claims 23 to 25, wherein controlling pests comprising incapacitating pests.

27. The use of a compound of formula (I) as defined in claim 1, for controlling pests in a covered environment, wherein said pests are exposed to an effective amount of a vapour form of said compound of formula (I) in said covered environment.

28. A kit comprising a compound of formula (I) as defined in claim 1, and a diffuser.

29. A diffuser containing a compound of formula (I) as defined in claim 1.

30. A refill vessel containing a compound of formula (I) as defined in claim 1, for fitting to a diffuser.

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