Methods of controlling an insect of the family pentatomidae

Abstract

A method of controlling or preventing infestation of or damage to a plant or propagation material thereof by an insect of the family Pentatomidae, the method comprising applying to the insect, plant, locus of the plant, or propagation material of the plant, a compound selected from: nodulisporic acid A, nodulisporic acid A1, nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof. Preferably, the compound is nodulisporic acid A. Suitably, the compound may be comprised in a fermentation broth, fermentation product, or agricultural composition. Use of the compound, or a fermentation broth or fermentation product comprising the compound in the manufacture of a composition for the control of an insect of the family Pentatomidae.

Description

[0001] METHODS OF CONTROLLING AN INSECT OF THE FAMILY PENTATOMIDAE

[0002] The present invention relates to methods of controlling or preventing infestation of or damage to plants or propagation material thereof by an insect of the family Pentatomidae. The method comprises applying to the insect, plant, locus of the plant, or propagation material of the plant, a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4, preferably nodulisporic acid A; or an agrochemically acceptable salt thereof.

[0003] Background

[0004] Insects of the family Pentatomidae are commonly known as stink bugs, referring to their ability to release a poignant defensive spray when threatened, disturbed, or crushed.

[0005] Several members of the family Pentatomidae are considered to be agricultural pests because they feed on agricultural crops, thereby causing serious damage and loss of production. They are a threat to many plants including agricultural crops. For example, ornamental trees, shrubs, vines, vegetables, nuts, and commodity crops such as cotton, corn, soybean, sorghum, and wheat can be affected. Their significance has further increased in recent years as they have emerged as invasive pest species in many different countries.

[0006] Chemical control of stink bugs is mainly employed through the use of broad-spectrum insecticides, such as organophosphates, neonicotinoids, pyrethroids, isoxazolines and mixtures thereof. However, the development of resistance by several stink bug species to such broad-spectrum insecticides restricts their utility. For example, the recommended dose of acephate for stink bug control in Brazil has increased four-fold from 2004 to 2018. Despite an increased rate of application, low control outcomes have become increasingly more common.

[0007] In addition, several of the aforementioned broad-spectrum insecticides face scrutiny in relation with their potential effect on the environment, leading to their restriction and ban in certain jurisdictions.

[0008] Therefore, there is an increasing need for the development of new methods for controlling or preventing infestation of plants by insects of the family Pentatomidae.

[0009] Summary of the invention

[0010] It has now been surprisingly found that nodulisporic acid A is highly effective at controlling or preventing infestation of or damage to plants by insects of the family Pentatomidae.

[0011] Nodulisporic acid A is an indole diterpene metabolite produced by the fungus Hypoxylon pulicicidum, formerly classified as Nodulisporium sp. Initial reporting indicated insecticidal activity of nodulisporic acid A against larvae of the blowfly, mosquito and fruit fries. Subsequent studies showed it was an effective systemic ectoparasiticidal agent against blood-feeding arthropods including fleas on dogs and cats. Nodulisporic acid A has been reported to exert its effects by binding to arthropod-specific glutamate-gated chloride channels.

[0012] Since its initial discovery, several naturally produced nodulisporic acid A congeners with minor structural variations have been identified. These exhibit similar insecticidal profiles similar to nodulisporic acid A. For instance, nodulisporic acid A1 and nodulisporic acid A2 were identified by Hensens et al., Tetrahedron Letters, 1999, 40(30), 5455-5458, doi: 10.1016 / S0040-4039(99)01064-3, and nodulisporic acid A4 by Singh et al., J. Nat. Prod., 2004, 67(9), 1496-1506, https: / / doi.org / 10.1021 / np0498455. The chemical structures and biological activities of various indole diterpenoids are reviewed in Niu et al, Natural Products and Bioprospecting, 2023, 13(1):3, https: / / doi.org / 10.1007 / s13659-022-00368-7. Various derivatives of nodulisporic acid A have been prepared and assessed for their efficacy as ectoparasiticidal agents in mammals or birds (US 2002 / 0045653, US 2004 / 0077703).

[0013] The present invention therefore provides a method of controlling or preventing infestation of or damage to a plant or propagation material thereof by an insect of the family Pentatomidae, the method comprising applying to the insect, plant, locus of the plant, or propagation material of the plant, a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof.

[0014] According to another aspect of the invention, there is provided a use of a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof, for controlling Euschistus heros on soybean, corn, cotton, or wheat, or a propagation material thereof according to the method of the invention, optionally wherein the soybean, corn, cotton, or wheat is genetically modified.

[0015] According to another aspect of the invention, there is provided a use of a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof, for controlling an insect of a genus selected from Chinavia, Chlorochroa, Dichelops, Edessa, Euschistus, Halyomorpha, Nezara, and Piezodorus, on soybean, corn, cotton, wheat, or fruits and vegetables or a propagation material thereof according to the method of the invention, optionally wherein the soybean, corn, cotton, or wheat is genetically modified.

[0016] According to another aspect of the invention, there is provided a use of a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof, or a fermentation broth or fermentation product comprising a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof, in the manufacture of a composition for the control of an insect of the family Pentatomidae, or of an insect of a genus selected from Chinavia, Chlorochroa, Dichelops, Edessa, Euschistus, Halyomorpha, Nezara, and Piezodorus.

[0017] Throughout the description and claims of this specification, the words “comprise” and “contain” and variations of them mean “including but not limited to”, and they are not intended to (and do not) exclude other moieties, additives, components, integers or steps.

[0018] Throughout the description and claims of this specification, the singular encompasses the plural unless the context otherwise requires. In particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise.

[0019] Features, integers, characteristics, compounds, chemical moieties or groups described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith.

[0020] The patent, scientific, and technical literature referred to herein establish knowledge that was available to those skilled in the art at the time of filing. The entire disclosures of the issued patents, published, and pending patent applications, and other publications that are cited herein are hereby incorporated by reference to the same extent as if each was specifically and individually indicated to be incorporated by reference. In the case of any inconsistencies, the present disclosure will prevail.

[0021] Unless defined otherwise herein, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. For example, Singleton and Sainsbury, Dictionary of Microbiology and Molecular Biology, 2d Ed., John Wiley and Sons, NY (1994); and Hale and Marham, The Harper

[0022] Collins Dictionary of Biology, Harper Perennial, NY (1991) provide those of skill in the art with a general dictionary of many of the terms used in the invention. Although any methods and materials similar or equivalent to those described herein find use in the practice of the present invention, the preferred methods and materials are described herein. Accordingly, the terms defined herein are more fully described by reference to the specification as a whole. Also, as used herein, the singular terms "a", "an," and "the" include the plural reference unless the context clearly indicates otherwise. It is to be understood that this invention is not limited to the particular methodology, protocols, and reagents described, as these may vary, depending upon the context they are used by those of skill in the art.

[0023] Various aspects of the invention are described in further detail below.

[0024] Brief description of the figures

[0025] Embodiments of the invention are further described hereinafter with reference to the accompanying drawings, in which:

[0026] Figure 1 shows photographs of soybean plants protected by different concentrations of nodulisporic acid A seven days after infestation by Euschistus heros.

[0027] Further details of the figures are disclosed in the examples below.

[0028] Detailed description of the invention

[0029] The present invention relates to a method of controlling or preventing infestation of or damage to a plant or propagation material thereof by an insect of the family Pentatomidae, the method comprising applying to the insect, plant, locus of the plant, or propagation material of the plant, a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof.

[0030] Suitably, the compound is selected from nodulisporic acid A, nodulisporic acid A1 , or nodulisporic acid A2; or an agrochemically acceptable salt thereof. Suitably, the compound is selected from nodulisporic acid A, nodulisporic acid A1 , or nodulisporic acid A4; or an agrochemically acceptable salt thereof. Suitably, the compound is selected from: nodulisporic acid A or nodulisporic acid A1 ; or an agrochemically acceptable salt thereof. Suitably, the compound is selected from: nodulisporic acid A or nodulisporic acid A4; or an agrochemically acceptable salt thereof. Preferably, the compound is nodulisporic acid A or an agrochemically acceptable salt thereof.

[0031] As used herein, the terms "controlling" and “controlling or preventing infestation” refer to reducing the number of pests, eliminating pests and / or preventing further pest damage such that damage to a plant or to a plant derived product or plant propagation material is reduced.

[0032] As used herein, the term "pest" refers to insects that are found in agriculture, horticulture, forestry, the storage of products of vegetable origin (such as fruit, grain, and timber); and those pests associated with the damage of man-made structures. The term pest encompasses all stages in the life cycle of the pest.

[0033] Nodulisporic acid A4 is typically represented by formula (IV):

[0034] The term “compound of the present disclosure” as used herein refers to a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof. Suitably, the compound of the present disclosure is a compound selected from nodulisporic acid A, nodulisporic acid A1 , or nodulisporic acid A2; or an agrochemically acceptable salt thereof. Suitably, the compound of the present disclosure is selected from nodulisporic acid A, nodulisporic acid A1 , or nodulisporic acid A4; or an agrochemically acceptable salt thereof. Suitably, the compound of the present disclosure is selected from: nodulisporic acid A or nodulisporic acid A1 ; or an agrochemically acceptable salt thereof. Suitably, the compound of the present disclosure is a compound selected from: nodulisporic acid A or nodulisporic acid A4; or an agrochemically acceptable salt thereof. Preferably, the compound of the present disclosure is nodulisporic acid A or an agrochemically acceptable salt thereof.

[0035] The nodulisporic acid compounds are referred to herein and above by a so-called "ISO common name" or another "common name" being used in individual cases or a trademark name. The nodulisporic acid compounds are known and are commercially available and / or can be prepared using procedures known in the art and / or procedures reported in the literature.

[0036] Nodulisporic acids are compounds produced by the filamentous fungus Hypoxylon pulicicidum, formerly classified as Nodulisporium sp. Nodulisporic acids F, E, D, C, and B are biosynthetic precursors of nodulisporic acid A, while nodulisporic acids A, A1 , A2, and A4 are biosynthetic end products (Richardson et al., Angew Chem Int Ed Engl, 2022, 61 (49), doi: 10.1002 / anie.202213364).

[0037] Nodulisporic acid A is registered under CAS 163120-03-4 and is commercially available, for instance from BioAustralis Fine Chemicals, Smithfield, Australia. Nodulisporic acid A may be obtained via fermentation of Hypoxylon pulicicidum. Nodulisporic acids F, D, C, and B may be chemically synthesized by procedures known in the art. Subsequent heterologous biosynthesis of nodulisporic acids A, A1 , A2, and A4 has been proposed as an alternative approach of production.

[0038] Heterologous biosynthesis of nodulisporic acid F (a precursor to nodulisporic acid A) in Penicillium paxilli is described in WO 2019 / 064243, together with the identification of genes of Hypoxylon pulicicidum from strain ATCC 74245 responsible for the production of nodulisporic acid. This was also reported in Bittner et al., JACS 2018, 140, 582-585, https: / / doi.org / 10.1021 / jacs.7b10909. Heterologous biosynthesis of the whole biosynthetic pathway was later reported, resulting in production of the end products nodulisporic acids A, A1 , A2, and A4 (Richardson et al., Angew Chem Int Ed Engl, 2022, 61 (49), doi: 10.1002 / anie.202213364). Thus, nodulisporic acids A, A1 , A2, and A4 can be prepared by methods known to the person skilled in the art. They can be either purchased or prepared using synthetic or semi-synthetic chemistry or fermentation processes.

[0039] For example, a fermentation broth, a fermentation product, or a composition comprising nodulisporic acid A, A1 , A2, and / or A4 can be obtained from a process of fermentation of a strain of Hypoxylon pulicicidum. The fermentation broth or fermentation product may not require purification. Alternatively, one or more of nodulisporic acids A, A1 , A2, and / or A4 can be isolated from the fermentation broth or fermentation product and purified, e.g. by chromatography using a sorbent (e.g., silica and reverse phase silica gels, optically active sorbents, resins) or one or more solvents (e.g., partitioning, counter current separation, mixture of polyphasic solvents) or other chemical means (e.g., crystallization, recrystallization, salt formation, and precipitation) to achieve the final degree of purity.

[0040] The skilled person may select particular suitable Hypoxylon pulicicidum strains and use procedures known in the art and / or procedures reported in the literature for the production of nodulisporic acid A, A1 , A2, and / or A4, for example as disclosed in Hensens et al., Tetrahedron Letters, 1999, 40(30), 5455-5458, https: / / doi.Org / 10.1016 / S0040-4039(99)01064-3, Singh et al., J. Nat. Prod., 2004, 67(9), 1496-1506, https: / / doi.org / 10.1021 / np0498455, or Bills et al., PLoS One, 2012, 7(10): e46687, doi:10.1371 / journal. pone.0046687. In particular, suitable fermentation conditions and media are described in Bills et al., 2012. Several fermentation media are described, the optimal being the LSFM medium. A fermentation broth, a fermentation product, or a composition comprising nodulisporic acid A, A1 , A2, and / or A4 may be obtained according to the same procedures.

[0041] Suitable Hypoxylon pulicicidum strains known to produce Nodulisporic acid A in addition to other congeners such as nodulisporic acid D and / or nodulisporic acid F include: MF-5954 (deposited as ATCC 74245) disclosed and characterized in US 5399582; MUCL 49879; CBS 122622; MF6321 ; MF6378. As disclosed in Bills et al., PLoS One, 2012, 7(10): e46687, doi:10.1371 / journal. pone.0046687 other Hypoxylon pulicicidum strains are mentioned to produce nodulisporic acids, but with an alternative or unknown composition of congeners: strains MF6263; MF6315; MF6230; MF6245; MF6379; MF6377; MF6324.

[0042] As used herein, the term “fermentation broth” refers to a composition obtained from a process of fermentation of a microorganism, for example a particular strain of the microorganism. A fermentation broth may contain microorganism cells as well as products resulting from the fermentation process. The microorganism cells in the fermentation broth may be live or inactivated. Inactivated cells have been killed or rendered inactive with a suitable inactivation treatment. Inactivation of the microorganism cells may be achieved through methods known to the person skilled in the art. Inactivation treatments include, for instance, heat treatments, such as sterilisation or pasteurisation, high-pressure processing, irradiation, sonication, and combinations thereof.

[0043] Inactivation may also be achieved with a biocide, i.e. a chemical substance, mixture, or microorganism intended to control microorganisms in another way than the inactivation methods described in the previous paragraph. Inactivation with a biocide may be combined with the inactivation methods described in the previous paragraph. Benzisothiazolinone is a known biocide which may be used in plant protection products.

[0044] Inactivation may be verified through methods known to the person skilled in the art. For instance, a sample of the inactivated fermentation broth may be inoculated on an agar plate and cultured to check for any cells that would give rise to biomass growth. If a cell growth is observed, this may indicate that the inactivation treatment was not effective.

[0045] Suitably, the fermentation broth or fermentation product according to the disclosure is a fermentation broth or fermentation product obtained from Hypoxylon pulicicidum. Preferably, the fermentation broth is inactivated, meaning that the microorganism cells in the fermentation broth have been inactivated. Suitably, the fermentation broth according to the disclosure is an inactivated fermentation broth obtained from Hypoxylon pulicicidum followed with an inactivation treatment.

[0046] According to the method of the invention, the compound may be applied as part of a composition. Suitably, the composition is a fermentation broth, fermentation product, or agricultural composition. Suitably, the composition is an insecticidal composition. Optionally, the fermentation broth, fermentation product, or agricultural composition of the disclosure may further comprise an agriculturally acceptable adjuvant, carrier, surfactant, and / or diluent.

[0047] Accordingly, the method of the invention may suitably comprise applying a fermentation broth, fermentation product, or agricultural composition comprising a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof to the insect, plant, locus of the plant, or propagation material of the plant, optionally wherein the broth, product, or composition further comprises an agriculturally acceptable adjuvant, carrier, surfactant, and / or diluent.

[0048] Suitably, the compound is selected from nodulisporic acid A, nodulisporic acid A1 , or nodulisporic acid A2; or an agrochemically acceptable salt thereof. Suitably, the compound is selected from nodulisporic acid A, nodulisporic acid A1 , or nodulisporic acid A4; or an agrochemically acceptable salt thereof. Suitably, the compound is selected from: nodulisporic acid A or nodulisporic acid A1 ; or an agrochemically acceptable salt thereof. Suitably, the compound is selected from: nodulisporic acid A or nodulisporic acid A4; or an agrochemically acceptable salt thereof. Preferably, the compound is nodulisporic acid A or an agrochemically acceptable salt thereof.

[0049] Suitably, the fermentation broth, fermentation product, or agricultural composition may comprise nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and / or nodulisporic acid A4. Suitably, the fermentation broth, fermentation product, or agricultural composition comprises nodulisporic acid A, nodulisporic acid A1 , and / or nodulisporic acid A2. Suitably, the fermentation broth, fermentation product, or agricultural composition may comprise nodulisporic acid A, nodulisporic acid A1 , or nodulisporic acid A4. Suitably, the fermentation broth, fermentation product, or agricultural composition may comprise nodulisporic acid A or nodulisporic acid A1 . Suitably, the fermentation broth, fermentation product, or agricultural composition comprises nodulisporic acid A and / or nodulisporic acid A4. Preferably, the fermentation broth, fermentation product, or agricultural composition comprises nodulisporic acid A. Hence, the present invention also relates to a method of controlling or preventing infestation of or damage to a plant or propagation material thereof by an insect of the family Pentatomidae, the method comprising applying a fermentation broth, fermentation product, or agricultural composition comprising a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof to the insect, plant, locus of the plant, or propagation material of the plant, optionally wherein the broth, product, or composition further comprises an agriculturally acceptable adjuvant, carrier, surfactant, and / or diluent.

[0050] Suitably, the fermentation broth, fermentation product, or compositions of the disclosure may further comprise an agriculturally acceptable adjuvant, carrier, surfactant, and / or diluent, preferably an agriculturally acceptable adjuvant. Acceptable adjuvants, carriers, surfactants, and diluents for agricultural use are well known in the art. Those skilled in the art can select suitable adjuvants, carriers, surfactants, and diluents.

[0051] As used herein, the term “composition” is understood to encompass the “agricultural composition” according to the disclosure.

[0052] The compositions of the disclosure may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EG), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0053] Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers, and optionally other formulating ingredients). Also, conventional slow release formulations may be employed where long lasting efficacy is intended. Particularly, formulations to be applied in spraying forms, such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain compounds that provide adjuvancy effects.

[0054] A seed dressing formulation is applied in a manner known per se to the seeds employing the compound according to the disclosure and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredient in encapsulated form, e.g. as slow release capsules or microcapsules.

[0055] Suitably, the agricultural composition of the present disclosure may be a seed dressing formulation for application to plant propagation materials, comprising a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof, and further comprising a diluent. Preferably, the seed dressing formulation is in the form of an aqueous suspension or in a dry powder form having good adherence to the plant propagation materials. Preferably, the seed dressing formulation may comprise the active agents in an encapsulated form, preferably a slow-release capsules and / or microcapsules.

[0056] In general, the compositions or formulations include from 0.01 to 90% by weight of active agent and of from 0 to 20% agriculturally acceptable surfactant. Advantageously, the formulation further comprises of from 10 to 99.99% solid or liquid formulation inerts, conservatives, and / or adjuvants. The active agent consists of at least a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof, and optionally other active agents, particularly microbiocides or conservatives or the like.

[0057] Suitably, the agricultural composition of the present disclosure may be a concentrated composition for dilution by the user, wherein the composition comprises of from 2 to 80% by weight, preferably between 5 and 70% by weight, of active agents comprising at least a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof, and optionally other active agents.

[0058] Generally, a compound as defined in any one of embodiments according to the disclosure is used in the form of a composition (e.g., formulation) containing a carrier. A compound as defined in any one of embodiments according to the disclosure and compositions thereof can be used in various forms such as aerosol dispenser, capsule suspension, cold fogging concentrate, dustable powder, emulsifiable concentrate, emulsion oil in water, emulsion water in oil, encapsulated granule, fine granule, flowable concentrate for seed treatment, gas (under pressure), gas generating product, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, powder for dry seed treatment, seed coated with a pesticide, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), ultra-low volume (ulv) liquid, ultra-low volume (ulv) suspension, water dispersible granules or tablets, water dispersible powder for slurry treatment, water soluble granules or tablets, water soluble powder for seed treatment and wettable powder.

[0059] Compositions of this disclosure, including all of the above disclosed embodiments and preferred examples thereof, can be mixed with one or more further pesticides including further fungicides, insecticides, nematicides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection.

[0060] A formulation typically comprises a liquid or solid carrier and optionally one or more customary formulation auxiliaries, which may be solid or liquid auxiliaries, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, clays, inorganic compounds, viscosity regulators, surfactant, binders and / or tackifiers. The composition may also further comprise a fertilizer, a micronutrient donor or other preparations which influence the growth of plants as well as comprising a combination containing the compound of the invention with one or more other biologically active agents, such as bactericides, fungicides, nematicides, plant activators, acaricides, and insecticides. The compositions are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and / or compressing a solid compound of the present invention and in the presence of at least one auxiliary for example by intimately mixing and / or grinding the compound of the present invention with the auxiliary (auxiliaries). In the case of solid compounds of the invention, the grinding / milling of the compounds is to ensure specific particle size.

[0061] Examples of compositions for use in agriculture are emulsifiable concentrates, suspension concentrates, microemulsions, oil dispersibles, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise - at least - a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof, and the type of composition is to be selected to suit the intended aims and the prevailing circumstances.

[0062] As a rule, the compositions comprise 0.1 to 99 %, especially 0.1 to 95 %, of a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof, as defined in any one of embodiments according to the disclosure, and 1 to 99.9 %, especially 5 to 99.9 %, of at least one solid or liquid carrier, it being possible as a rule for 0 to 25 %, especially 0.1 to 20%, of the composition to be surfactants (% in each case meaning percent by weight). Whereas concentrated compositions tend to be preferred for commercial goods, the end consumer as a rule uses dilute compositions which have substantially lower concentrations of active ingredient.

[0063] The compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof according to the disclosure may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they may be conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g., in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating, or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.

[0064] Suitable carriers and adjuvants, e.g., for agricultural use, can be solid or liquid and are substances useful in formulation technology, e.g., natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders, or fertilizers. Such carriers are for example described in WO 1997 / 33890.

[0065] Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate. Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller’s earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.

[0066] Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other nonvolatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

[0067] Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required. Typical carriers for granular formulations include sand, fuller’s earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials which absorb or which can be coated with the active compound. Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and / or stickers such as dextrins, glue or synthetic resins.

[0068] Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours, and other organic and inorganic solids which act as dispersants and carriers.

[0069] The active ingredients can also be contained in microcapsules. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g., slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene / butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane, or chemically modified polymers, and starch xanthates, or other polymers that are known to the person skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.

[0070] Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter. The enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores. Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust, and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

[0071] Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurised sprayers, wherein the active ingredient is dispersed in finely divided form because of vaporisation of a low boiling dispersant solvent carrier, may also be used.

[0072] Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to a person skilled in the art.

[0073] Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2-ethyl hexanol, ethylene carbonate, 1 ,1 ,1-trichloroethane, 2-heptanone, alpha pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octyl amine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerine and N-methyl-2-pyrrolidinone. Water is generally the carrier of choice for the dilution of concentrates.

[0074] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, fuller’s earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.

[0075] A broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application. These agents, when used, normally comprise from 0.1 % to 15% by weight of the formulation. They can be anionic, cationic, non-ionic or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surface-active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub. 18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub. 16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.

[0076] Other adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti-foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.

[0077] The compound, fermentation broth, fermentation product, or agricultural composition according to the disclosure can suitably be applied to the insect, plant, locus of the plant, or propagation material of the plant according to the method of the invention.

[0078] Suitably, the method according to the invention comprises applying an effective amount of the compound.

[0079] As used herein, the term "effective amount" refers to the amount of the compound, or a salt thereof, which, upon single or multiple applications provides the desired effect.

[0080] An effective amount is readily determined by the skilled person in the art, using known techniques and by observing results obtained under analogous circumstances. In determining the effective amount, a number of factors are considered including, but not limited to the type of plant or derived product to be applied; the pest to be controlled and its lifecycle; the particular compound applied; the type of application; and other relevant circumstances.

[0081] Preferably, an “effective” amount herein refers to an amount of the active ingredient that shows sufficient control or insecticidal activity, e.g., at least 10 %, more preferably at least 20%, yet more preferably at least 50%, and again more preferably at least 70 % effectiveness, compared to a control. In the present case, the method according to the invention preferably comprises applying at least 0.01 ppm, more preferably at last 0.025 ppm of active ingredient (ai), more preferably at least for example 0.8 ppm, 1.563 ppm, 3 ppm, 6.25 ppm, 13 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, or 400 ppm.

[0082] The active ingredient (ai) of the present disclosure is a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof. Suitably, the active ingredient is a compound selected from: nodulisporic acid A, nodulisporic acid A1 , or nodulisporic acid A2; or an agrochemically acceptable salt thereof. Suitably, the active ingredient is a compound selected from: nodulisporic acid A, nodulisporic acid A1 , or nodulisporic acid A4; or an agrochemically acceptable salt thereof. Suitably, the active ingredient is a compound selected from: nodulisporic acid A or nodulisporic acid A1 ; or an agrochemically acceptable salt thereof. Suitably, the active ingredient is a compound selected from: nodulisporic acid A or nodulisporic acid A4; or an agrochemically acceptable salt thereof. Preferably, the active ingredient is nodulisporic acid A or an agrochemically acceptable salt thereof.

[0083] Suitably, the compound, fermentation broth, fermentation product, or agricultural composition may be applied at a rate of at least 0.01 ppm ai. Suitably, the compound, fermentation broth, fermentation product, or agricultural composition is applied at a rate of at least 0.025 ppm ai, at least 0.8 ppm ai, at least 1 .563 ppm ai, at least 3 ppm ai, at least 6.25 ppm ai, at least 13 ppm ai, at least 25 ppm ai, at least 50 ppm ai, at least 75 ppm ai, at least 100 ppm ai, at least 125 ppm ai, at least 150 ppm ai, at least 175 ppm ai, at least 200 ppm ai, at least 300 ppm ai, at least 400 ppm ai, at least 500 ppm ai, at least 600 ppm ai, at least 700 ppm ai, at least 800 ppm ai, at least 900 ppm ai, at least 1000 ppm ai, at least 1100 ppm ai, at least 1200 ppm ai, at least 1300 ppm ai, at least 1400 ppm ai, at least 1500 ppm ai, at least 2000 ppm ai, or at least 2500 ppm ai.

[0084] A preferred method according to the invention comprises a method of controlling or preventing infestation of or damage to a plant or propagation material thereof by an insect of the family Pentatomidae, the method comprising applying to the insect, plant, locus of the plant, or propagation material of the plant nodulisporic acid A or an agrochemically acceptable salt thereof, wherein the compound is applied at a rate of at least 100 ppm ai, preferably at least 200 ppm ai, more preferably at least 400 ppm ai. Preferably, the insect is an insect of the genus Euschistus. Preferably, the insect is an adult.

[0085] Suitably, the compound, fermentation broth, fermentation product, or agricultural composition may be applied at a rate of from 1 to 5000 g ai / ha.

[0086] Suitably, the compound, fermentation broth, fermentation product, or agricultural composition is applied at a rate of from 5 to 2500 g ai / ha, of from 5 to 2000 g ai / ha, of from 5 to 1500 g ai / ha, of from 5 to 1000 g ai / ha, of from 5 to 500 g ai / ha, of from 5 to 400 g ai / ha, of from 5 to 350 g ai / ha, of from 5 to 300 g ai / ha, of from 5 to 250 g ai / ha, of from 5 to 225 g ai / ha, of from 5 to 200 g ai / ha, of from 5 to 190 g ai / ha of from 5 to 180 g ai / ha of from 5 to 170 g ai / ha, of from 5 to 160 g ai / ha, of from 5 to 150 g ai / ha, of from 5 to 140 g ai / ha of from 5 to 130 g ai / ha of from 5 to 120 g ai / ha, of from 5 to 110 g ai / ha, or of from 5 to 100 g ai / ha.

[0087] Suitably, the compound, fermentation broth, fermentation product, or agricultural composition is applied at a rate of from 10 to 2500 g ai / ha, of from 10 to 2000 g ai / ha, of from 10 to 1500 g ai / ha, of from 10 to 1000 g ai / ha, of from 10 to 500 g ai / ha, of from 10 to 400 g ai / ha, of from 10 to 350 g ai / ha, of from 10 to 300 g ai / ha, of from 10 to 250 g ai / ha, of from 10 to 225 g ai / ha, of from 10 to 200 g ai / ha, of from 10 to 190 g ai / ha of from 10 to 180 g ai / ha of from 10 to 170 g ai / ha, of from 10 to 160 g ai / ha, of from 10 to 150 g ai / ha, of from 10 to 140 g ai / ha of from 10 to 130 g ai / ha of from 10 to 120 g ai / ha, of from 10 to 110 g ai / ha, or of from 10 to 100 g ai / ha.

[0088] Suitably, the compound, fermentation broth, fermentation product, or agricultural composition is applied at a rate of from 20 to 2500 g ai / ha, of from 20 to 2000 g ai / ha, of from 20 to 1500 g ai / ha, of from 20 to 1000 g ai / ha, of from 20 to 500 g ai / ha, of from 20 to 400 g ai / ha, of from 20 to 350 g ai / ha, of from 20 to 300 g ai / ha, of from 20 to 250 g ai / ha, of from 20 to 225 g ai / ha, of from 20 to 200 g ai / ha, of from 20 to 190 g ai / ha of from 20 to 180 g ai / ha of from 20 to 170 g ai / ha, of from 20 to 160 g ai / ha, of from 20 to 150 g ai / ha, of from 20 to 140 g ai / ha of from 20 to 130 g ai / ha of from 20 to 120 g ai / ha, of from 20 to 110 g ai / ha, or of from 20 to 100 g ai / ha.

[0089] Suitably, the compound, fermentation broth, fermentation product, or agricultural composition is applied at a rate of from 30 to 2500 g ai / ha, of from 30 to 2000 g ai / ha, of from 30 to 1500 g ai / ha, of from 30 to 1000 g ai / ha, of from 30 to 500 g ai / ha, of from 30 to 400 g ai / ha, of from 30 to 350 g ai / ha, of from 30 to 300 g ai / ha, of from 30 to 250 g ai / ha, of from 30 to 225 g ai / ha, of from 30 to 200 g ai / ha, of from 30 to 190 g ai / ha of from 30 to 180 g ai / ha of from 30 to 170 g ai / ha, of from 30 to 160 g ai / ha, of from 30 to 150 g ai / ha, of from 30 to 140 g ai / ha of from 30 to 130 g ai / ha of from 30 to 120 g ai / ha, of from 30 to 110 g ai / ha, or of from 30 to 100 g ai / ha.

[0090] Suitably, the compound, fermentation broth, fermentation product, or agricultural composition is applied at a rate of from 40 to 2500 g ai / ha, of from 40 to 2000 g ai / ha, of from 40 to 1500 g ai / ha, of from 40 to 1000 g ai / ha, of from 40 to 500 g ai / ha, of from 40 to 400 g ai / ha, of from 40 to 350 g ai / ha, of from 40 to 300 g ai / ha, of from 40 to 250 g ai / ha, of from 40 to 225 g ai / ha, of from 40 to 200 g ai / ha, of from 40 to 190 g ai / ha of from 40 to 180 g ai / ha of from 40 to 170 g ai / ha, of from 40 to 160 g ai / ha, of from 40 to 150 g ai / ha, of from 40 to 140 g ai / ha of from 40 to 130 g ai / ha of from 40 to 120 g ai / ha, of from 40 to 110 g ai / ha, or of from 40 to 100 g ai / ha.

[0091] Suitably, the compound, fermentation broth, fermentation product, or agricultural composition is applied at a rate of from 50 to 2500 g ai / ha, of from 50 to 2000 g ai / ha, of from 50 to 1500 g ai / ha, of from 50 to 1000 g ai / ha, of from 50 to 500 g ai / ha, of from 50 to 400 g ai / ha, of from 50 to 350 g ai / ha, of from 50 to 300 g ai / ha, of from 50 to 250 g ai / ha, of from 50 to 225 g ai / ha, of from 50 to 200 g ai / ha, of from 50 to 190 g ai / ha of from 50 to 180 g ai / ha of from 50 to 170 g ai / ha, of from 50 to 160 g ai / ha, of from 50 to 150 g ai / ha, of from 50 to 140 g ai / ha of from 50 to 130 g ai / ha of from 50 to 120 g ai / ha, of from 50 to 110 g ai / ha, or of from 50 to 100 g ai / ha.

[0092] Suitably, the compound, fermentation broth, fermentation product, or agricultural composition is applied at a rate of at least 5 g ai / ha. Suitably, the compound, fermentation broth, fermentation product, or agricultural composition is applied at a rate of at least 10 g ai / ha, at least 15 g ai / ha, at least 20 g ai / ha, at least 25 g ai / ha, at least 30 g ai / ha, at least 35 g ai / ha, at least 40 g ai / ha, at least 45 g ai / ha, at least 50 g ai / ha, at least 55 g ai / ha, at least 60 g ai / ha, at least 65 g ai / ha, at least 70 g ai / ha, at least 75 g ai / ha, at least 80 g ai / ha, at least 85 g ai / ha, at least 90 g ai / ha, at least 95 g ai / ha, at least 100 g ai / ha, at least 110 g ai / ha, at least 120 g ai / ha, at least 130 g ai / ha, at least 140 g ai / ha, or at least 150 g ai / ha.

[0093] Suitably, the compound, fermentation broth, fermentation product, or agricultural composition is applied at a rate of at most 5000 g ai / ha. Suitably, the compound, fermentation broth, fermentation product, or agricultural composition is applied at a rate of at most 2500 g ai / ha, at most 2000 g ai / ha, at most 1500 g ai / ha, at most 1000 g ai / ha, at most 500 g ai / ha, at most 400 g ai / ha, at most 350 g ai / ha, at most 300 g ai / ha, at most 250 g ai / ha, at most 200 g ai / ha, at most 190 g ai / ha, at most 180 g ai / ha, at most 170 g ai / ha, at most 160 g ai / ha, or at most 150 g ai / ha.

[0094] Preferably, the compound is applied at the aforementioned indicated rates. Preferably, the compound, fermentation broth, fermentation product, or agricultural composition is applied to the insect, plant, or locus of the plant at the aforementioned indicated rates. More preferably, the compound, fermentation broth, fermentation product, or agricultural composition is applied to the plant or locus of the plant at the aforementioned indicated rates. Preferably, the compound is applied at the aforementioned indicated rates.

[0095] The term “g ai / ha” as used herein refers to the application rate given in gram [g] of active ingredient [ai] per unit of surface [ha]. The unit hectare (symbol ha) is the metric unit of area that equals a square with 100 m side (1 hm2) or 10,000 square meters. Hectare is a commonly used unit of area in the metric system.

[0096] A preferred method according to the invention comprises a method of controlling or preventing infestation of or damage to a plant or propagation material thereof by an insect of the family Pentatomidae, the method comprising applying to the insect, plant, locus of the plant, or propagation material of the plant nodulisporic acid A or an agrochemically acceptable salt thereof, wherein the compound is applied at a rate of at least 10 g ai / ha, preferably at least 50 g ai / ha, more preferably at least 100 g ai / ha. Preferably, the insect is an insect of a genus selected from: Chinavia, Chlorochroa, Dichelops, Edessa, Euschistus, Halyomorpha, Nezara, and Piezodorus, more preferably an insect of a genus selected from: Dichelops, Euschistus, Halyomorpha, Nezara, and Piezodorus, and even more preferably an insect of the genus Dichelops, Euschistus, Nezara, and Piezodorus. In a most preferred embodiment, the insect is an insect of the genus Euschistus, such as Euschistus heros and Euschistus servus.

[0097] The term "plant propagation material” as used herein denotes all generative parts of a plant, for example seeds or vegetative parts of plants such as cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes, and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably, “plant propagation material” is understood to denote seeds. In a further aspect, the present invention also relates to plant propagation material coated with the compound, fermentation broth, fermentation product, or agricultural composition according to the disclosure.

[0098] As used herein, the term "seed" denotes any resting stage of a plant that is physically detached from the vegetative stage of a plant and / or may be stored for prolonged periods of time and / or can be used to re-grow another plant individual of the same species. Here, the term "resting" refers to a state wherein the plant retains viability, within reasonable limits, in spite of the absence of light, water and / or nutrients essential for the vegetative (i.e. non-seed) state. In particular, the term refers to true seeds but does not embrace plant propagules such as suckers, corms, bulbs, fruit, tubers, grains, cuttings and cut shoots.

[0099] Suitably, the compound, fermentation broth, fermentation product, or agricultural composition according to the disclosure is applied to seed at a rate of from 0.001 to 50 g active ingredient per kg of seed. Suitably, the compound, fermentation broth, fermentation product, or agricultural composition according to the disclosure is applied to seed at a rate of from 0.005 to 40, of from 0.01 to 30, or of from 0.01 to 10 g active ingredient per kg of seed.

[0100] The compound, fermentation broth, fermentation product, or agricultural composition according to the disclosure may be applied with any suitable application method, such as foliar, drench, spraying, atomizing, dusting, scattering, coating, or pouring, to be chosen in accordance with the intended objectives and the prevailing circumstances.

[0101] The compound, fermentation broth, fermentation product, or agricultural composition according to the disclosure may suitably be applied to the insect, plant, locus of the plant, or propagation material of the plant according to the method of the invention by means of foliar application, soil application, in furrow application, or drench application.

[0102] Suitably, the compound, fermentation broth, fermentation product, or agricultural composition is applied to the leaves of the plants. Suitably, the compound, fermentation broth, fermentation product, or agricultural composition is applied to the soil in or on which the plants are growing and / or will grow.

[0103] A suitable means is readily determined by the skilled person in the art, using known techniques and by observing results obtained under analogous circumstances. In determining the suitable means, a number of factors are considered including, but not limited to the type and / or age of plant or derived product to be applied; the pest to be controlled and its lifecycle; the particular compound applied; and other relevant circumstances.

[0104] The term “foliage” as used herein refers to those portions of a plant that normally grow above the ground, including, but not limited to, leaves, stalks, stems, flowers, fruiting bodies, nuts, and fruits.

[0105] The term “foliar application” as used herein refers to the application of an active ingredient to the foliage of a plant (e.g., to the leaves of the plant). Application may be effected by any suitable means, including, but not limited to, spraying the plant with a composition comprising the active ingredient. Suitably, the active ingredient may be applied to the leaves, stems and / or stalk of the plant, and not to the flowers, fruiting bodies, nuts, or fruits of the plant.

[0106] In an example, the compound, fermentation broth, fermentation product, or agricultural composition of the disclosure is applied in the field to the foliage of the plant (foliar application), thus allowing to select frequency and rate of application to match the danger of infestation with the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by drenching the locus of the plants in the field with a liquid composition or by incorporating the active ingredient in solid form into the locus of the plants in the field, for example into the soil or furrow, such as in the form of granules. In the case of paddy rice crops, such granules can be metered into the flooded paddy-field.

[0107] Suitably, the method according to the invention may comprise applying to the insect, plant, locus of the plant, or propagation material of the plant, a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof, by means of foliar application, soil application, in furrow application, or drench application. Suitably, the compound is selected from nodulisporic acid A, nodulisporic acid A1 , or nodulisporic acid A2; or an agrochemically acceptable salt thereof. Suitably, the compound is selected from nodulisporic acid A, nodulisporic acid A1 , or nodulisporic acid A4; or an agrochemically acceptable salt thereof. Suitably, the compound is selected from: nodulisporic acid A or nodulisporic acid A1 ; or an agrochemically acceptable salt thereof. Suitably, the compound is selected from: nodulisporic acid A or nodulisporic acid A4; or an agrochemically acceptable salt thereof. Preferably, the compound is nodulisporic acid A or an agrochemically acceptable salt thereof.

[0108] Suitably, the method according to the invention may comprise applying a fermentation broth, fermentation product, or agricultural composition comprising a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof to the insect, plant, locus of the plant, or propagation material of the plant by means of foliar application, soil application, in furrow application, or drench application, optionally wherein the broth, product, or composition further comprises an agriculturally acceptable adjuvant, carrier, surfactant, and / or diluent.

[0109] Preferably, controlling or preventing infestation of or damage to a plant or propagation material thereof by an insect of the family Pentatomidae according to the method of the invention comprises controlling or preventing infestation of or damage to a plant or propagation material thereof by an adult insect of the family Pentatomidae. Adult insects of the family Pentatomidae typically cause more damage to plants or propagation material thereof and therefore are preferably controlled.

[0110] According to the method of the invention, an insect of the family Pentatomidae is controlled or prevented to infest or damage a plant or propagation material thereof. The method according to the invention may be effective against especially certain genera or species of the family Pentatomidae.

[0111] Suitably, the insect of the family Pentatomidae is an insect of the subfamily Pentatominae.

[0112] Suitably, the insect of the family Pentatomidae is an insect of a tribe selected from: Cappaeini, Carpocorini, and Nezarini.

[0113] Suitably, the insect of the family Pentatomidae is an insect of a genus selected from: Chinavia, Chlorochroa, Dichelops, Edessa, Euschistus, Halyomorpha, Nezara, and Piezodorus. Suitably, the insect of the family Pentatomidae is an insect of a genus selected from: Dichelops, Euschistus, Halyomorpha, Nezara, and Piezodorus. Suitably, the insect of the family Pentatomidae is an insect of a genus selected from: Dichelops, Euschistus, Nezara, and Piezodorus. Suitably, the insect of the family Pentatomidae is an insect of the genus Euschistus.

[0114] Suitably, the insect of the family Pentatomidae is an insect selected from: Chinavia hilaris, Chinavia impicticornis, Chlorochroa sayi, Dichelops furcatus, Dichelops melacanthus, Edessa meditabunda, Euschistus heros, Euschistus impictiventris, Euschistus servus, Halyomorpha halys, Nezara viridula, and Piezodorus guildinii. Suitably, the insect of the family Pentatomidae is an insect selected from: Dichelops furcatus, Dichelops melacanthus, Euschistus heros, Euschistus servus, Halyomorpha halys, Nezara viridula, and Piezodorus guildinii. Suitably, the insect of the family Pentatomidae is an insect selected from: Dichelops furcatus and Euschistus heros. Suitably, the insect of the family Pentatomidae is an insect selected from: Dichelops melacanthus and Euschistus heros. Suitably, the insect of the family Pentatomidae is an insect selected from: Euschistus heros and Halyomorpha halys. Suitably, the insect of the family Pentatomidae is an insect selected from: Euschistus heros and Nezara viridula. Suitably, the insect of the family Pentatomidae is an insect selected from: Euschistus heros and Piezodorus guildinii. Suitably, the insect of the family Pentatomidae is Euschistus heros.

[0115] The method according to the invention is particularly effective against Euschistus heros. Euschistus heros may be considered as a representative organism for the family Pentatomidae.

[0116] It is noted that the genus Dichelops was formerly classified as Diceraeus spp. Insects of the genus Dichelops that were formerly classified as the genus Diceraeus are therefore also encompassed by the genus Dichelops as used herein. For example, Dichelops furcatus and Diceraeus furcatus are used interchangeably, as well as Dichelops melacanthus and Diceraeus melacanthus.

[0117] A preferred method according to the invention comprises a method of controlling or preventing infestation of or damage to a plant or propagation material thereof by an insect of the family Pentatomidae, the method comprising applying to the insect, plant, locus of the plant, or propagation material of the plant nodulisporic acid A or an agrochemically acceptable salt thereof, wherein the insect is an insect of a genus selected from: Chinavia, Chlorochroa, Dichelops, Edessa, Euschistus, Halyomorpha, Nezara, and Piezodorus. Preferably, the insect is an insect of a genus selected from: Dichelops, Euschistus, Nezara, and Piezodorus. More preferably, the genus is Euschistus.

[0118] The compound, fermentation broth, fermentation product, or agricultural composition according to the disclosure may be used to control or prevent infestation of or damage to any suitable plant or propagation material thereof by an insect of the family Pentatomidae according to the method of the invention. Hence, the following lists of plants do not represent any limitation.

[0119] Suitably, the plant is a plant selected from: grains, fruits and tree nuts, vegetables, field crops, oil seed crops, fibre crops, forage crops, forest plants, horticulture crops, floriculture, greenhouse and nursery plants, culinary herbs and spices, and medicinal herbs.

[0120] Suitably, the plant is a plant selected from selected from: grains, fruits and tree nuts, vegetables, oil seed crops, and fibre crops.

[0121] Suitably, the plant is a plant selected from selected from: soybean (Glycine max (L.) Merr.), corn (Zea mays L.), cotton (Gossypium spp.) and wheat (Triticum aestivum L.). Preferably, the plant is soybean.

[0122] The term “plants” as used herein refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.

[0123] The term “locus” as used herein is understood to mean fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation. Preferably, the locus may be the soil.

[0124] The compound, fermentation broth, fermentation product, or agricultural composition according to the disclosure may be used to control or prevent infestation of or damage to a genetically modified plant or propagation material thereof by an insect of the family Pentatomidae according to the method of the invention. Hence, suitably, the plant may be a genetically modified or transgenic plant.

[0125] The plants and / or crops to be protected in accordance with the disclosure include conventional as well as genetically enhanced or engineered varieties such as, for example, insect resistant (e.g., Bt. and VIP varieties) as well as disease resistant, herbicide tolerant (e.g., glyphosate- and glufosinateresistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®) and nematode tolerant varieties. By way of example, suitable genetically enhanced or engineered plant varieties include the Stoneville 5599BR cotton and Stoneville 4892BR cotton varieties.

[0126] Examples of soybean varieties that have been rendered resistant to insects of the family Pentatomidae, including Euschistus heros, have been developed by the Campinas Agronomic Institute in Brazil, which are soybean genotypes PI274453, PI274454, IAC73-228, IAC78-2318, IAC 80-596-2, and IAC 80-4228.

[0127] The terms "plants" and / or “crops” is to be understood as including also plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol- pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a plant that has been rendered tolerant to imidazolinones, e.g., imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of plants that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.

[0128] The terms "plants" and / or “crops” is to be understood as including those which naturally are or have been rendered resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesizing one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria. Examples of toxins which can be expressed include d-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonizing nematodes, and toxins produced by scorpions, arachnids, wasps, and fungi. An example of a plant that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut® (Syngenta Seeds). An example of a plant comprising more than one gene that codes for insecticidal resistance and thus expresses more than one toxin is VipCot® (Syngenta Seeds). Plants or seed material thereof can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification). For example, a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

[0129] The terms "plants" and / or “crops” is to be understood as also including plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis- related proteins" (PRPs, see e.g., EP0392225A). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP0392225A, WO95 / 33818, and EP0353191A. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

[0130] Toxins that can be expressed by transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae or insecticidal proteins from Bacillus thuringiensis, such as d- endotoxins, e.g. CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3 hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.

[0131] Further, in the context of the present disclosure there are to be understood by d-endotoxins, for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins, and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02 / 15701). Truncated toxins, for example a truncated CrylAb, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see W003 / 018810).

[0132] Suitably, the genetically modified or transgenic plant according to the disclosure expresses an insecticidal protein. Suitably, the insecticidal protein is an insecticidal Bacillus thuringiensis d-endotoxin, including hybrid, truncated, and modified variants thereof.

[0133] The combination of a genetically modified or transgenic plant according to the disclosure expressing an insecticidal protein and the compound according to the disclosure, which provides an insecticidal effect, may suitably reduce the development of resistance of insects feeding on the plant.

[0134] The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

[0135] The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).

[0136] Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1 Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a CrylAc toxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a CrylAb toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt1 1 corn borer (CB) trait) and Protecta®.

[0137] Further examples of such transgenic plants are:

[0138] 1. Bt1 1 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.

[0139] 2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylAb toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.

[0140] 3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03 / 018810.

[0141] 4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.

[0142] 5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0143] 6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize for the expression of the protein Cry1 F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.

[0144] 7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B 1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.

[0145] The compound, fermentation broth, fermentation product, or agricultural composition according to the disclosure may be used to control or prevent infestation of or damage to a genetically modified plant selected from: soybean, corn, cotton, and wheat; or propagation material thereof by an insect of the family Pentatomidae according to the method of the invention.

[0146] Suitably, the plant according to the disclosure is a genetically modified plant selected from selected from: soybean, corn, cotton, and wheat. Suitably, the genetically modified soybean, corn, cotton, or wheat plant expresses an insecticidal protein. Suitably, the insecticidal protein is an insecticidal Bacillus thuringiensis d-endotoxin, including hybrid, truncated, and modified variants thereof.

[0147] Examples of commercially available genetically modified soybean plants, which can preferably be treated according to the invention, include, but not limited to, commercially available products such as plant seeds Intacta®, lntacta®2, Intacta® Roundup Ready™ 2 Pro (lntacta®RR2 PRO), lntacta®2 Xtend™, Cultivance, Conkesta Soybean, Conkesta Enlist E3™ Soybean, Enlist™ Soybean, Enlist E3™ Soybean, Roundup Ready™ Soybean, Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready 2 Yield™, Herbicide-tolerant Soybean line, Optimum GAT™, Liberty Link™ Soybean, Vistive Gold™, Verdeca HB4 Soybean, Treus™, Plenish™.

[0148] Examples of commercially available genetically modified cotton plants, which can preferably be treated according to the invention, include, but not limited to, commercially available products such as plant seeds Bollgard®, Bollgard II™ Cotton, LibertyLink®, Roundup Ready™, WideStrike™ Cotton, Bollgard® III x Roundup Ready™ Flex™, GlyTol™, GlyTol™ Liberty Link™, Glytol™ x Twinlink™, GlyTol LibertyLink TwinLink® Plus, Fibermax™ Liberty Link™, Bollgard™ Cotton, Ingard™, Roundup Ready™ Bollgard™ Cotton, Roundup Ready™ Flex™ Cotton, Roundup Ready™ Flex™ Bollgard II™ Cotton, TwinLink™ Cotton, BXN™ Cotton.

[0149] In another aspect, the present invention provides a use of a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof, for controlling or preventing infestation of Euschistus heros on soybean, corn, cotton, or wheat, or a propagation material thereof according to the method of the invention, optionally wherein the soybean, corn, cotton, or wheat is genetically modified.

[0150] Preferably, the compound is nodulisporic acid A.

[0151] In another aspect, the present invention provides a use of a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof, or a fermentation broth or fermentation product comprising a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4, in the manufacture of a composition for the control of an insect of the family Pentatomidae. Suitably, the compound is selected from nodulisporic acid A, nodulisporic acid A1 , or nodulisporic acid A2; or an agrochemically acceptable salt thereof. Suitably, the compound is selected from nodulisporic acid A, nodulisporic acid A1 , or nodulisporic acid A4; or an agrochemically acceptable salt thereof. Suitably, the compound is selected from: nodulisporic acid A or nodulisporic acid A1 ; or an agrochemically acceptable salt thereof. Suitably, the compound is selected from: nodulisporic acid A or nodulisporic acid A4; or an agrochemically acceptable salt thereof. Preferably, the compound is nodulisporic acid A or an agrochemically acceptable salt thereof.

[0152] Suitably, the insect of the family Pentatomidae is an insect of a genus selected from: Chinavia, Chlorochroa, Dichelops, Edessa, Euschistus, Halyomorpha, Nezara, and Piezodorus. Suitably, the insect of the family Pentatomidae is an insect of a genus selected from: Dichelops, Euschistus, Halyomorpha, Nezara, and Piezodorus. Suitably, the insect of the family Pentatomidae is an insect of the genus Euschistus.

[0153] Suitably, the insect of the family Pentatomidae is an insect selected from: Chinavia hilaris, Chinavia impicticornis, Chlorochroa sayi, Dichelops furcatus, Dichelops melacanthus, Edessa meditabunda, Euschistus heros, Euschistus impictiventris, Euschistus servus, Halyomorpha halys, Nezara viridula, and Piezodorus guildinii. Suitably, the insect of the family Pentatomidae is an insect selected from: Dichelops furcatus, Dichelops melacanthus, Euschistus heros, Halyomorpha halys, Nezara viridula, and Piezodorus guildinii. Suitably, the insect is Euschistus heros.

[0154] Methods and means for manufacturing a suitable composition for the control of insects are known in the art, examples and embodiments of which are set out in detail herein.

[0155] The methods and uses of the present invention do not comprise a method for treatment of the human or animal body by surgery or therapy or a diagnostic method practiced on the human or animal body. Thus, they exclude a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practiced on the human or animal body.

[0156] The Examples which follow serve to illustrate the invention and are not meant in any way to limit the invention.

[0157] Examples

[0158] The compounds according to the disclosure, in particular nodulisporic acid A, are tested for their biological (insecticidal) activity in the following Examples. It can be observed that the compounds provide a highly effective means of controlling or preventing infestation of or damage to plants or propagation material thereof by insects of the family Pentatomidae.

[0159] Example 1 : Nymphs

[0160] Euschistus heros (Neotropical brown stink bug), N2 nymphs, feeding / contact .

[0161] Two-week old soybean plants were sprayed in a spray chamber with diluted spray solutions containing different concentrations of nodulisporic acid A. After drying of the spray solution, the soybean plants were cut and placed into Petri dishes (15 cm diameter) with wetted filter papers. The cut plants were then infested with 10 N2 nymphs. Two soybean seeds were added on the filter paper. The Petri dishes were then closed with a lid. Relevant controls and standards were included and performed as expected.

[0162] The samples were assessed 6 days after infestation for mortality of the nymphs in comparison to untreated samples (including controls). Results are shown in Table 1.

[0163] Table 1 : insecticidal activity of nodulisporic acid A against Euschistus heros as described above

[0164] This test shows that nodulisporic acid A is active against nymphs of Euschistus heros already at a concentration of 3 ppm, and that it would provide almost complete control of nymphs of Euschistus heros at a concentration of 13 ppm.

[0165] Example 2: Nymphs

[0166] Euschistus heros (Neotropical brown stink bug), N2 nymphs, feeding / contact.

[0167] Two-week old soybean plants were sprayed in a spray chamber with diluted spray solutions containing different concentrations of nodulisporic acid A. After drying of the spray solution, the soybean plants were cut and placed into Petri dishes (15 cm diameter) with wetted filter papers. The cut plants were then infested with 10 N2 nymphs. Two soybean seeds were added on the filter paper. The Petri dishes were then closed with a lid. Relevant controls and standards were included and performed as expected.

[0168] The samples were assessed for living, affected and dead individuals in comparison to untreated samples at 1 , 2, 3, 4, and 7 days after infestation. The insects are considered as “affected” when they show various symptoms including any behavioural changes such as feeding interruptions, paralysis, etc. Results are shown in Table 2.

[0169] Table 2: Insecticidal activity of nodulisporic acid A against Euschistus heros as described above

[0170] Affected insects are unable to properly feed on the plant, thereby preventing them from causing plant damage. As shown in this test, nymphs are fully controlled (affected + dead) at rates of 6.25 ppm and above already 2 days after infestation. At a rate of 25 ppm, all the nymphs are controlled 1 day after infestation.

[0171] Example 3: Preventative efficacy on whole plants - Adults

[0172] Euschistus heros (Neotropical brown stink bug), adults, feeding / contact

[0173] Two-week old soybean plants were sprayed in a spray chamber with diluted spray solutions containing different concentrations of nodulisporic acid A. After drying off, the whole plants were placed in plastic test boxes and they were infested with 10 freshly moulted Euschistus heros adults. Then, 3 soybean seeds were added. Relevant controls and standards were included and performed as expected The samples were assessed for % of living, affected and dead individuals in comparison to untreated samples, 4 hours, 1 , 4, and 7 days after infestation. The insects are considered as “affected” when they show various symptoms including any behavioural changes such as feeding interruptions, paralysis, etc. Results are shown in Table 3 and Figure 1 .

[0174] Figure 1 shows photographs of soybean plants protected by different concentrations of nodulisporic acid A 7 days after infestation by Euschistus heros adults. Near complete necrosis and wilting of the stems and leaves can be observed in the untreated control plant. Substantial necrosis of most of the stems and leaves as well as wilting of most leaves can be observed in the plant treated with 50 ppm nodulisporic acid A, in addition to stunting of overall growth of the plant. Varying degrees of necrosis of stems and leaves as well as wilting of some leaves can be observed in the plant treated with 100 ppm nodulisporic acid A, in addition to stunting of overall growth of the plant. Some necrosis and wilting of several leaves can be observed in the plant treated with 200 ppm nodulisporic acid A, but no apparent stunting of growth. The plant appears generally healthy. Several small areas of necrosis in leaves and wilting of one leaf can be observed in the plant treated with 400 ppm nodulisporic acid A, and no apparent stunting of growth. The plant appears generally healthy. Table 3: insecticidal activity of nodulisporic acid A against Euschistus heros adults as described above

[0175] Over 80% of adults were controlled at 200 ppm four days after infestation. It was also observed that about 50% of adults were controlled already 1 day after infestation with 100 ppm of nodulisporic acid A. Indeed, affected insects are unable to properly feed on the plant, thereby preventing them from causing plant damage.

[0176] Example 4 - Stink bug field trial

[0177] The following outlines a method for conducting a field trial to evaluate the efficacy of nodulisporic acid A against Euschistus heros on soybean.

[0178] Formulations of experimental compounds may be applied as water-based solutions to a defined area of the host crop (plot) when stink bug populations (nymphs and / or adults) are present (curative control) or anticipated (preventative control). Typically, plot size may vary between 5m2 and 50m2, with 2 to 6 replications per experimental treatment. Soybean plants may be in the reproductive growth stage at the time of application. Experimental solutions may be applied using locally available pesticide application equipment, typically a backpack boom sprayer with multiple nozzles, at water volumes for the relevant crops, typically between 100-500 L / ha. Stink bug populations within plots may be naturally occurring or supplemented by collecting stink bugs from surrounding areas and releasing them evenly amongst the experimental plots. These populations include adults and various nymph stages. Insect counts per experimental plot are recorded before application and at defined periods after application, such as 1 , 3, and 7 days.

[0179] Application rates may range from 30 to 180 g ai / ha. Commercially available organophosphate, neonicotinoid, or pyrethroid insecticide, which are typically used to control infestation of Pentatomidae insects may be applied as controls following the same method.

[0180] Results of a single trial are shown in Table 4.

[0181] Table 4: Euschistus heros on soybean NA5909RR in a field trial (Holambra, Brazil)

[0182] Nodulisporic acid A was formulated as a wettable powder containing 5% of the active ingredient. Euschistus heros was tested in the open field in Holambra, Brazil, with rates of 30, 60, and 180 gai / ha. Efficacy of the Nodulisporic acid A formulation was >50% for all treatments and at all assessment timings demonstrating high levels of control. At 180gai / ha, nozzles clogged which in turn did not allow for sufficient spray coverage. Thus, results at the highest rate did not demonstrate a measurable improvement compared to the lower rates due to technical application issues but still provided sufficient control of Euschistus heros populations.

[0183] Example 5 - Stink bug laboratory trial

[0184] For this experiment, 1000 mL plastic pots were used to create microenvironments for each replication of the test. Small holes were made in the lids with a soldering iron to allow airflow, and the pots were labelled with a permanent marker according to the treatment. A 30 mL plastic container was prepared for each microenvironment and filled with water. A hole was made in the lid using a soldering iron, and dental cotton was inserted through it to enable insects to drink water by capillary action. The pots were soaked for 30 minutes in a mixture of 4.8 L of water and 200 mL of bleach, then rinsed thoroughly and allowed to dry naturally or with paper towels.

[0185] For each microenvironment, the required number of insects for the test (1 to 4 insects) was placed inside, along with 1 or 2 pods for feeding. When the test includes oviposition analysis, one male, one female, and a piece of raw cotton fabric fixed with duct tape to the side of the pot are placed in each microenvironment.

[0186] 500 mL of each required syrup was prepared in PET bottles with application rates ranging from 30-180gai / ha. The product was applied to the insects inside each pot using a portable applicator or sprayer. Insect mortality was assessed at 3 and 7 days after application. Results are summarized in Table 5. Table 5: Dichelops melacanthus in the laboratory in Holambra, Brazil

[0187] Nodulisporic acid A was formulated as a wettable powder containing 5% of the active ingredient. Dalbulus maidis was tested at 30, 60, and 180gai / ha. While control levels were low at 30gai / ha, formulated nodulisporic acid A demonstrated >60% efficacy at 60 and 180gai / ha 3 and 7 days after application.

[0188] Example 6 - Stink bug greenhouse trial

[0189] Pots were filled with a mixture consisting of one bag of substrate, one bucket of soil, and one bucket of sand. The pots were then placed in the greenhouse, arranged on benches, and labelled with permanent markers on identification plates, indicating treatments and replicates. Corn was planted and left to grow until emergence, which typically takes 15-20 days. After emergence, cages were prepared using wires and fine mesh nets.

[0190] Each cage was infested with 3 insects. Products were then prepared in PET bottles and applied directly over the cages (with mesh nets) for contact assays. Two applications were made with a 7-day spray interval. Insect mortality was evaluated 1 , 3, and 7 days after the first application (DAA) and 3 days after the second application (DAB). Results are summarized in Table 6.

[0191] Table 3: Dichelops melacanthus in the greenhouse in Holambra, Brazil

[0192] Nodulisporic acid A was formulated as a wettable powder containing 5% of the active ingredient. Dalbulus maidis was tested at 30, 60, and 180gai / ha. On the first day after application, no mortality was observed, while mortality ranged between 5-13% at later assessments.

[0193] Particular embodiments

[0194] The following are particular embodiments of the invention:

[0195] Embodiment 1 . A method of controlling or preventing infestation of or damage to a plant or propagation material thereof by an insect of the family Pentatomidae, the method comprising applying to the insect, plant, locus of the plant, or propagation material of the plant, a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof. Embodiment 2. The method of embodiment 1 , wherein the compound is nodulisporic acid A or an agrochemically acceptable salt thereof.

[0196] Embodiment 3. The method of embodiment 1 or 2, wherein the insect is an insect of a genus selected from: Chinavia, Chlorochroa, Dichelops, Edessa, Euschistus, Halyomorpha, Nezara, and Piezodorus Embodiment 4. The method of any one of embodiments 1 to 3, wherein the insect is an insect selected from: Chinavia hilaris, Chinavia impicticornis, Chlorochroa sayi, Dichelops furcatus, Dichelops melacanthus, Edessa meditabunda, Euschistus heros, Euschistus impictiventris, Halyomorpha halys, Nezara viridula, and Piezodorus guildinii.

[0197] Embodiment 5. The method of any one of embodiments 1 to 4, wherein the insect is Euschistus heros. Embodiment s. The method of any one of embodiments 1 to 5, wherein the method comprises applying a fermentation broth, fermentation product, or agricultural composition comprising the compound as defined in embodiment 1 or 2 to the insect, plant, locus of the plant, or propagation material of the plant, optionally wherein the broth, product, or composition further comprises an agriculturally acceptable adjuvant, carrier, surfactant, and / or diluent

[0198] Embodiment 7. The method of any one of embodiments 1 to 6, wherein the compound as defined in embodiment 1 or 2 or the broth, product, or composition as defined in embodiment 6 is applied by means of foliar application, soil application, in furrow application, or drench application

[0199] Embodiment 8. The method of any one of embodiments 1 to 7, wherein the compound, broth, product, or composition is applied at a rate of at least 5 g active ingredient (ai) / ha and / or at a rate of at most 5000 g ai / ha.

[0200] Embodiment 9. The method of any one of embodiments 1 to 8, wherein the compound, broth, product, or composition is applied at a rate of from 20 to 2500 g ai / ha.

[0201] Embodiment 10. The method of any one of embodiments 1 to 9, wherein the plant is a plant selected from: grains, fruits and tree nuts, vegetables, field crops, oil seed crops, fibre crops, forage crops, forest plants, horticulture crops, floriculture, greenhouse and nursery plants, culinary herbs and spices, and medicinal herbs.

[0202] Embodiment 11. The method of any one of embodiments 1 to 10, wherein the plant is selected from: soybean (Glycine max (L.) Merr.), corn (Zea mays L.), cotton (Gossypium spp.) and wheat (Triticum aestivum L.).

[0203] Embodiment 12. The method of any one of embodiments 1 to 11 , wherein the plant is a genetically modified or transgenic plant.

[0204] Embodiment 13. The method of embodiment 12, wherein the genetically modified or transgenic plant expresses an insecticidal protein.

[0205] Embodiment 14. Use of the compound as defined in embodiment 1 or 2 for controlling or preventing infestation of Euschistus heros on soybean, corn, cotton, or wheat, or a propagation material thereof according to the method of any one of embodiments 1 to 13, optionally wherein the soybean, corn, cotton, or wheat is genetically modified.

[0206] Embodiment 15. Use of the compound as defined in embodiment 1 or 2 or the fermentation broth or fermentation product as defined in embodiment 6 in the manufacture of a composition for the control of an insect of the family Pentatomidae.

Claims

Claims1 . A method of controlling or preventing infestation of or damage to a plant or propagation material thereof by an insect of the family Pentatomidae, the method comprising applying to the insect, plant, locus of the plant, or propagation material of the plant, a compound selected from: nodulisporic acid A, nodulisporic acid A1 , nodulisporic acid A2, and nodulisporic acid A4; or an agrochemically acceptable salt thereof.

2. The method according to claim 1 , wherein the compound is nodulisporic acid A or an agrochemically acceptable salt thereof.

3. The method according to claim 1 or 2, wherein the insect is an insect of a genus selected from: Chinavia, Chlorochroa, Dichelops, Edessa, Euschistus, Halyomorpha, Nezara, and Piezodorus.

4. The method according to any one of claims 1 to 3, wherein the insect is an insect selected from: Chinavia hilaris, Chinavia impicticornis, Chlorochroa sayi, Dichelops furcatus, Dichelops melacanthus, Edessa meditabunda, Euschistus heros, Euschistus impictiventris, Halyomorpha halys, Nezara viridula, and Piezodorus guildinii.

5. The method according to any one of claims 1 to 4, wherein the insect is Euschistus heros.

6. The method according to any one of claims 1 to 5, wherein the method comprises applying a fermentation broth, fermentation product, or agricultural composition comprising the compound as defined in claim 1 or 2 to the insect, plant, locus of the plant, or propagation material of the plant, optionally wherein the broth, product, or composition further comprises an agriculturally acceptable adjuvant, carrier, surfactant, and / or diluent.

7. The method according to any one of claims 1 to 6, wherein the compound as defined in claim 1 or 2 or the broth, product, or composition as defined in claim 6 is applied by means of foliar application, soil application, in furrow application, or drench application.

8. The method according to any one of claims 1 to 7, wherein the compound, broth, product, or composition is applied at a rate of at least 5 g active ingredient (ai) / ha and / or at a rate of at most 5000 g ai / ha.

9. The method according to any one of claims 1 to 8, wherein the compound, broth, product, or composition is applied at a rate of from 20 to 2500 g ai / ha.

10. The method according to any one of claims 1 to 9, wherein the plant is a plant selected from: grains, fruits and tree nuts, vegetables, field crops, oil seed crops, fibre crops, forage crops, forest plants, horticulture crops, floriculture, greenhouse and nursery plants, culinary herbs and spices, and medicinal herbs.11 . The method according to any one of claims 1 to 10, wherein the plant is selected from: soybean (Glycine max (L.) Merr.), corn (Zea mays L.), cotton (Gossypium spp.), and wheat (Triticum aestivum L.).

12. The method according to any one of claims 1 to 11 , wherein the plant is a genetically modified or transgenic plant.

13. The method according to claim 12, wherein the genetically modified or transgenic plant expresses an insecticidal protein.

14. Use of the compound as defined in claim 1 or 2 for controlling or preventing infestation of Euschistus heros on soybean, corn, cotton, or wheat, or a propagation material thereof according to the method of any one of claims 1 to 13, optionally wherein the soybean, corn, cotton, or wheat is genetically modified.

15. Use of the compound as defined in claim 1 or 2 or the fermentation broth or fermentation product as defined in claim 6 in the manufacture of a composition for the control of an insect of the family Pentatomidae, or of an insect of a genus selected from: Chinavia, Chlorochroa, Dichelops, Edessa, Euschistus, Halyomorpha, Nezara, and Piezodorus.

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