<smallcaps / >? ? ?delottococcus aberiae? ? ? ? ?attractant composition of thespecies, uses thereof, methods for detection, monitoring and / or control of the pest

Abstract

The present invention relates to the use of compound of (3,4,5,5-tetramethylcyclopent-2-en-1-yl) methyl acetate, to a composition comprising at least said compound and its use for controlling and / or monitoring populations of insects of the Delottococcus aberiae species; preferably as an attractant, more preferably as a sex pheromone composition for insects of said species. The present invention relates also to a device comprising said compound or said composition and to a method of control and / or monitoring of the populations of insects of the species Delottococcus aberiae.

Description

[0001] ATTRACTANT COMPOSITION OF THE DELOTTOCOCCUS ABERIAE SPECIES, USES THEREOF, METHODS FOR DETECTION, MONITORING AND / OR CONTROL OF THE PEST.

[0002] FIELD OF INVENTION

[0003] The present invention falls within the technical field of agricultural pest control, in particular it relates to the use of compounds and compositions for controlling and / or monitoring populations of insects of the Delottococcus abericie species; preferably as an attractant for, more preferably as a sex pheromone for insects of said species.

[0004] PRIOR ART

[0005] Delottococcus aberiae (De Lotto) (Hemiptera: Pseudococcidae) is a pest recently introduced in the crops of the Mediterranean area. The first samples of Delottococcus aberiae were detected in 2009 in the town of Benifairo de les Valls (Valencia), causing considerable deformations in fruits of sweet orange and clementine that entail their complete commercial depreciation (Beltra, A.; Garcia Mari, F; Soto, A. 2013. El cotonet de les Valls, Delottococcus aberiae, nueva plaga de los citricos. Levante Agricola 419, 348-352). Furthermore, like the rest of pseudococcids, it feeds on sap and produces honeydew that causes the proliferation of saprophytic fungi, as well as a decrease in the photosynthetic rate and the loss of plant vigor.

[0006] This species is native to sub-Saharan Africa and its presence had only been described in some countries of central and southern Africa: Kenya, Mozambique, Swaziland, South Africa, Tanzania and Zimbabwe (as described in, Garcia Morales M, Denno BD, Miller DR, Miller GL, Ben-Dov Y, Hardy NB. 2016. ScaleNet: A literature-based model of scale insect biology and systematics. Database, doi: 10.1093 / database / bavl l8. http: / / scalenet.info), therefore its introduction into Spain had to be related to the importation of material plant from one of these countries.

[0007] Delottococcus aberiae is a polyphagous insect cited in tropical as well as subtropical and temperate crops, such as coffee, guava or olive (De Lotto, G. 1961. New Pseudococcidae (Homoptera: Coccoidea) from Africa. Bull. Br. Mus. (Nat. Hist.) Entomol. 10: 211-238), but it had never been described before as damaging for citrus fruits. It is due to this recent invasion that, unfortunately, there are no specific means for fighting it, being this a new pest for the cultivation of citrus fruits worldwide. In addition to the commercial depreciation of the affected fruit, its presence can cause serious quarantine problems for citrus exports as it is a new pest for citrus fruits in Europe, hitherto restricted to date to Africa. Currently, the active substances that are recommended against pseudococcids are mineral oil, spirotetramat, acetamiprid and sulfoxaflor (IVIA - Institute Valenciano de Investigaciones Agrarias. 2022. Gestion Integrada de Plagas y Enfermedades en Citricos, http: / / gipcitricos.ivia.es), since the substances chlorpyrifos and methyl-chlorpyrifos, the most active against Delottococcus abericie were withdrawn by the European Commission on February 16, 2020 (modification of Directive 91 / 414 / EEC). Since then, the available tools are scarce and of questionable effectiveness, thus alternative tools are needed to manage this pest. Regarding the biological control, Delottococcus abericie has been shown to have a strong defensive response and is capable of encapsulating the eggs of several generalist parasitoids of pseudococcids, such as Acerophagus angustifrons (Gahan), Anagyrus sp. near pseudoccoci (Girault), and Leptomastix algirica Trjapitzin (Hymenoptera: Encyrtidae) (Tena, A., J. Garcia-Bellon, and A. Urbaneja. 2017. Native and naturalized mealybug parasitoids fail to control the new citrus mealybug pest Delottococcus aberiae. J. Pest Sci. 90: 659-667). Considerable efforts are being made to import and release parasitoids from the area of origin, but in the meantime, the only strategy that could be used in the short term is to advance the action of Cryptolaemus montrouzieri by releasing this predatory coccinellid.

[0008] Detection and monitoring of populations of pseudococcids is key to the improvement of its control both in agricultural and ornamental ecosystems, but sometimes, consist of laborious visual inspection of plant material in search of live forms and the count of all stages of the insect. Alternatively, corrugated cardboard traps for seasonal sampling of live forms and / or sticky traps can be used to track the flight of males (Martinez-Blay, V., Perez-Rodriguez, J., Tena, A., & Soto, A. (2018). Density and phenology of the invasive mealybug Delottococcus aberiae on citrus: implications for integrated pest management. Journal of Pest Science, 91(2), 625-637). This last technique requires the availability of species-specific attractants, such as sex pheromones.

[0009] On the other hand, the use of sex pheromones in commercial treatments for the control of Coccoid pests (Aonidiella aurantii Maskell (Scalebur®, Ecologia y Protection Agricola, Valencia) and Pianococcus ficus Signoret (CheckMate® VMB-XL, Suterra, Bend, USA)) through the use of techniques such as mating disruption, where the male is not able to find the female through the action of different mechanisms causing the mating interruption, is known.

[0010] Currently, the existence of a treatment through the use of the attractant compound for the species Delottococcus aberiae, 4,5,5-trimethyl-3-methylenecyclopent-l-en-l-yl)methyl acetate, is known, as described in W02020099705A1, and has proven to be effective in the control and specific monitoring of the pest, and particularly in methods based on attraction and affectation.

[0011] There are related compounds that are defense pheromones of other species as is the case of alpha trans necrodol in the case of the carrion beetle (Roach, B., Eisner, T., & Meinwald, J. (1990). Defense mechanisms of arthropods. 83. Alpha-and beta-Necrodol, novel terpenes from a carrion beetle (Necrodes surinamensis, Silphidae, Coleoptera). The Journal of Organic Chemistry, 55(13), 4047-4051), or sex pheromones in the case of alpha trans necrodol isobutyrate or gamma trans necrodol isobutyrate for the species Pseudococcus maritimus or Nipaecoccus viridis respectively (Figadere, B.A., McElfresh, J.S., Borchardt, D., Daane, K.M., Bentley, W., & Millar, J. G. 2007. Trans-a-Necrodyl isobutyrate, the sex pheromone of the grape mealybug, Pseudococcus maritimus. Tetrahedron Letters, 48(48), 8434-8437; Levi-Zada, A., Steiner, S., Fefer, D., & Kaspi, R. 2019. Identification of the sex pheromone of the spherical mealybug Nipaecoccus viridis. Journal of chemical ecology, 45(5), 455-463; WO2021064719 - Compositions and methods for mealybug monitoring and control).

[0012] It is worth noting that the attraction of insects to sex pheromones can be particularly sensitive to the composition of the pheromonal complex, being the male insects able to respond to the separate compounds as well as to the composition of the pheromonal blend with different intensity. Additionally, although the attraction of any of these components is effective separately, it could as well generate a natural bias towards those individuals who respond best to some of the other components of the complex (Carlos, F.J., Cocco, A., Lucchi, A., Mendel, Z., Suma, P., Vacas, S., Mansour, R. and Navarro-Llopis, V. 2022. Scientific and technological developments in mating disruption of scale insects. Entomology Generalis, 42(2), 251-273). Thus, it may be of importance to know and apply the complete pheromonal blend released by the female to prevent the appearance of resistance to this type of control methods.

[0013] Therefore, the improvement in the methods of treatment and control of this pest, as well as the identification of new compounds, methods and devices effective in the treatment of said species, which at the same time can prevent the appearance of resistance, are necessary. Additionally, the identification and development of new attractants that can be additionally obtained from natural sources, provide a clear techno-economic and environmental advantage.

[0014] BRIEF DESCRIPTION OF THE INVENTION

[0015] Surprisingly, a new minor compound present in the pheromonal blend emitted by Delottococcus aberiae has been reliably identified.

[0016] The present invention solves the problems described in the state of the art since it provides a natural compound of low toxicity, present in the pheromonal blend, which is an attractant and is effective for controlling and / or monitoring the species Delottococcus aberiae and that, additionally, can be obtained naturally.

[0017] Thus, the present invention relates to a compound of formula I (also referred to as the compound of the present invention):

[0018] The present invention refers to (3,4,5,5-tetramethylcyclopent-2-en-l-yl)methyl acetate as compound of formula I. The compound of formula I is also known by the name of alpha-necrodil acetate, being a mixture of diastereoisomers formed by compounds la, lb, Ic and Id:

[0019] The first aspect of the invention refers to the use of a compound of formula I as defined above for controlling and / or monitoring populations of insects of the Delottococcus abericie species, preferably as an attractant for, and more preferably as a sex pheromone for insects of the Delottococcus abericie species.

[0020] In a second aspect, the present invention refers to the use of an attractant composition comprising a compound of formula I according to first aspect of the invention and, optionally, further comprising the compound of formula II: for controlling and / or monitoring populations of insects of the Delottococcus aberiae species, preferably as an attractant for, and more preferably as a sex pheromone for insects of the Delottococcus aberiae species.

[0021] In the present invention, the compound of formula la refers to (( lR,4R)-3, 4,5,5- tetramethylcyclopent-2-en-l-yl)methyl acetate. The compound of formula la is also known by the name of alpha-trans-necrodyl acetate and has the following CAS number: 709026-14-2. Compound II refers to (4,5,5-trimethyl-3-methylenecyclopent-l-en-l-yl)methyl acetate.

[0022] A third aspect of the invention refers to the use of a plant extract comprising the compound of formula I as defined above for controlling and / or monitoring populations of insects of the Delottococcus aberiae species; preferably as an attractant for, more preferably as a sex pheromone for insects of said species. A fourth aspect of the invention refers to a composition (also referred to as the composition of the present invention) for controlling and / or monitoring populations of insects of the Delottococcus aberiae species, preferably as an attractant for, more preferably as a sex pheromone for insects of said species, comprising a compound of formula I as defined in the first aspect of the invention, said composition being further characterized in that it is formulated as a tablet, capsule, powder, granule, paste, liquid, gel, emulsion, microencapsulated solution, dispersion or aerosol.

[0023] A fifth aspect of the invention refers to a combination (also referred to as the combination of the present invention) of a compound of formula I as defined above, and a compound of formula (II): for controlling and / or monitoring populations of insects of the Delottococcus aberiae species; preferably as an attractant for, more preferably as a sex pheromone for insects of said species. Said combination shows good activity and efficacy against insects of the species Delottococcus aberiae. Advantageously and unexpectedly, said combination has a synergistic effect against insects of the species Delottococcus aberiae. Furthermore, the combination of the fifth aspect has the advantage that both compounds are compatible and do not interact, can be easily formulated and applied directly to an agricultural crop as attractants of insects of the species Delottococcus aberiae.

[0024] A sixth aspect of the invention refers to a device for controlling and / or monitoring populations of insects of the Delottococcus aberiae species; preferably for attracting insects of said species, comprising the composition of the fourth aspect or the combination of the fifth aspect. In a preferred embodiment, the device of the present invention comprises a trap or is a trap device.

[0025] A seventh aspect of the invention refers to a method for controlling and / or monitoring populations of Delottococcus aberiae (also referred to as the method of the present invention) comprising the use of the compound of formula I or la of the present invention or the combination of the compound I, or la, and the compound of formula II or the composition of the present invention, wherein the method comprises at least the following steps: i) providing a device according to the sixth aspect of the present invention and placing it in an agricultural crop; ii) leaving the device from step i) in an agricultural crop for at least 3 hours to release at least the substance of formula I or la or the combination of compounds of formula I, or la, and II.

[0026] Preferably, the method of the present invention may comprise the use of the device of the present invention. In a preferred embodiment, the method of control and / or monitoring of the present invention is performed by attracting male individuals belonging to the species of Delottococcus aberiae and / or through mating disruption of male individuals belonging to the species of Delottococcus aberiae and / or through disruption, attraction, affectation and / or death of male individuals belonging to the Delottococcus aberiae species.

[0027] Lastly, the present invention refers to the use of the composition or combination of the present invention, or use of the device according to the sixth aspect of the invention for the control and / or monitoring of populations of insects of the Delottococcus aberiae species; preferably for attracting insects of said species.

[0028] DETAILED DESCRIPTION OF THE INVENTION

[0029] The present invention provides a specific and effective attractant compound for insects of the Delottococcus aberiae species, said compound having low toxicity.

[0030] Thus, in a first aspect, the present invention refers to the use of a compound of formula I (also referred to as compound of the present invention): for controlling and / or monitoring populations of insects of the Delottococcus aberiae species. In a particular embodiment, the first aspect refers to the use of the compound of formula I as an attractant, preferably as a sex pheromone, for insects of the Delottococcus aberiae species.

[0031] In the present invention, the compound of formula I is referred to as (3, 4,5,5- tetramethylcyclopent-2-en-l-yl)methyl acetate. The compound of formula I is also known by the name of alpha-necrodyl acetate and is a mixture of diastereoisomers of formulas la, lb, Ic, Id: la lb Ic Id

[0032] In a preferred embodiment of the first aspect of the invention, the compound of formula I is a mixture of diastereoisomers of formulas la, lb, Ic, Id; more preferably said compound is compound la. In the present invention the compound of formula la or ((lR,4R)-3, 4,5,5- tetramethylcyclopent-2-en-l-yl)methyl acetate with CAS number 709026-14-2, has been identified as the sex pheromone of Delottococcus aberiae, also naturally present in plant extracts, more preferably from Lavender stoechas subsp. Luisieri.

[0033] As stated above, in a second aspect, the present invention refers to the use of a composition comprising a compound of formula I as defined in the first aspect of the invention and, optionally, further comprising the compound of formula II: for controlling and / or monitoring populations of insects of the Delottococcus aberiae species, preferably as an attractant for, and more preferably as a sex pheromone for insects of the Delottococcus aberiae species.

[0034] In an embodiment, the second aspect of the present invention refers to the use of an attractant composition which comprises: i) a compound of formula I, preferably a mixture of diastereoisomers of formulas la, lb, Ic, Id, more preferably compound la, and ii) at least one chemically acceptable excipient.

[0035] In another embodiment, the second aspect of the present invention refers to the use of an attractant composition which comprises: i) a compound of formula I, preferably a mixture of diastereoisomers of formulas la, lb, Ic, Id, more preferably compound la; ii) the compound of formula II, and iii) at least one chemically acceptable excipient. In a particular embodiment, the compounds I and II are used in a 50:50 weight ratio. In another particular embodiment, compounds I and II are used in a weight ratio different from 50:50, preferably the weight ratio between I and II is comprised between 90: 10 and 1:99, more preferably between 75:25 and 5:95, even more preferably between 60:40 and 10:90. Specific weight ratios between I and II can be 99: 1, 95:5, 90: 10, 85: 15, 80:20, 75:25, 70:30, 60:40, 40:60, 30:70, 25:75, 20:80, 15:85, 10:90, 5:95 or 1:99. In a preferred embodiment, the weight ratio between I and II is about 10:90.

[0036] A third aspect of the invention refers to the use of a plant extract comprising a compound of formula I as defined above for controlling and / or monitoring populations of insects of the Delottococcus aberiae species, preferably as an attractant for, and more preferably as a sex pheromone for insects of the Delottococcus aberiae species.

[0037] In a preferred embodiment of the third aspect, the compound of formula I is compound la. In a particular embodiment of the third aspect, the compound la is comprised in a plant extract obtained by Lavandula stoechas, L. luisieri (rozeira), L. luisieri x necrodolis, L. luisieri x L. pedunculata, L. luisieri x L. pedunculata subspecies sampaioana, L. luisieri x L. pedunculata vd lusitanica,' preferably from a plant extract of Lavender Stoechas subsp. Luisieri, more preferably said plant extract comprises an extract of Lavanda stoechas sub. Luisieri. A fourth aspect of the invention refers to a composition for controlling and / or monitoring populations of insects of the Delottococcus aberiae species, preferably an attractant composition, more preferably a sex pheromone composition for insects of said species, comprising a compound of formula I as defined in the first aspect of the invention, said composition being further characterized in that it is formulated as a tablet, capsule, powder, granule, paste, liquid, gel, emulsion, microencapsulated solution, dispersion or aerosol. In a preferred embodiment, the composition of the invention is formulated as a tablet, capsule, powder, granule, paste, gel, emulsion, microencapsulated solution, dispersion or aerosol. In a particular embodiment of the fourth aspect, the compound of formula I is a mixture of diastereoisomers of formulas la, lb, Ic, Id; preferably, the compound is la.

[0038] In a particular embodiment, the fourth aspect of the invention refers to a composition comprising the compound of the present invention and at least one chemically acceptable excipient.

[0039] In a preferred embodiment of the fourth aspect, the composition of the present invention, comprises an amount of the compound of the present invention between 0.001 to 1000 mg. Preferably, the effective amount is comprised in a range between 0.001 to 200 mg.

[0040] The amount of compound may vary depending on the type of area, zone, crop, technique to be used or object to be treated, as well as the environmental conditions and the number of days of attraction required.

[0041] In the context of the present invention, the term “chemically acceptable excipient” refers to inert components that have no pharmacological and / or active effect against insects of the species Delottococcus aberiae, and are incorporated into the composition to perform at least one specific function. Preferably, the chemically acceptable excipient is selected from the list consisting of, antioxidants, diluents, dyes, disintegrating, lubricants, binders, UV radiation protectors, and mixtures thereof.

[0042] In the context of the present invention, the term “antioxidant” refers to any substance capable of delaying or preventing the oxidation of one or more components of the composition of the present invention. Preferably, the antioxidant agent of the composition of the present invention is selected from ascorbic acid, erythorbic acid, sodium ascorbate, calcium ascorbate, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), sulfur dioxide, sodium erythorbate, ascorbyl stearate, propyl gallate, octyl gallate, dodecyl gallate, sodium hydrosulfite, lecticin, ascorbyl palmitate, tert-butylhydroquinone (TBHQ), natural and / or synthetic tocopherols, and any combination of the above antioxidants. In a preferred embodiment, the antioxidant is comprised in the attractant composition of the present invention in a ratio by weight (w / w) between 1 : 1000 to 1 :20 based on the weight content of (4, 5,5 -trimethyl-3-methylenecy clopent- 1- en-l-yl)methyl acetate. Preferably, the antioxidant is comprised in a weight ratio between 1:500 to 1:50 based on the content by weight of (4,5,5-trimethyl-3-methylenecyclopent-l-en-l- yl)methyl acetate, more preferably, in a weight ratio between 1 :300 up to 1 :80 with respect to the content by weight of (4,5,5-trimethyl-3-methylenecyclopent-l-en-l-yl)methyl acetate.

[0043] In the context of the present invention, the term “UV radiation protector” refers to any compound capable of protecting and preserving one or more components of the composition of the present invention from solar degradation. Preferably, the UV radiation protectors of the present invention refer to derivatives of PABA, salicylates, cinnamates, benzophenones, benzimidazoles, anthralinates, terpene derivatives, inorganic oxides and any combination thereof. Preferably, they refer to 4-aminobenzoic acid, 4-hydroxybenzophenone, 2-ethylhexyl salicylate, 2-ethylhexyl trans-4-methoxycinnamate, ethylhexyl 2-cyano-3,3-diphenylacrylate, titanium oxide and / or zinc oxide and any combination thereof. In a preferred embodiment, in the attractant composition of the present invention, the UV radiation protector is comprised in a weight ratio from 1 :200 to 1 :20 with respect to the content by weight of (4,5,5-trimethyl-3-methylenecyclopent-l-en-l-yl)methyl acetate. Preferably, the UV radiation protector is comprised in a weight ratio between 1: 100 to 1:30 with respect to the content by weight of (4,5,5-trimethyl-3-methylenecyclopent-l-en-l-yl) methyl acetate; more preferably, in a weight ratio between 1:70 to 1:50 with respect to the content by weight of (4,5,5-trimethyl-3-methylenecyclopent-l-en-l-yl)methyl acetate.

[0044] In a preferred embodiment of the fourth aspect, the composition may contain other active substances against insects of the species Delottococcus aberiae or against other insects. Preferably, the composition of the present invention may contain other active substances selected from the list consisting of pheromones, kairomones, and insect control agents.

[0045] In the context of the present invention, the term “pheromone” is any substance secreted by an animal that elicits a specific reaction or behavior in a member of the same species. Preferably, the pheromone is a sex pheromone. In the context of the present invention, the term “sex pheromone” is that substance secreted by one of the genera of the species causing an attraction and mating response in the other. In the context of the present invention, the term “kairomone” refers to any substance secreted by an organism and involved in the communication between individuals of different species, benefiting the organism receiving it.

[0046] In the context of the present invention, the term “insect control agent” refers to a chemical substance that causes the death of the insect. Preferably, the insect control agent is an insecticide, more preferably the insecticide is select from the list consisting of organochlorines, organophosphates, carbamates, pyrethroids, pyrethrins, neonicotinoids, tetramic acids, biorationals, natural extracts with biocidal activity and combination thereof.

[0047] In a more preferred embodiment of the fourth aspect, the composition of the invention further comprises the compound of formula II:

[0048] In a particular embodiment, the compounds I and II are used in a 50:50 weight ratio. In another particular embodiment, compounds I and II are used in a weight ratio different from 50:50, preferably the weight ratio between I and II is comprised between 90: 10 and 1 :99, more preferably between 75:25 and 5:95, even more preferably between 60:40 and 10:90. Specific weight ratios between I and II can be 99: 1, 95:5, 90: 10, 85: 15, 80:20, 75:25, 70:30, 60:40, 40:60, 30:70, 25:75, 20:80, 15:85, 10:90, 5:95 or 1:99. In a preferred embodiment, the weight ratio between I and II is about 10:90.

[0049] In a preferred embodiment of the fourth aspect of the invention, the composition of the present invention further comprises a carrier. Thus, in an embodiment, the composition of the fourth aspect further comprises a carrier and is formulated as a tablet, capsule, powder, granule, paste, liquid, gel, emulsion, microencapsulated solution, dispersion or aerosol; preferably further comprises a carrier and is formulated as a tablet, capsule, powder, granule, paste, gel, emulsion, microencapsulated solution, dispersion or aerosol. Preferably, the composition of the present invention is deposited, absorbed, adsorbed and / or physically or chemically coated on the carrier. More preferably, at least the compound(s) of the present invention comprised in said composition is (are) deposited, absorbed, adsorbed, or physically or chemically coated on the carrier.

[0050] In the context of the present invention, the term “carrier” refers to a substrate or matrix capable of carrying or containing the compound of the present invention or the composition of the present invention.

[0051] Preferably the carrier can be a wax, preferably paraffin, or the carrier is selected from the list consisting of a matrix which is selected from the list consisting of a polymeric, wooden, ceramic, metallic and leather matrix; preferably wherein the polymeric matrix is woven or non-woven and comprises a polymer selected from the list consisting of polyamide, polyester, cotton, thermosetting polymer, resins and rubber. In a preferred embodiment, the polymer matrix is a non-woven polymer matrix comprising a polymer selected from the list consisting of polyamide, polyester, cotton, thermosetting polymer, resins and rubber.

[0052] A fifth aspect of the invention refers to a combination (also referred to as the combination of the present invention) of a compound of formula I as defined above, and a compound of formula (II): for the control and / or monitoring of populations of insects of the Delottococcus aberiae species; preferably as an attractant, more preferably as a sex pheromone for insects of said species.

[0053] In a particular embodiment, the compound of formula I is a mixture of diastereoisomers of formulas la, lb, Ic and Id as shown above.

[0054] In a preferred embodiment, the combination of the fifth aspect of the invention comprises, preferably consists of, the compounds of formula la (CAS: 709026-14-2) and II:

[0055] In a particular embodiment, the compounds I and II are used in a 50:50 weight ratio. In another particular embodiment, compounds I and II are used in a weight ratio different from 50:50, preferably the weight ratio between I and II is comprised between 90: 10 and 1 :99, more preferably between 75:25 and 5:95, even more preferably between 60:40 and 10:90. Specific weight ratios between I and II can be 99: 1, 95:5, 90: 10, 85: 15, 80:20, 75:25, 70:30, 60:40, 40:60, 30:70, 25:75, 20:80, 15:85, 10:90, 5:95 or 1:99. In a preferred embodiment, the weight ratio between I and II is about 10:90.

[0056] Said combination shows good activity and efficacy against insects of the species Delottococcus aberiae. Advantageously and unexpectedly, said combination presents a synergistic effect against insects of the species Delottococcus aberiae.

[0057] Furthermore, the combination of the fifth aspect has the advantage that both compounds are compatible and do not interact with each other, can be easily formulated and applied directly to an agricultural crop as an attractant for insects of the species Delottococcus aberiae.

[0058] The combination of the fifth aspect may be comprised in a composition. Said composition can have all the characteristics and embodiments of the composition of the first aspect.

[0059] The sixth aspect of the invention refers to a device for controlling and / or monitoring populations of insects of the Delottococcus aberiae species; preferably for attracting insects of said species, comprising the composition of the fourth aspect or the combination of the fifth aspect. In a preferred embodiment, the device of the present invention comprises a trap. In the context of the present invention, the term “trap” refers to any artifice or to a device that catches insects and / or retains and / or affects them. In a preferred embodiment, the device comprises a toxic or pathogenic substance for the target insect.

[0060] In a preferred embodiment, the device comprises a trap that contains a surface comprising an adhesive.

[0061] In a seventh aspect, the present invention refers to a method for the control and / or monitoring of populations of Delottococcus abericie (also referred to as the method of the present invention) comprising the use of the compound of formula I or la or the combination of the compound of formula I or la with the compound of formula II or the composition of the present invention wherein the method comprises at least the following steps: i) providing a device according to the sixth aspect of the present invention and placing it in an agricultural crop; ii) leaving the device from step i) in an agricultural crop for at least 3 hours to release at least the substance of formula I or la or the combination of the compounds of formula I, or la, with II.

[0062] Preferably, the method of the present invention comprises the use of the device of the present invention.

[0063] In a preferred embodiment, the method of control and / or monitoring of populations of Delottococcus abericie of the present invention is performed by attracting male individuals belonging to the Delottococcus aberiae species.

[0064] In another preferred embodiment, the method of control and / or monitoring of populations of Delottococcus aberiae is carried out by mating disruption of male individuals belonging to the species Delottococcus aberiae.

[0065] In another particular embodiment, the method of control and / or monitoring of populations of Delottococcus aberiae is carried out through the death and / or affectation of male individuals belonging to the Delottococcus aberiae species.

[0066] Lastly, the present invention refers to the use of the composition or combination of the present invention, or use of the device according to the sixth aspect of the invention for the control and / or monitoring of populations of insects of the Delottococcus aberiae species; preferably for attracting insects of said species.

[0067] Brief description of figures

[0068] Figure 1: Figure 1 represents the detection by gas chromatography of (( lR,4R)-3, 4,5,5- tetramethylcyclopent-2-en-l-yl)methyl acetate (TN A) in: (A) sample corresponding to the isolated and purified TNA (19.31 minutes); (B) sample of volatiles of virgin female individuals of Delottococcus aberiae reared in the laboratory, where the TNA compound is also detected at 19.31 min; and (C) sample of volatiles from females individuals of Delottococcus aberiae after mating, where the TNA compound is no longer detected.

[0069] It is observed that the peak with a retention time of 19.31 min detected in the samples of virgin females (B) does not appear in samples of mated females (C), and it matches with the isolated sample of a plant extract of Lavender stoechas subsp. Luisieri of (( lR,4R)-3, 4,5,5- tetramethylcyclopent-2-en-l-yl)methyl acetate (A).

[0070] Examples

[0071] Example 1: Detection of ((lR,4R)-3.4.5.5-tetramethylcvclopent-2-en-l-yl)methyl acetate in samples from virgin females of Delottococcus aberiae using volatile collection techniques.

[0072] For the collection of volatiles emitted by Delottococcus aberiae females in different mating status, individuals from the laboratory colony maintained on organically grown lemon trees at the Centro de Ecologia Quimica Agricola (Universitat Politecnica de Valencia, Valencia) were used. The rearing is kept in a room under controlled conditions, at 23 ± 2°C and with 60-70% relative humidity.

[0073] The sampling of the volatiles emitted by the insects was carried out by means of the aeration of individuals and collection of effluvia in glass cartridges filled with the adsorbent matrix Porapak- Q. Groups of 200-300 individuals were placed on the rearing substrate in 5L glass containers, through which a filtered air flow of 0.4 l / min was passed. Every 7-8 days, the adsorbent material was washed with 20 ml of pentane to elute the captured substances. The eluents were analyzed by gas chromatography coupled to mass spectrometry (GC-MS). The chromatography analysis was performed on a Clarus 600 GC-MS equipment (PerkinElmer Inc.), equipped with a ZB-5MS capillary column (30 m x 0.25 mm i.d. x 0.25 pm; Phenomenex Inc.) and the following temperature program: 40 °C for 2 min; 5 °C / min up to 180 °C and then increase to 280 °C at 10 °C / min, holding at 280 °C for 1 min. Helium was used as carrier gas with a flow of 1 ml / min. The detection was made in electron impact mode (70 eV) and the temperature of the ionization source and the transfer line was 200 °C and 250 °C, respectively. Once detected a characteristic peak of the samples of virgin females, this was isolated from the eluted mixture by the following procedure: (1) gravity chromatography of the total extract with pentane: diethyl ether mixtures (100:0, 95:5, 80:20, 0: 100) as eluents; (2) positioning of the peak in the corresponding fraction by means of GC-MS; (3) isolation of the substance in the fraction by preparative GC. Preparative gas chromatography was carried out using a Clarus 500 GC (Perkin Elmer) equipped with a flame ionization detector and a TRB-1 capillary column (30 m x 0.53 mm, i.d. x 0.5pm; Teknokroma Analitica SA, Sant Cugat del Valles, Barcelona, Spain). The oven temperature was programmed at 40 °C for 2 min, then rising at 3 °C / min up to 100 °C and at 30 °C / min up to 280 °C, which is finally maintained for 12 min. After isolation, the structural elucidation was performed with the data provided by the GC-MS spectrum and the nuclear magnetic resonance (NMR) spectrum in a 600 MHz equipment (Bruker). Finally, the spectra of the natural substance were compared with those of a sample synthesized by Ecologia y Protection Agricola SL (Carlet, Valencia).

[0074] Chromatographic analysis revealed a peak that appeared exclusively in the samples of volatiles emitted by virgin females and not by those of females that copulated or by immature individuals, as it can be seen in Figure 1. This peak corresponded to ((lR,4R)-3,4,5,5-tetramethylcyclopent- 2-en-l-yl)methyl acetate, identified by spectrometry data, and subsequently confirmed by comparison with a sample isolated and purified in laboratory as described in example 2.

[0075] Example 2: Preparation of ((lR.4R)-3.4.5.5-tetramethylcvclopent-2-en-l-yl)methyl acetate.

[0076] Compound I was isolated from extracts of Lavender Stoechas sub. Luisieri, from specimens grown in greenhouses at the facilities of the Universitat Politecnica de Valencia starting from seeds of the species purchased from the company Semillas Cantueso SL.

[0077] To do so, 100 grams of fresh plant material (stems, leaves and flowers) were cut and extracted with 500 ml of toluene by using a Soxhlet for 12 h. The toluene extract was concentrated by evaporation and the obtained residue (4.3 g) was subjected to chromatography by gravity column filled with silica gel (60 x 3.5 cm, 80 g, hexane: diethyl ether 99: 1 as eluant).

[0078] The obtained fractions were analyzed by gas chromatography, using a chromatograph coupled to a Claras 600 GC-MS mass spectrometry apparatus (PerkinElmer Inc., Waltham, MA) equipped with a ZB-5MS capillary column (30 m x 0.25 mm i.d. x 0.25 pm; Phenomenex Inc., Torrance, CA). Fractions where the presence of compound I was identified in a concentration greater than 90 %, as measured by integration of the peak area, were concentrated again and the crude obtained (ca. 250 mg) was further purified via silica gel-filled gravity column chromatography (60 x 3.5 cm, 60 g, hexane: diethyl ether 99: 1 as eluant). The obtained fractions were analyzed with a chromatograph coupled to a mass spectrometry apparatus Claras 600 GC-MS (PerkinElmer Inc., Waltham, MA) equipped with a capillary column ZB-5MS (30 m x 0.25 mm i.d. x 0.25 pm; Phenomenex Inc., Torrance, CA), and those fractions where compound I was obtained with greater purity were re-concentrated by evaporation of the solvent thus obtaining 120 mg of ((lR,4R)-3,4,5,5- tetramethylcyclopent-2-en-l-yl)methyl acetate with a purity of 99% as determined by GC (gas chromatography), whose spectroscopic data were fully matching with those described in the literature (Garcia-Vallejo, M. C. M. I., Sanz, J., Bernabe, M., & Velasco- Negueraela, A. (1994). Necrodane (1, 2, 2, 3, 4-pentamethylcyclopentane) derivatives in Lavandula luisieri, new compounds to the plant kingdom. Phytochemistry, 36(1), 43-45). Spectroscopic data of ((lR,4R)-3,4,5,5-tetramethylcyclopent-2-en-l-yl) methyl acetate.

[0079] 5H (300 MHz, CDC13) 5.16 (1H, d, br), 4.10 (1H, dd, J 10.7, 6.5 Hz), 3.94 (1H, d, J7.4 Hz), 2.48 (1 H, d, J 1.9 Hz), 2.90 (1 H, dd, J7.3, 1.1 Hz), 2.04 (3 H, s), 1.66 (3 H, s), 0.95 (3H, s), 0.88 (3H, d, 7.5Hz).

[0080] MS (70 eV) m / z: 196 (M+, 1), 154 (2), 136 (60), 123 (50), 121 (100), 107 (23), 105 (50), 93(65), 91(52), 81(63), 79(58), 67(49).

[0081] Example 3: Biological assays for the activity of acetate ((lR.4R)-3 ,4,5,5- tetramethylcyclopent- 2-en-l-yl)methyl, under laboratory conditions.

[0082] The response of Delottococcus abericie males to ((lR,4R)-3,4,5,5-tetramethylcyclopent-2-en-l- yl)methyl acetate (TNA, compound la), was evaluated at Centro de Ecologia Quimica Agricola (UPV, Valencia), by means of an activity assay in a glass Petri dish. The tests were carried out with light and in the same rearing conditions, at 23 ± 2°C and 60-70% relative humidity.

[0083] For these tests, males from the stock colony were used, separated in Petri dishes just at the beginning of the formation of the cottony cocoon. After pupating and finally emerging from the cocoon, the insects are observed under the binocular to confirm their state before being selected for the trial.

[0084] The procedure used is described as follows: during each test, in opposite ends of the Petri dish a TNA sample and a negative control were placed (pentane solvent without activity), arranged on 1 cm2filter paper in a quantity of 5 pl. Immediately, groups of males are carefully deposited with help of a very fine brush on the test plate. Then, the behavior of individuals towards stimulus sources is observed and registered for 10 min. Once the test is finished, the insects are discarded, in such a way that each insect is exposed to olfactory stimuli only once. The data obtained was analyzed using the Chi square test (%2test, P < 0.05).

[0085] The results shown in Table 1 indicate that there is a significant attractive response of the males towards the pieces of filter paper impregnated with the TNA compound.

[0086] Table 1. Results of the biological assays of the activity of ((lR,4R)-3,4,5,5-tetramethylcyclopent- 2-en-l-yl)methyl acetate (TNA, la), under laboratory conditions. * Percentage of males of Delottococcus aberiae who chooses each of the tested substances (compound la or control), of the total number of responsive males.

[0087] ** Percentage values followed by different letters (a and b) are significantly different (%2test, P < 0.05).

[0088] Example 4a: Field attraction response assays o Delottococcus aberiae males to ((!R.4R)-3,4.5.5- tetramethylcvclopent-2-en-l-yl)methyl acetate (TNA, la)

[0089] The response of Delottococcus aberiae males to ((lR,4R)-3,4,5,5-tetramethylcyclopent-2-en-l- yl)methyl acetate (TNA, compound la) was evaluated in two field trials conducted in a citrus orchard var. Marisol, located in the town of Sagunto (Valencia).

[0090] In a first test (carried out during the month of November 2021) 3 blocks of 2 devices were installed: (A) a device with a carrier, without attractant, and a trap consisting of a white cardboard with an adhesive (95 x 150 mm), (B) a device with carrier loaded with 100 pg of TNA and a trap consisting of a white cardboard with an adhesive. Within each block the devices were located at a distance of 20 m from each other, while the distance between blocks was at least 30 m. Carriers loaded with TNA were of the septa type and were placed in the center of the trap.

[0091] The captures obtained in each of the traps were reviewed weekly and the captured individuals were taken to the laboratory to be identified and counted. Each week, intrablock trap rotation was performed to eliminate possible date bias due to the trap position.

[0092] The number of males captured per trap per day was compared by means of an analysis of the variance (ANOVA; LSD test for comparison of means, P < 0.05), previous transformation (ln(x+l)) of the data in order to homogenize the variance.

[0093] The results show that the devices loaded with TNA have a power of significantly higher attraction than traps without attractant, as shown in table 2 (trial 1). On average, 5 captures per trap per day in the field were obtained in the traps baited with TNA compared to the 0.9 captures in the controls, which means a significant difference in the analysis of variance (Table 2; F = 10.74; P = 0.008).

[0094] In a second trial (carried out during the months of June and July 2021), 2 blocks of 3 devices were installed: (A) a carrier device loaded with 100 pg of compound II and a trap consisting of a white cardboard with adhesive, (B) a device with a carrier loaded with 100 pg of ((1R, 4R)-3, 4,5,5- tetramethylcyclopent-2-en-l-yl)methyl acetate (TNA) and a trap consisting of a white cardboard with an adhesive (95 x 150 mm), and (C) a device with a carrier loaded with 200 pg of the mixture of compound II + ((lR,4R)-3,4,5,5-tetramethylcyclopent-2-en-l-yl)methyl acetate (TNA) (1 : 1) and a trap consisting of a white cardboard with an adhesive. The captures obtained in each of the traps were reviewed weekly following the protocol described above.

[0095] The results show that devices loaded with compound II +TNA have a synergistic effect for the attraction of D. aberiae males. Devices loaded only with compound II or TNA captured an average of 106.3 and 72.3 males / trap / day, respectively, while the mixture obtained an average of 229.8 males / trap / day, which is a value 5 times greater than the sum of the catches obtained by the components separately (Table 2; F = 21.94; P = 0.016).

[0096] Table 2. Results of the tests to evaluate the attraction in the field of TNA

[0097] * Capture values followed by a different letter (a and b in table 2, “Captures”) are significantly different. Statistical significance of the results (ANOVA, LSD test, P < 0.05).

[0098] Example 4b: Attraction response assays in the field to a mixture of diastereoisomers of (3,4.5.5- tetramethylcvclopent-2-en-l-yl)methyl acetate (TNAm),

[0099] The mixture of diastereoisomers (TNAm) was synthesized according to the method proposed by Schulte K. H. et al. for the synthesis of necrodol starting from 2-(2,2,3-trimethylcyclopent-3-en- I-yl)-acetaldehyde which was acetylated by standard methods (Schulte-Elte, K. H., & Pamingle, H. (1989). Conversion of Campholene to Necrodane-Type Monoterpenes. A short stereoselective synthesis of (-)-(R, R)-P-necrodol and its three stereoisomers. Helvetica chimica acta, 72(5), 1158-1163; Pamingle, H., Snowden, R.L., & Schulte-Elte, K.H. (1991). Stereoselective Conversion of Campholene to Necrodane-Type Monoterpenes. Novel Access to (-)-(R, R)-and (R, S)-a-Necrodol and the Enantiomeric y-Necrodols. Helvetica chimica acta, 74(3), 543-548). The response of Delottococcus aberiae males to the (3,4,5,5-tetramethylcyclopent-2-en-l-il) methyl acetate obtained synthetically (TNAm) was evaluated in a field trial conducted in a citrus plot var. Clemenules, located in the town of Sagunto (Valencia), in the month of May 2021.

[0100] In the test, 2 blocks of 2 devices were installed: (A) a device with a carrier, without attractant, and a trap consisting of a white cardboard with an adhesive (95 x 150 mm), (B) a device with a carrier loaded with 100 pg of TNAm and a trap consisting of a white cardboard with an adhesive. Within each block, the devices were placed at a distance of 20 m from each other, while the distance between blocks was at least 30 m. Carriers loaded with TN Am were septa type and placed inserted in the center of the trap.

[0101] The captures obtained in each of the traps were reviewed weekly and the captured individuals were taken to the laboratory to be identified and counted. The intra-block trap rotation was carried out every week to eliminate possible date bias due to the traps position.

[0102] The number of males captured per trap per day was compared by means of an analysis of the variance (ANOVA; LSD test for comparison of means, P < 0.05), following to the transformation (ln(x+l)) of the data in order to homogenize the variance. The results show that the devices loaded with TNAm have a power of significantly higher attraction than traps without attractant, as shown in table 3. On average, 9.5 captures per trap per day in the field were obtained in the traps baited with TNAm with respect to the 0.5 captures in the controls, which means a significant difference in the analysis of variance (Table 3; F = 10.74; P = 0.008). Table 3. Results of the test to evaluate the attraction in the field by TNAm.

[0103] * Capture values followed by a different letter (a and b in table 3, ’’Captures”) are significantly different (ANOVA, LSD test, P < 0.05).

[0104] Example 5, Synthesis of (3,4,5,5-tetramethylcyclopent-2-en-l-yl)methyl acetate (compound I).

[0105] An alternative route to compound I as diastereomeric mixture is shown below:

[0106]

[0107] 4 5

[0108] (4,5,5 -trimethyl-3 -oxocyclopent- 1 -en- 1 -yl)methyl 3 ,3 -dimethyl-2-oxobutanoate , 2 :

[0109] Compound 1 was followed as previously described in “Vacas, S., Navarro, I., Marzo, J., Navarro- Llopis, V., & Primo, J. (2019). Sex pheromone of the invasive mealybug citrus pest, Delottococcus aberiae (Hemiptera: Pseudococcidae). A new monoterpenoid with a necrodane skeleton. Journal of agricultural and food chemistry, 67(34), 9441-9449”. Compound 1 (5 g, 24.6 mmol) was dissolved in tert-butyldimethyl ether (25 ml) under inert atmosphere, and potassium pivalate (5.2 g, 37,5 mmol) was added. The reaction was monitored by GC-MS until compound 1 was completely consumed and after 24 h of continuous stirring, the suspension was filtered off, the organic solution was subsequently washed with solutions of NaHCCh sat. (2 x 10 ml), HC1 IM, brine (1 x 10 ml) and the solvent evaporated under vacuum to afford 6.4 g of a yellow oil (85% purity as determined by GC-FID). A solution of HMSDLi in THF (34 ml, 1 M) was cooled down to -35 °C and a solution of the crude material obtained in the previous step in anhydrous THF (5 ml) was added dropwise during 30 min. After 2 h of continuous stirring, Mel (10.2 g, 72 mmol) was added, and the solution was kept at this temperature for 15 h. After this time, NH4CI sat. (15 ml) was added and the mixture was warmed up to room temperature. The mixture was extracted with ethyl acetate (2 x 40 ml) and the combined organic phases were subsequently washed with solutions of HC1 IM (2 x 20 ml), NaHCCF sat. (2 x 20 ml), brine (1 x 30 ml). Rotary evaporation of the solvent afforded 5.2 g of a crude material, which was purified by column chromatography using silica gel as stationary phase and a mixture of hexane: ethyl acetate (9: 1) as eluent, to afford compound 2 as a yellow oil (4.9 g, 85% yield). Spectroscopical data of compound 2: ’H NMR (300 MHz, CDC13) 5 5.99 (t, J= 1.7 Hz, 1H), 4.92 (dd, J = 3.8, 1.6 Hz, 2H), 2.24 (q, J = 7.4 Hz, 1H), 1.26 (s, 3H), 1.25 (s, 9H), 1.11 (s, 3H), 1.08 (d, J= 7.5 Hz, 3H).13C NMR (75 MHz, CDC13) 5 210.1, 180.4, 178.0, 125.9, 60.6, 53.7, 44.9, 39.0, 27.3, 26.2, 23.9, 9.7.

[0110] (2,2,3-trimethyl-4-oxocyclopentyl)methyl 3,3-dimethyl-2-oxobutanoate, 3:

[0111] Compound 2 (4.9 g, 20.6 mmol), was dissolved in ethyl acetate (40 ml) under nitrogen. Pd / C (245 mg, 5%) was added and after replacing nitrogen by H2 the reactor was pressurized (1.5 atm H2). The suspension was stirred for 24 h and after this period, the reactor was depressurized and purged with nitrogen. The suspension was filtered off though a celite pad and the organic solvent evaporated under vacuum to afford compound 3 (4.9 g, 95 % purity as determined by GC-FID, 95 % yield) as a mixture of a cislrans diastereoisomers (95:5) according to the GC-MS analysis and spectroscopical data of the sample. For clarity, only signals belonging to the main diastereoisomer are given below. Spectroscopical data of compound 3: ’H NMR (300 MHz, CDC13) 5 4.25 (dd, J= 11.2, 6.1 Hz, 1H), 4.09 (dd, J= 11.1, 7.6 Hz, 1H), 2.46 (ddd, J = 18.7, 8.4, 1.3 Hz, 1H), 2.36 - 2.19 (m, 1H), 2.11 - 1.87 (m, 2H), 1.21 (s, 3H), 1.20 (s, 9H), 0.95 (d, J = 7.0 Hz, 3H), 0.70 (s, 3H).13C NMR (75 MHz, CDC13) 5 217.8, 178.7, 64.4, 57.3, 44.2, 40.9, 39.2, 38.9, 27.3, 26.9, 16.1, 7.1.

[0112] (3 ,4,5 ,5 -tetramethylcyclopent-2-en- 1 -yl)methanol, 4 :

[0113] Dichlorodicyclopentadienyl titanium (10. 1 g, 40.8 mmol) was suspended in toluene (250 ml) and cooled to 0 °C under inert atmosphere. MeMgCl (27 ml, 3 M) was added, and the solution was warmed up to room temperature. After 2 h of continuous stirring, a solution of 3 (4.9 g, 20.4 mmol) in anhydrous toluene was added and the solution was heated to 90 °C for 6 h. After this time, the solution was cooled down to room temperature and the resulting suspension was filtered off though a celite pad and the organic solvent evaporated under vacuum to get a crude material which was used in the next step without further purification. The crude material obtained in the previous step was dissolved in MeOH, and BGCCh (1.8 g, 13 mmol, 10 eq) was added. The suspension was stirred for 20 h and after this period, the solid was filtered off and the solution poured into 25 ml of ethyl acetate. The combined organic phases were subsequently washed with solutions of HC1 IM (2 x 10 ml), NaHCO3sat. (2 x 10 ml), brine (1 x 10 ml). Rotary evaporation of the solvent afforded 4 g of a crude material, which was purified by column chromatography using silica gel as stationary phase and a mixture of hexane :Et2O (9: 1) as eluent, to afford compound 4 as a faint yellow oil (2.04 g, 65 % yield). Spectroscopical data of compound 4: ’H NMR (300 MHz, CDC13) 5 4.84 (dtd, J = 3.1, 2.1, 1.1 Hz, 1H), 4.74 (qd, J = 2.6, 1.1 Hz, 1H), 3.79 (dd, J = 10.5, 5.6 Hz, 1H), 3.54 (dd, J = 10.5, 8.2 Hz, 1H), 2.74 - 2.58 (m, 1H), 2.14 - 1.96 (m, 2H), 1.91 - 1.76 (m, 1H), 1.06 (s, 3H), 0.91 (d, J = 6.8 Hz, 3H), 0.53 (s, 3H).13C NMR (75 MHz, CDC13) 5 155.0, 104.5, 64.5, 50.7, 50.4, 42.3, 34.5, 26.56, 15.1, 10.5. (3 ,4,5 ,5 -tetramethylcyclopent-2-en- 1 -yl)methanol, 5 :

[0114] Isomerization of the exo-double bond was carried out according to the method described by “Zou, Y., Daane, K. M., Bentley, W. J., & Millar, J. G. (2010). Synthesis and bioassay of racemic and chiral trans-a-necrodyl isobutyrate, the sex pheromone of the grape mealybug Pseudococcus maritimus. Journal of agricultural and food chemistry, 58(8), 4977-4982”. Lithium metal (1 g, 145 mmol) was suspended in ethyl diamine (10 ml) under Argon atmosphere, and the suspension was heated to 90 °C for 30 min and cooled to 70 °C. A solution of the alcohol 4 (2.04 g) in anhydrous ethyl diamine (4 ml), was added over the blue color solution of the metal. After 10 min of stirring, the solution was cooled down to room temperature and poured over ice / water and subsequently extracted with ethyl acetate / DCM, washed with solutions of HC1 IM (2 x 10 ml), NaHCO3sat. (2 x 10 ml), brine (1 x 10 ml). Rotary evaporation of the solvent afforded 4 g of a crude material as a 7:3 mixture of a-necrodol and y-necrodol, which was purified by column chromatography using silica gel as stationary phase and amixture of hexane: ether (95:5) as eluent, to afford compound 5 as a yellow oil (1.33 g, 65 % yield). Spectroscopical data of compound 5:3H NMR (300 MHz, CDC13) 5 5.23 (dd, J= 3.3, 1.6 Hz, 1H), 3.63 (dd, J= 10.5, 5.9 Hz, 1H), 3.52 (dd, J = 10.5, 6.7 Hz, 1H), 2.39 - 2.30 (m, 1H), 2.17 - 2.06 (m, 1H), 1.68 (dt, J = 12, 1.4 Hz, 3H), 1.07 (s, 3H), 0.89 (d, J = 7.4 Hz, 3H), 0.82 (s, 3H).13C NMR (75 MHz, CDC13) 5 145.5, 1233, 63.9, 57.8, 53.3, 43.3, 30.7, 18.4, 1544, 13.8.

[0115] (3,4,5,5-tetramethylcyclopent-2-en-l-yl)methyl acetate), compound I:

[0116] Alcohol 5 (1.33 g, 8.6 mmol) was dissolved in DCM and Et3N (1 ml, 77 mmol), DMAP (catalytic amount) and Ac2O (0.7 ml, 77 mmol) were subsequently added. The reaction was stirred at room temperature for 4 h and after this period, the solution was subsequently washed with solutions of HC1 IM (2 x ml), NaHCO3sat. (2 x ml) and brine (l x ml). Rotary evaporation of the solvent afforded compound I as a crude material, which was purified by column chromatography using silica gel as stationary phase and a mixture of hexane: ether (95:5) as eluent, to afford compound I as a yellow oil (1.6 g, 95 % yield) whose spectroscopical data were fully match with those previously reported in the literature. Spectroscopical analysis of compound I displayed a composition of ca. 95:5 mixture of enantiomeric pairs Ic+Id and la+Ib respectively. Quantitative analysis of I using a standard sample of la, isolated from Lavanda luisieri essential oil, confirmed the previous composition of the diastereoisomeric mixture present in I. For clarity, only signals referring to the main diastereoisomer are given. Spectroscopical data of I: ’H NMR (400 MHz, CDC13) 5 5.17 (d, J = 1.7 Hz, 1H), 4.05 (dd, J = 10.8, 7.0 Hz, 1H), 3.95 (dd, J = 10.8, 7.6 Hz, 1H), 2.53 - 2.45 (m, 1H), 2.19 - 2.10 (m, 1H), 2.04 (s, 3H), 1.65 (m, 3H), 1.08 (s, 3H), 0.89 (d, J = 7.4 Hz, 4H), 0.77 (s, 3H).13C NMR (101 MHz, CDC13) 5 171.4, 144.8, 123.2, 65.8, 53.7, 53.1, 43.9, 29.6, 21.2, 18.1, 15.2, 13.3. Example 6: Atraction response tests of Delottococcus aberiae males to synthetic (3,4,5, 5- tetramethylcyclopent-2-en-l-yl)methyl acetate in the field.

[0117] The response of male individuals of Delottococcus aberiae to (3,4,5,5-tetramethylcyclopent-2- en-l-yl)methyl acetate (compound I), obtained according to example 5, was evaluated in a field trial carried out in a citrus orchard var. Clemenules, located in the town of Vila-real (Castellon). In the test, 4 blocks of 2 devices were installed: (A) a device with a carrier, without atractant, and a trap consisting of a white cardboard with adhesive (95 x 150 mm), (B) a device with a carrier loaded with 100 pg of compound I and a trap consisting of a white cardboard with adhesive. Within each block, the devices were placed at a distance of 20 m from each other, while the distance between blocks was at least 30 m. The carriers loaded with compound I were of the septum type and were inserted in the center of the trap.

[0118] The captures obtained in each of the traps were reviewed weekly and the captured individuals were taken to the laboratory to be identified and counted. Intrablock trap rotation was performed every week to eliminate possible biases in the data due to their position.

[0119] The number of males captured per trap per week was compared using an analysis of variance (ANOVA; LSD test for comparison of means, P < 0.05), following (ln(x+l)) transformation of the data in order to homogenize the variance.

[0120] The results show that the devices baited with compound I have a significantly higher atractant power than the traps without atractant, as shown in table 4. On average, 5.13 captures per trap per week were obtained in the field in the traps baited with compound I compared to the 0.75 captures in the control traps, which means a significant difference in the analysis of variance (Table 4; F = 17.20; P = 0.002).

[0121] Table 4. Results of the test to evaluate the field atraction of compound I. Captures (males / trap / week) . .

[0122] Substance Statistics* mean ± ee

[0123] Compound I 5.13 ± 1.88 a F = 17.20

[0124] Control 0.75 ± 0.31 b P = 0,002

[0125] * Capture values followed by different leters (a and b in table 4, “Captures”) are significantly different (ANOVA, LSD test, P < 0.05).

Claims

CLAIMS1. Use of a compound of formula I:I for controlling and / or monitoring populations of insects of the Delottococcus abericie species.

2. Use of a compound of formula I according to claim 1, wherein said compound is used as an attractant, preferably as a sex pheromone, for insects of the Delottococcus aberiae species.

3. Use of a compound of formula I according to claim 1 or 2, wherein said compound is a mixture of diastereoisomers of formula la, lb, Ic and Id:preferably said compound is compound la.

4. Use of a composition comprising a compound of formula I as defined in any of claims 1-3, and optionally a compound of formula II:for controlling and / or monitoring populations of insects of the Delottococcus aberiae species, preferably as an attractant for, more preferably as a sex pheromone for said species.

5. Use of a plant extract comprising the compound of formula I:preferably compound la,la for controlling and / or monitoring populations of insects of the Delottococcus abericie species; preferably as an attractant for, more preferably as a sex pheromone for insects of said species; said plant extract preferably comprising an extract of Lavcindci stoechas sub. Luisieri.

6. Composition for controlling and / or monitoring populations of insects of the Delottococcus aberiae species; preferably as an attractant for, more preferably as a sex pheromone for insects of said species, comprising a compound of formula I:I preferably wherein said compound is a mixture of diastereoisomers of formula la, lb, Ic and Id:more preferably wherein the compound of formula I is compound la;said composition being characterized in that it is formulated as tablet, capsule, powder, granule, paste, gel, emulsion, microencapsulated solution, dispersion or aerosol.

7. Composition according to claim 6, wherein said composition further comprises at least a chemically acceptable excipient.

8. Composition according to claim 7, wherein the at least a chemically acceptable excipient is selected from antioxidants, diluents, dyes, disintegrating, lubricants, binders, UV radiation protectors, or mixtures thereof.

9. Composition according to any of claims 6 to 8, which further comprises an additional compound selected from pheromones, kairomones, or insect control agents.

10. Composition according to any of claims 6 to 9, wherein said composition further comprises a carrier.

11. Composition according to claim 10, wherein the composition is deposited, absorbed, adsorbed, physically coated or chemically coated on the carrier.

12. Composition according to claim 10, wherein at least compound I, or at least the mixture of diastereoisomers of formula la, lb, Ic and Id or at least compound la is deposited, absorbed, adsorbed, physically coated or chemically coated on the carrier.

13. Composition according to any of claims 10 to 12, wherein the carrier is:- a wax, preferably a paraffin, or- a matrix selected from a polymeric matrix, a wood matrix, a ceramic matrix, a metallic matrix, a leather matrix, preferably, wherein the polymeric matrix comprises a polymer, preferably a woven or non-woven polymer, more preferably a non-woven polymer selected from the list consisting of polyamide, polyester, cotton, thermosetting polymer, resins, and rubber.

14. Composition according to any of claims 6 to 13, wherein the composition further comprises the compound of formula II:

15. Combination which comprises, preferably consists of, a compound of formula I,preferably a mixture of diastereoisomers of formula la, lb, Ic and Id,more preferably the compound la, and a compound of formula II:for controlling and / or monitoring populations of insects of the Delottococcus aberiae species; preferably as an attractant for, more preferably as a sex pheromone for insects of said species.

16. Device for controlling and / or monitoring populations of insects of the Delottococcus aberiae species; preferably for attracting insects of said species, which comprises a composition according to any of claims 6 to 14 or a combination according to claim 15.

17. Trap device for insects of the Delottococcus aberiae species which comprises a composition according to any of claims 6 to 14 or a combination according to claim 15.

18. Method for controlling and / or monitoring populations of insects of the Delottococcus aberiae species which comprises at least the following steps: i) providing a device according to any of claims 16-17 and placing it in an agricultural crop;ii) leaving the device of step i) in an agricultural crop for at least 3 hours to release at least the compounds of formula I as defined in claims 1 to 3 or at least the combination of compounds of formula I with II as defined in claim 15.

19. Method for controlling and / or monitoring Delottococcus abericie populations according to claim 18, wherein the control and / or monitoring is carried out by attracting male individuals belonging to the Delottococcus abericie species; and / or through mating disruption of male individuals belonging to the Delottococcus aberiae species; and / or through the affectation / death of male individuals belonging to the Delottococcus aberiae species.

20. Use of the composition according to any of claims 6 to 14, the combination according to claim 15 or the device according to any of claims 16-17 for controlling and / or monitoring populations of insects of the Delottococcus aberiae species; preferably for attracting insects of said species.

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