Compounds and compositions that attract the long-tailed mealybug species, attracting devices, and attracting devices and methods for controlling and / or monitoring pests.

Abstract

The present invention relates to ester compounds comprising a 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl core and compositions comprising the compound for attracting the long-tailed mealybug species. The present invention also relates to long-tailed mealybug attractants comprising the compound or the composition, preferably incorporated into a carrier, methods for controlling and / or monitoring insect populations of the long-tailed mealybug species, and the use of the compounds, compositions or apparatus of the present invention for controlling and / or monitoring pests. Finally, the present invention provides methods for preparing the ester compounds of the present invention.

Description

[Technical Field]

[0001] This invention relates to the field of agricultural pest control, and in particular to the long-skinned mealybug ( Pseudococcus longispinus This invention relates to compounds and compositions that attract insects of the following species. [Background technology]

[0002] The long-tailed mealybug (Targioni-Tozzetti; Hemiptera: Coccoidea: Mealybugidae), also known as the long-tailed mealybug, is a polyphagous, internationally recognized pest that damages a diverse range of plants, including fruit, vegetable, and ornamental plants, causing serious damage to leaves, bark, branches, fruits, and roots (Gillani, W., Copland, M. & Raja, S. (2011) Effect of different temperatures and host plants on the biology of the long-tailed mealybug). Pseudococcus longispinus(Targioni and Tozzetti) (Homoptera: Pseudococcidae). Biological Sciences-PJSIR, 54(3), 142-151). This Meerley bug gets its name from the pair of waxy threads at the rear of the female adult's abdomen that are as long as or longer than the rest of its body. The database contains descriptions of 209 genera from 98 families (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), but it is known as an extremely harmful pest to many economically important crops, particularly apples, pears, persimmons, grapes, citrus fruits, avocados, bananas, and other tropical fruits (Mani, M. & Shivaraju, C. (2016) Management of Mealybugs in Agricultural and Horticultural Crops, in Mani, M. and Shivaraju, C. (Eds.) Mealybugs and their management in agricultural and horticultural crops. Springer India, New Delhi, India, pp. 239-653). Like other mealybugs, it feeds on tree sap, producing honeydew that promotes the growth of saprophytic fungi, slows photosynthesis, reduces plant vitality, and causes premature ripening and fruit drop. Furthermore, due to its feeding habits, the long-tailed mealybug has the ability to acquire and transmit viruses, particularly those of the Betaflexiviridae family (GVA, La Notte, P., Buzkan, N., Choueiri, E., Minafra, A. & Martelli, GP (1997) Acquisition and transmission of grapevine virus A by the mealybug Pseudococcus longispinus(Journal of Plant Pathology, 79-85) and Closteroviruses (GLRaV-3, Petersen, CL & Charles, JG (1997) Transmission of grapevine leafroll-associated closteroviruses by Pseudococcus longispinus and P. calceolariae. Effective propagation methods are known from sources such as Plant Patholology, 46(4), 509-515).

[0003] Because their habits are unknown and they have overlapping generations, controlling these insects is difficult, and current control of the long-tailed mealybug relies on the application of conventional chemical treatments, with only a few effective substances currently available, such as mineral oil and spirotetramat (IVIA 2022. Gestion integrada de Plagas y Enfermedades en Caqui).

[0004] The European Commission's ban on the use of methylchlorpyrifos in January 2020 has raised significant concerns among farmers, as there are still few recommended and available materials with extremely limited effectiveness. Meanwhile, the timing of applying these control measures is crucial for achieving effective control. While this timing is not precisely defined, it must coincide with the period when the pest's sensitive form is at its peak, and determining this is difficult for less synchronous species. Regarding biological control measures, Acerophagus angustifrons ( Acerophagus angustifrons )(Gahan), Anagyrus fusciventris ( Anagyrus fusciventris )(Girault), Cryptanosia Comperei ( Cryptanusia comperei )(Timberlake), Leptomasticus argyrica trypitsin ( Leptomastix algirica TrjapitzinStudies are being conducted to evaluate the effectiveness of several parasitic wasps of the family Chalcididae, such as ). As for predators, the ladybug species *Epilachna vigintioctopunctata* ( Cryptolaemus montrouzieri Mulsant is used in biological control programs against mealybugs, including the citrus mealybug (Citrus mealybug) in citrus fruits. Planococcus citri It was first introduced in Spain to control the population of Risso. The large red ladybug (Ladybug japonica) has been observed feeding on the long-tailed mealybug (Ladybug rhynchophylla) in fields, exhibiting control effects during the summer months. However, it is not effective in persimmon cultivation in Spain, or on other crops such as avocados, citrus fruits, grapes, pears, persimmons, and pineapples (Faber B. A et al. 2007, UC IPM pest management guidelines: Avocado. UC ANR Publication 3436. University of California Agriculture and Natural Resources; Furness GO 1976, Australian Journal of Zoology 24: 237-247; Dentener PR et al. 1997, Postharvest Biology and Technology 12: 255-264), as well as on cycads in Australia, the United States, Asia, and European countries (Culbert 2010. Florida Coonties and Atala Butterflies: ENH117 / MG347, rev. 3 / 2010). In the case of ornamental plants, including species of EDIS, 2010(2)) and orchids (Kot et al. 2015, Bulletin of Entomological Research 105: 373-380; Ray and Hoy 2014, Florida Entomologist 97: 972-978), it is not possible to control the population by itself at the end of the season (September to December).

[0005] In this regard, it is clear that there is no effective method for controlling the long-tailed mealybug, and farmers and producer organizations need both direct control measures and tools for detecting and monitoring populations. In both agricultural and ornamental ecosystems, the detection and monitoring of mealybug populations is crucial for improving the control of the pest in question. However, this usually consists of laborious visual inspection of plant material to look for insects at multiple stages. Sticky traps using sex pheromones are an excellent tool for monitoring male flight in a more comfortable and sensitive way than visual inspection (Navarro-Llopis, V., Primo, J., Navarro, I., & Vacas, S (2019) Seguimiento y distribucion del cotonet de Sudafrica Delotococcus aberiae Delotto (Hemiptera: Pseudococcidae) en la Comunidad Valenciana mediante trampas cebadas con su feromona sexual. Phytoma Espana, 311, 56-61). Many economically important species of mealybugs reproduce sexually, with females producing sex pheromones to attract males of the same species. To date, the chemical structures of sex pheromones from 32 species of scale insects belonging to the superfamilies Coccoidea, Coccidae, Coccidae, and Mealybuidae have been identified (Franco, JC, Cocco, A., Lucchi, A., Mendel, Z., Suma, P., Vacas, S., Mansour, R. & Navarro-Llopis, V. (2021) Scientific and technological developments in mating disruption of scale insects. Entomologia Generalis 42, 251-273), and some of these are used for the detection and monitoring of their populations. On the other hand, pests of the superfamilies Coccoidea (e.g., the red scale insect ( Aonidiella aurantii Maskell; Scalebur (registered trademark), Ecologia y Proteccion Agricola, Valencia) and mealybugs ( Planococcus ficus The use of these sex pheromones in commercially available treatments for the direct control of Signoret (CheckMate® VMB-XL, Suterra, Bend, USA) is known, characterized by the use of mating disruption techniques (where males are unable to find females through various mechanisms that cause mating disruption) or the attraction and death of males (Delottococcus aberiae De Lotto; A. aurantii, P. citri, Vynyty®, Bayer Cropscience).

[0006] The sex pheromone of the longtailed mealybug species was described by Millar et al. (Sex pheromone of the longtailed mealybug: a new class of monoterpene structure. Organic Letters 2009, 11, 2683-2685) as compound 2-(1,5,5-trimethylcyclopenta-2-en-1-yl)ethyl acetate in populations of this species collected in the United States. However, this substance was found to be ineffective in attracting longtailed mealybug populations in persimmon cultivation in Valencia. In a preliminary study conducted by the Polytechnic University of Valencia (UPV), traps using unmated female longtailed mealybugs as bait captured 100 times more males than traps using the synthetic pheromone described by Millar. These results led to the most likely hypothesis that the pheromone complex of the Spanish population of the long-tailed mealybug differs from that of the US population sampled in 2009. This is not unusual, and this phenomenon is typical of mealybugs. P. ficus) Regarding this, it is described that while the California population produces a single-component pheromone, the Israeli population produces an additional compound (Zada, A., Dunkelblum, E., Assael, F., Harel, M., Cojocaru, M. & Mendel, Z. (2003) Sex pheromone of the vine mealybug, Planococcus ficus in Israel: occurrence of a second component in a mass-reared population. Journal of Chemical Ecology, 29, 977-988).

[0007] From all of the above, the pheromones previously described for the Nagaokona beetle were not effective. Therefore, there is a need for new compounds that can enable the control and specific monitoring of these Nagaokona beetle populations, and in addition to being effective, can be used in environmentally sustainable control methods.

Summary of the Invention

[0008] The present invention provides an attracting compound for insects of the Nagaokona beetle species, as well as an attracting composition and device comprising said compound, thereby solving the problems described in the prior art.

[0009] Thus, in a first aspect, the present invention relates to a compound of formula I (hereinafter "the compound of the present invention"):

Chemical formula

Chemical formula

[0010] In a second embodiment, the present invention relates to a composition comprising the compound of the present invention (hereinafter referred to as "the composition of the present invention"). In particular, the composition is useful for attracting insects of the species *Euproctis similis*.

[0011] In a third aspect, the present invention relates to a carrier containing the compound or composition of the present invention.

[0012] In a fourth aspect, the present invention relates to a device for attracting the long-tailed mealybug, comprising a carrier containing the compound of the present invention or the composition of the present invention.

[0013] In a fifth aspect, the present invention relates to a method for controlling and / or monitoring a population of the long-tailed mealybug, comprising the use of the compound or composition of the present invention.

[0014] In a further embodiment, the present invention relates to the use of the compounds or compositions of the present invention for the control and / or monitoring of populations of the long-tailed mealybug.

[0015] Finally, the present invention relates to a method for preparing the compounds of the present invention. [Brief explanation of the drawing]

[0016] [Figure 1] Figure 1 shows the detection of 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl acetate in volatile samples of long-skinned mealybugs reared on lemon trees in the laboratory. (A) Synthetic 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl acetate as a racemic compound, (B) volatile substance sample from unmated females, and (C) GC traces of volatile substance sample from mated females. The peak with a retention time of 20.69 minutes detected in the unmated female sample (B) was not observed in the mated female sample (C), and is consistent with the trace of the synthetic sample of 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl acetate (A). [Modes for carrying out the invention]

[0017] As described above, a first aspect of the present invention relates to a compound of formula I: [ka] , its stereoisomers: [ka] These refer to solvates and mixtures, where R is the group -C(=O)R'; R' is selected from C1-C6 alkyl or C3-C6 cycloalkyl.

[0018] The compound of formula I is an ester derived from the 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl core.

[0019] The compound of formula I may exist as a pure stereoisomer or as a mixture of stereoisomers in any ratio, and for example, carbon atoms 1 and 5 of the five-membered ring may have an absolute R,S configuration (assigned according to the Kahn-Ingold-Prelogue priority rule). In particular, since the substituted cyclopentenyl ring of the compound of formula I is characterized by two stereocenters, there may be four stereoisomers, the structures of which are shown below. [ka] (wherein R is defined in this invention)

[0020] In one embodiment, the compound of formula I encompasses four possible stereoisomers in any possible molar ratio between them. In a particular embodiment, the compound of formula I is a pair of enantiomers (1R,5R)-I and (1S,5S)-I. In another particular embodiment, the compound of formula I is a pair of enantiomers (1S,5R)-I and (1R,5S)-I.

[0021] The R group in the side chain of the compound of formula I may contain a variety of acyl groups that are optionally substituted. Biologically equivalent substitutions of the -OC(=O)R' group are also permissible, as those skilled in the art will understand that such substitutions do not alter the biological activity of the compound of formula (I) (J. Med. Chem. 1989, 32, 2282). Certain biologically equivalent fragments of the ester group include, but are not limited to, amides, ketones, oximes, oxazoles, triazoles, and oximidazoles.

[0022] In one embodiment, the acyl group of the side chain of the compound of formula (I) is the group -C(=O)R', where R' is selected from C1-C6 alkyl or C3-C6 cycloalkyl. In this regard, the term "side chain" refers to the substituent CH2CH2OR of the cyclopentenyl ring.

[0023] C1-C6 alkyl groups or C3-C6 cycloalkyl groups may be optionally substituted. This substitution can occur at one or more CH positions of the R' group, and unless otherwise specified, these substituents at each substitution site are independently selected from C1-C4 alkyl groups, C3-C6 cycloalkyl groups, or halogens.

[0024] As used herein, the following terms have the following definitions:

[0025] Halogen represents fluorine, chlorine, bromine, or iodine, preferably fluorine or chlorine.

[0026] The "C1-C6 alkyl" group represents a branched saturated aliphatic or linear hydrocarbon with 1 to 6 carbon atoms. Typical alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, 2-butyl, pentyl, and hexyl. Similarly, C1-C4 alkyl groups refer to alkyl groups having 1 to 4 carbon atoms.

[0027] "C3-C6 cycloalkyl" refers to a non-aromatic, partially saturated or fully saturated cyclic aliphatic hydrocarbon group containing 3 to 6 carbon atoms. Examples of C3-C6 cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0028] In certain embodiments, the group R' is selected from C1-C4 alkyl or C3-C6 cycloalkyl. In more detailed embodiments, the group R' is selected from C1-C4 alkyl or cyclopropyl.

[0029] In preferred embodiments, the R' group is a C1-C4 alkyl group; preferably methyl, ethyl, propyl, butyl, or isobutyl; more preferably, R' is methyl or ethyl.

[0030] In a more detailed embodiment, the compound of formula I has the chemical structure: [ka] 2-((1R,5R)-1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl acetate, having chemical structure: [ka] 2-((1S,5S)-1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl acetate, chemical structure: [ka] 2-((1R,5R)-1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethylpropionate, having chemical structure: [ka] Selected from 2-((1S,5S)-1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethylpropionate or a mixture thereof, having the following properties.

[0031] In another specific embodiment, the compound of formula I has the chemical structure: [ka] 2-((1R,5S)-1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl acetate, chemical structure: [ka] 2-((1S,5R)-1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl acetate, having the chemical structure: [ka] 2-((1R,5S)-1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethylpropionate, having chemical structure: [ka] Selected from 2-((1S,5R)-1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethylpropionate or a mixture thereof, having the following properties.

[0032] Compounds of formula (I) may exist as enantiomers and / or diastereomer pairs. A mixture of two enantiomers having absolute configurations 1R,5R and 1S,5S may consist of two enantiomers in different ratios, such as 99:1 to 1:99, 90:10 to 10:90, 75:25 to 25:75, or 50:50 (ratios expressed as molar ratios). In a preferred embodiment, a mixture of compounds of formula (I) may consist of a racemic mixture (two enantiomers in a 50:50 ratio). In another embodiment, a mixture of two enantiomers of absolute configurations 1R,5R and 1S,5S may consist of two enantiomers in any ratio other than 50:50, such as 99:1 to 1:99, 90:10 to 10:90, or 75:25 to 25:75. In further embodiments, the compound of formula (I) consists of racemic enantiomers of absolute configuration 1R,5R and 1S,5S.

[0033] In yet another embodiment, the compound of formula (I) consists of a mixture of two enantiomers of absolute configuration 1R,5S and 1S,5R, preferably in a ratio of 50:50, or also in any other ratio such as 99:1 to 1:99, 90:10 to 10:90, or 75:25 to 25:75, respectively.

[0034] The ratio between diastereomers (expressed as a molar ratio) can also be varied from 99:1 to 1:99, 90:10 to 10:90, 75:25 to 25:75, or 50:50. Preferably, the diastereomer ratio can be varied from 99:1 to 75:25; more preferably, such a ratio is about 90:10.

[0035] In a particular embodiment of the first aspect of the present invention, the compound of formula (I) refers to a compound in which R is the group -C(=O)R', R' is selected from methyl and ethyl, and the stereoisomers are 1R,5R and 1S,5S in a 50:50 molar ratio.

[0036] In another specific embodiment of the first aspect of the present invention, the compound of formula (I) refers to a compound in which R is the group -C(=O)R', R' is selected from methyl and ethyl, and the stereoisomers are 1S,5R and 1R,5S in a 50:50 molar ratio.

[0037] In a second embodiment, the present invention relates to a composition comprising one or more compounds of the present invention, preferably one compound of formula I. The composition can be used to attract, control, and / or monitor populations of the long-tailed mealybug.

[0038] In more detailed embodiments, the compositions of the present invention comprise an effective amount of the compound of the present invention or a mixture of the compounds of the present invention in an effective amount of 0.001 mg to 100 g. Preferably, the effective amount is in the range of 0.001 mg to 1 g; more preferably, in the range of 0.001 to 100 mg. The effective amount is defined as the amount of the compound of formula I or a mixture thereof that acts on the long-tailed mealybug, either alone or in combination with other components in the composition, to effectively control the pests caused by the aforementioned species.

[0039] Alternatively, the weight percentage of the compound of formula I contained in the composition is 0.001 to 99.9% by weight of the total weight of the composition; preferably 0.01 to 99.0% by weight, and more preferably 0.1 to 95% by weight.

[0040] As those skilled in the art will recognize, the amount of compound may vary depending on the type of area, region or object being treated, environmental conditions and the number of days required for induction, as well as the specific proportion of enantiomers present in the compound of the present invention used.

[0041] In a more detailed embodiment, the composition of the present invention may further comprise at least one additional component.

[0042] In the present invention, the term "component" refers to any active substance incorporated into a composition to perform at least one specific function.

[0043] More specifically, the ingredients are selected from antioxidants, radiation protectants, insecticides, pheromones, and mixtures thereof.

[0044] In the present invention, the term "antioxidant" refers to any substance that can delay or prevent the oxidation of one or more components of the composition of the present invention. Preferably, the antioxidants of the composition of the present invention are 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 dithionite, lecithin, ascorbyl palmitate, tert-butylhydroquinone (TBHQ), and natural and / or synthetic tocopherols, as well as any combination of the above antioxidants.

[0045] In more detailed embodiments, the attractant composition of the present invention contains an antioxidant in a weight ratio of 1:1000 to 1:20 relative to the weight content of the compound of formula I. Preferably, the antioxidant contains an antioxidant in a weight ratio of 1:100 relative to the weight content of the compound of formula I.

[0046] In the present invention, the term "ultraviolet protective agent" refers to any compound that can protect and preserve one or more components of the composition of the present invention from photodegradation. Preferably, the ultraviolet protective agents of the present invention refer to PABA derivatives, salicylates, cinnamates, benzophenones, benzimidazoles, anthraphosphates, terpene derivatives, inorganic oxides, and any combination of the above ultraviolet protective agents. Preferably, they refer to 4-aminobenzoic acid, 4-hydroxybenzophenone, 2-ethylhexyl salicylate, 2-ethylhexyl trans-4-methoxycinnamate, ethylhexyl 2-cyano-3,3-diphenylacrylate, titanium dioxide and / or zinc oxide, and any combination of the conventional ultraviolet protective agents.

[0047] In certain embodiments, the UV protective agent contained in the attractant composition of the present invention is present in weight ratios of 1:200 and 1:20 relative to the weight content of the compound of formula I. Preferably, the UV protective agent is present in weight ratio of 1:50 relative to the weight content of the compound of the present invention.

[0048] In this invention, the term "insecticide" refers to a chemical substance that causes the death of insects. More specifically, insecticides refer to pesticides, and more specifically, organochlorines, organophosphates, carbamates, pyrethroids, neonicotinoids, tetramic acids, biological pesticides, and combinations thereof.

[0049] In this invention, a pheromone is defined as any substance secreted by an animal that elicits a specific response or behavior from others of the same species, and a sex pheromone is defined as one secreted by one species that elicits an attractive and mating response from the other. On the other hand, the term "kairomone" refers to a substance secreted by an organism that mediates communication between individuals of different species and provides benefits to the organism that receives it.

[0050] In more detailed embodiments, the composition of the present invention comprises at least one agriculturally acceptable excipient.

[0051] In the present invention, the term “agriculturally acceptable excipient” refers to any substance incorporated into the composition of the present invention to impart shape, viscosity, flavor, smell, color, etc. More specifically, excipients are selected from binders, diluents, solvents, disintegrants, lubricants, colorants, sweeteners, flavorings, preservatives, and mixtures thereof.

[0052] In certain embodiments, the compositions of the present invention are present in formulations selected from emulsions, solutions, dispersants, aerosols, liquids, gels, powders, granules, pastes, and tablets. Preferably, the formulation is selected from emulsions, solutions, aerosols, or tablets.

[0053] The compounds and compositions of the present invention as previously defined may be incorporated into the carrier, which constitutes a further embodiment of the present invention.

[0054] In the context of the present invention, the term "carrier" refers to a base or matrix that can hold or contain the compound or composition of the present invention. More specifically, the carrier is selected from among polymer matrices, wood, ceramics, metals, leather, nylon, rubber, paraffin, wax, cotton, foam, fabric, granules, polymers, silica, resins, and adhesive tapes.

[0055] In more detailed embodiments, the compounds or compositions of the present invention may be deposited, absorbed, adsorbed, pulverized, or coated, or found by any physical or chemical method that allows for incorporation into a carrier, depending on the properties of the compounds, compositions, and carriers. When the compounds or mixtures of the present invention are incorporated into a carrier, the weight percent of the compound of formula I contained in the carrier is 0.001 to 99.9% by weight, preferably 0.01 to 99.0% by weight, and more preferably 0.1 to 95% by weight, relative to the total weight of the carrier.

[0056] In a fourth embodiment, the present invention relates to a device for attracting the long-tailed mealybug, comprising a carrier containing a compound or composition of the present invention as defined in the embodiments described above. In certain embodiments, the device of the present invention comprises a trap.

[0057] In the present invention, the term “trap” refers to any device that captures and / or affects insects, and / or holds insects. In certain embodiments, the trap comprises a substance that is toxic or pathogenic to the target insect. In more detailed embodiments, the trap is a surface comprising an adhesive.

[0058] In certain embodiments, the trap includes a carrier for the apparatus of the present invention.

[0059] In certain embodiments, the carrier of the apparatus of the present invention is separated from the trap.

[0060] A certain amount of compound I is released from the attractant device, and a population of long-tailed mealybugs is attracted into the device. The effective average release rate of compound I is at least 0.1, at least 0.5, at least 1.0, at least 2.0, and at least 5.0 μg / day. In another embodiment, the effective average release rate of compound I is 0.1 to 500 μg / day. In yet another embodiment, the effective average release rate of compound I is 0.1 to 250 μg / day. In a preferred embodiment, the effective average release rate of compound I is 0.1 to 100 μg / day, more preferably 0.1 to 50 μg / day. Alternatively, the effective average release rate of compound I may be at least 0.001, at least 0.01, at least 0.1, at least 1.0, and at least 10 μg / day / ha (where "ha" refers to 1 hectare). In another embodiment, the effective average release of the compound of formula I is 0.001 to 500 μg / day / ha. In yet another embodiment, the effective average release of the compound of formula I is 0.01 to 250 μg / day / ha. In a preferred embodiment, the effective average release of the compound of formula I is 0.01 to 100 μg / day / ha, more preferably 0.1 to 50 μg / day / ha. In the present invention, “effective average release” refers to the release stream of at least one compound of formula I released at a substantially constant rate, which acts on the long-tailed mealybug by attracting, capturing, trapping, interfering with mating, and / or killing male individuals belonging to the said species.

[0061] The present invention also relates to a method for controlling and / or monitoring a population of the long-tailed mealybug (hereinafter referred to as the "method of the present invention"), comprising the use of the compounds, compositions, or apparatus of the present invention as defined above. More specifically, the method of the present invention comprises the use of the apparatus of the present invention. Thus, the method of the present invention comprises the effective average release amount of one or more compounds of formula I as specified above.

[0062] In certain embodiments, control and / or monitoring methods are carried out by attracting male individuals belonging to the species *Euproctis spp.*.

[0063] In another specific embodiment, the control and / or monitoring method is carried out by disrupting the mating of male individuals belonging to the species of the long-tailed mealybug.

[0064] In another specific embodiment, the control and / or monitoring method is carried out by means of killing male individuals belonging to the species of the long-tailed mealybug.

[0065] In further embodiments, the present invention relates to the use of the compounds, compositions, or apparatus of the present invention for the control and / or monitoring of populations of the long-tailed mealybug. In particular, the present invention relates to the use of the compounds of the present invention with an "effective average release" contained in the compositions or apparatus of the present invention for the control and / or monitoring of populations of the long-tailed mealybug. Such an effective average release is defined as described above.

[0066] Finally, in a further embodiment, the present invention also relates to a method for preparing a compound of formula I of the present invention (as shown above), i. Compounds of formula 1: [ka] Compound of formula 2 is formed by the aldol condensation of p-formaldehyde: [ka] The process of obtaining; ii. A step of protecting the hydroxyl group of compound 2 with the hydroxyl protecting group PG1; iii. Reduce the carbonyl group of the product from step ii, and protect the resulting -OH group with the hydroxyl protecting group PG2 to obtain the compound of formula 3: [ka] The process of obtaining; iv. Rearrange compound 3 to form compound 4: [ka] The process of obtaining; v. Reduce the carboxyl group of compound 4, and protect the resulting hydroxyl group with an acetyl group to obtain compound 5: [ka] The process of obtaining; vi. Deprotect the PG1-protected hydroxyl group and iodate the deprotected compound to obtain compound 6: [ka] The process of obtaining; vii. Dehydrohalogenation of compound 6 yields compound I with R=Ac, or dehydrohalogenation of compound 6 is followed by hydrolysis of the acetyl group to obtain compound I: [ka] The process involves reacting the compound with an anhydride [wherein R' is selected from C2-C6 alkyl or C3-C6 cycloalkyl] to obtain a compound of formula I where R≠Ac. Regarding methods that include

[0067] All steps of the above method can be carried out in a solvent or using undiluted reagents. Preferably, all reagents are dissolved in an organic solvent and the reaction is carried out with stirring until no further inversion is observed.

[0068] In step i), the aldol condensation is preferably carried out in the presence of a base. A suitable base may be an organic or inorganic base; in certain embodiments, the base is selected from potassium t-butoxide, potassium hydroxide, sodium hydride, lithium bis(trimethylsilyl)amide, lithium diisopropylamide, and methyllithium. Preferably, the base is lithium bis(trimethylsilyl)amide. The aldol condensation is also carried out at a low temperature so that side reactions are minimized. The temperature in step i) is -50°C to 0°C, preferably -40°C to -20°C, and more preferably 30°C.

[0069] In step ii), a hydroxyl protecting group is used to form a -CH2OPG1 protecting group. The introduction of protecting groups is common knowledge for those skilled in the art, and suitable reagents and conditions for this step will be readily found (see Peter GM Wuts, Theodora W. Greene, Greene's Protective Groups in Organic Synthesis, 4th edition, DOI:10.1002 / 0470053488). Preferred hydroxyl protecting groups include methoxymethyl ether (MOM), tetrahydropyranyl ether (THP), t-butyl ether, allyl ether, benzyl ether, t-butyldimethylsilyl ether (TBDMS), t-butyldiphenylsilyl ether (TBDPS), acetate, pivalate, and benzoate; preferably, THP is used as PG1. A catalytic amount of acid is required to carry out protection step i), and preferably, p-TsOH is used as the acid catalyst.

[0070] In step iii), the reduction of the carbonyl group of compound 2 is carried out in the presence of a metal hydride at a temperature of -10 to 10°C, more preferably about 0°C. Several metal hydrides, such as alkali hydrides, may be suitable for this step, with LiAlH4 being preferred. In this case as well, the protection of the resulting alcohol or alkoxide is carried out using a hydroxyl protecting group suitable for generating an -OPG2 group in the corresponding compound 3.

[0071] Next, in step iv), compound 3 undergoes the Ireland-Claisen rearrangement in the presence of TBDMSCl and a base, where the base is preferably an organolithium compound, more preferably LDA. Carboxylic acid 4 is obtained.

[0072] In step v), the reduction of carboxylic acids 4 to compound 5 is carried out in an aprotic solvent in the presence of a metal hydride, preferably lithium aluminum hydride. The alcohol or allalate product is protected with an acetyl group by using acetic anhydride as the acetyl precursor, but other acetyl precursors are also known and can be used.

[0073] Step vi) is carried out by deprotecting acetate 5 in an organic solvent or a mixture of organic solvents in the presence of a catalytic amount of acid, preferably p-TsOH. The amount of acid is variable, ranging from 0.01 to 10 mol%, preferably from 0.1 to 5 mol%, and more preferably about 1 mol%. Iodination of the protected alcohol is carried out under Appel conditions, in the presence of a triarylphosphine, preferably PPh3, an iodinating agent, preferably I2, and a base, preferably imidazole.

[0074] Finally, in step vii), the iodine derivative 6 is optionally dehalogenated in the presence of a base, preferably an N-heterocyclic base such as DBU, while the mixture is heated to a temperature of 40-80°C, more preferably about 60°C. A compound of formula I with R=Ac is then obtained. Alternatively, after dehalogenation of compound 6, the acetyl group is hydrolyzed to obtain a compound of formula: [ka] When reacted with an anhydride [wherein R' is selected from C2-C6 alkyl or C3-C6 cycloalkyl], a compound of formula I is obtained where R≠Ac. [Examples]

[0075] abbreviation Ac: Acetyl PG: Protecting group GC-MS: Gas Chromatography-Mass Spectrometry LDA: Lithium diisopropylamide TBDMSCl: tert-butyldimethylsilyl chloride HMDSLi: Lithium bis(trimethylsilyl)amide p-TsOH: p-toluenesulfonic acid DCM: Dichloromethane THF: Tetrahydrofuran

[0076] Example 1: Detection of 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl acetate in a sample from an unmated female of the long-tailed mealybug using volatile substance collection technology. To capture volatile substances released by female long-tailed mealybugs in different mating states, we used individuals from laboratory colonies reared on organically grown lemon trees at the Center for Agricultural Chemistry and Ecology (CEQA, Polytechnic University of Valencia, Valencia). The insect colonies were reared under controlled conditions of 23±2°C and 60-70% relative humidity in a chamber. Sampling of volatile substances released by the insects was performed by blowing air into the individuals and capturing the excretions in a glass cartridge filled with a Porapak-Q adsorption matrix.

[0077] Groups of 200-300 individuals were placed on a substrate in a 5L glass container and passed through a filtered airflow of 0.3L / min. Every 7-8 days, the adsorbent was washed with 20mL of pentane to elute the captured material. The eluate was analyzed by gas chromatography (GC-MS) connected to a mass spectrometer. Chromatographic analysis was performed on a Clarus 600 GC-MS instrument (PerkinElmer Inc.) equipped with a ZB-5MS capillary column (30m × 0.25mm inner diameter × 0.25μm; Phenomenex.Inc.) using the following temperature program: 40°C for 2 minutes; heating to 180°C at 5°C / min, then heating to 280°C at 10°C / min, and holding at 280°C for 1 minute. Helium was used as the carrier gas at a flow rate of 1mL / min. Detection was performed in electron shock mode (70 eV), with the ionization source and transfer line temperatures set to 200°C and 250°C, respectively. Once the exclusive peak of the unmated female sample was detected, the corresponding compound was isolated from the eluted mixture by gravity chromatography of the total extract using pentane:diethyl ether mixtures (100:0, 95:5, 80:20, 0:100) as the eluent. After isolation, the compound's structure was elucidated using data from GC-MS and nuclear magnetic resonance (NMR) (Bruker, 600 MHz). Finally, the spectrum of the natural substance was compared with the spectrum of the sample synthesized by Ecologia y Proteccion Agricola SL (Carlet, Valencia).

[0078] Chromatographic analysis, as shown in Figure 1, revealed a single peak that appeared only in samples of volatile substances released by unmated females, and not in samples from mated females or immature individuals. Spectroscopically, this peak was identified as 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl acetate, which was confirmed by comparison with a laboratory-prepared synthetic sample, as described later in Example 2. This is a novel substance, distinct from that described by Millar et al. in 2009.

[0079] Example 2: Synthesis of 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl acetate The synthesis of 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl acetate was carried out according to Scheme 1 shown below. [ka] Note: In the following procedure, two diastereomers were obtained in an approximately 9:1 ratio by NMR analysis, but for clarity, the major diastereomer was used. 1 H and 13 Only the 13C NMR signal is shown below.

[0080] Ketone 1 (5 g, 0.045 mol) was prepared according to Leviredend, ML; Conia, Sur JM, Sur la preparation de cyclopentenones par action de l'acide phosphorique sur les esters d'acides ethyleniques, Bulletin de la societe quimique de france, 8-9, 1970 (and its references). Ketone 1 was added dropwise to HMDSLi solution (65 mL, 0.9 M) in THF at -30°C for 90 minutes. This solution was warmed to 0°C, and p-formaldehyde (4.05 g, 3 equivalents) was added to it all at once. After 30 minutes, this solution was poured onto saturated ammonium chloride solution (45 mL) and extracted three times with ethyl acetate (30 mL). The combined organic phases were sequentially washed with HCl solution (1M), NaHCO3 solution (1M), and brine, and dried over anhydrous MgSO4. After evaporating the solvent, the crude substance was purified using column chromatography (silica gel, hexane:AcOEt 8:2) to obtain alcohol 2 (2.5g, yield 40%). 1 1H NMR (400 MHz, CDCl3) δ H 5.41 (1H, m), 3.92-3.72(2H, m), 2.65 (1H, m), 1.70 (3H, m), 1.71-1.66 (1H, m), 1.05 (3H, d, J 7.2 Hz); 13 C NMR (100 MHz) 210.2, 173.2, 127.8, 61.5, 57.3, 46.0, 18.2, 14.3. MS (70eV) m / z: 53 (3), 67 (2), 81 (8), 94 (7), 95 (7), 107 (1), 109 (7), 110 (4), 122 (4), 125 (2), 140 (7, M+).

[0081] Alcohol 2 (2.5 g, 0.018 mol) was dissolved in DCM (15 mL) and cooled to 0°C. 3,4-Dihydropyran (DHP) (1.89 mL, 0.021 mol) and a catalytic amount of p-TsOH (0.015 equivalents) were sequentially added to the solution. The reaction mixture was warmed to room temperature, monitored by TLC, and after 3 hours of continuous stirring, the solution was sequentially washed with NaHCO3 (1 M) and brine, and dried over anhydrous MgSO4. After evaporating the solvent, the mixture of hydroxyl-protected compound 2 was used in the next step without further purification. Crude hydroxyl-protected compound 2 was dissolved in anhydrous Et2O (7 mL) and added dropwise to a suspension of LiAlH4 (0.021 mol, 0.8 g) in anhydrous Et2O (25 mL) cooled to 0°C under an inert atmosphere (N2). This suspension was maintained at this temperature for a further 1.5 hours with stirring. After this period, acetic anhydride (0.042 mol, 1.96 mL) was added, and the reaction mixture was warmed to room temperature. The reaction was monitored by TLC, and after 15 hours of continuous stirring, saturated ammonium chloride solution (5 mL) was slowly added while passing a stream of N2 through the solution. This mixture was poured into ethyl acetate (30 mL), and the aqueous phase was separated. The organic layer was sequentially washed with HCl solution (1 M), NaHCO3 solution (1 M), and brine, and dried over anhydrous MgSO4. After evaporating the solvent, acetate 3 was purified by column chromatography (silica gel, Hex:AcOEt 9:1) to obtain a pale yellow oil (3.93 g, 70% yield in 2 steps). 1 1H NMR (400 MHz, CDCl3) δ H 5.47 (1H, m), 5.36 (1H, m), 4.6 (1H, m), 3.84-3.77 (2H, m), 3.56-3.45 (2H, m), 2.31 (1H, m), 2.01 (3H, s), 2.02-1.98 (1H, m), 1.85-1.75 (1H, m), 1.71 (3H, s), 1.70-1.49 (6H, m), 1.14 (3H, d, J 7.2 Hz); 1313C NMR (100 MHz) 171.2, 151.7, 122.7, 98.9, 81.6, 68.7, 62.1, 53.1, 45.2, 30.7, 25.6, 21.5, 19.8, 19.1, 15.01. MS (70 eV) m / z 51 (40), 43 (55), 55 (20), 57 (22), 60 (10), 65 (10), 67 (25), 77 (20), 79 (20), 85 (100), 91 (40), 93 (25), 95 (20), 106 (28), 107 (28), 109 (25), 124 (10), 141 (10), 183 (2), 208 (1), 226 (1).

[0082] A solution of acetate 3 (2.5 g, 9.3 mmol) in dry THF (10 mL) was added dropwise to a solution of LDA in THF (11.9 mL, 0.9 M) at -78 °C over 60 minutes. To this solution, chlorotert-butyldimethylsilane (11.1 mmol, 1.68 g, 1.2 equivalents) in dry THF (6 mL) was added in one portion. The solution was warmed to room temperature over 3 hours and then refluxed for 24 hours. After cooling to room temperature, NaOH solution (2 M, 20 mL) was added and the resulting biphasic mixture was stirred for 1 hour. The solution was acidified to pH 4 - 5 with aqueous citric acid (20%) and extracted three times with ethyl acetate (25 mL). The organic layer was washed successively with HCl (1 M), NaHCO3 (1 M), and brine solution and dried over anhydrous MgSO4. After evaporation of the solvent, the crude residue was purified using column chromatography (silica gel, Hex:AcOEt 8:2) to obtain acid 4 as an oil (1.2 g, 48% yield). 1 1H NMR (400 MHz, CDCl3) δ H5.87 (1H, dd, J 5.9, 2.5 Hz), 5.74 (1H, dt, J 22, 2.5 Hz), 4.61 (1H, ddd, J 13.5, 4.2, 2.8 Hz), 3.95-3.80 (1H, m), 3.80-3.58 (1H, m), 3.65-3.50 (1H, m), 3.45-3.30 (1H, m), 2.65-2.52 (1H, m), 2.35-2.2 (2H, m), 1.85-1.75 (1H, m), 1.73-1.50 (8H, m), 1.24 (3H, s), 1.05 (3H, d, J 7.2 Hz); 13 MS (70eV) m / z 55 (3), 67 (3), 79 (2), 85 (36), 91 (3), 107 (9), 121 (3), 166 (4), 238 (0.1, M+).

[0083] A solution of acid 4 (1.2 g, 4.5 mmol) was added dropwise to a LiAlH4 suspension cooled to 0°C under an inert atmosphere (N2) in anhydrous THF (6 mL). The suspension was maintained at this temperature for 1.5 hours with continuous stirring. After this period, acetic anhydride (10 mmol, 0.43 mL) was added, and the reaction mixture was warmed to room temperature and monitored by TLC. After 15 hours of continuous stirring, saturated ammonium chloride solution was slowly added while passing a stream of N2 through the solution. This mixture was extracted three times with ethyl acetate (20 mL). The organic layer was sequentially washed with HCl (1 M), NaHCO3 (1 M), and brine solutions, and dried over anhydrous MgSO4. After evaporation of the solvent, the crude material was purified by column chromatography (silica gel, hexane:AcOEt 9:1) to obtain acetate 5 as oil (0.86 g, 65% yield in 2 steps). 1 1H NMR (400 MHz, CDCl3) δ H5.74-5.5 (2H, m), 4.61 (1H, ddd, J 10.8, 3.2, 3.2 Hz), 4.15-3.90 (2H, m), 3.91-3.80 (1H, m), 3.79-3.55 (1H, m), 3.55-3.45 (1H, m), 3.43-3.25 (1H, m), 2.62-2.50 (1H, m), 2.03 (3H, s), 1.85-1.75 (1H, m), 1.73-1.48 (8H, m), 1.07 (3H, s), 1.03 (3H, d, J 7.2 Hz); 13 C NMR (125 MHz) 171.3, 139.7, 131.8, 99.3, 70.5, 62.3, 62.1, 52.3, 48.8, 48.7, 48.5, 34.9, 30.8, 25.6, 21.2, 19.7, 12.6. MS (70eV) m / z 43 (6), 55 (3), 57 (3), 67 (2) 77(1), 85 (37), 91 (3), 93 (3), 107 (6), 119 (2), 121 (1), 134 (5), 194 (1), 266 (0.1)。

[0084] Acetate 5 (0.86 g, 2.92 mmol) was dissolved in a DCM / MeOH mixture (8 mL; 1:1), and a catalytic amount of p-TsOH (0.01 equivalent) was added to this solution. The reaction was monitored by TLC, and after 3 hours of continuous stirring, the solution was poured into 10 mL of DCM, washed sequentially with NaHCO3 (1 M) and brine, and dried over anhydrous MgSO4. After removing the solvent under reduced pressure, the crude material was dissolved in anhydrous DCM (15 mL) and PPh3 (1.08 g, 2.92 mmol), and I2 (1.027 g, 2.92 mmol) and imidazole (0.46 g, 7.3 mmol) were added sequentially. After 3 hours of continuous stirring, the suspension was filtered to remove the precipitate, washed sequentially with a solution of HCl (1 M), NaHCO3 (1 M), and brine, and dried over anhydrous MgSO4. After evaporating the solvent, acetate 5 was purified using column chromatography (silica gel, Hex:AcOEt 9:1) to obtain iodide 6 as a pale yellow oil (0.85 g, 90% yield in 2 steps). Spectroscopic data: 1 1H NMR (400 MHz, CDCl3) δ H 5.72 (1H, dd, J 5.9, 1.1Hz), 5.62 (1H, dd, J 5.9, 2.0 Hz), 4.18-3.90 (2H, m), 3.46 (1H, dd, J 9.8, 4.1 Hz), 3.07 (1H, dd, J 9.8, 7.2), 2.48 (1H, m), 2.03 (3H, s), 1.65-1.55 (2H, m), 1.09 (3H, s), 1.01 (3H, d, J 7.2 Hz); 13 MS (70eV) m / z 48 (8), 55(2), 67 (1), 79 (3), 91 (6), 93 (10), 108 (13), 119 (1), 135 (18), 235 (5), 247 (0.3), 262 (0.1).

[0085] Iodide 6 (500 mg, 1.6 mmol) was dissolved in toluene (12 mL), and DBU (2.1 mmol, 0.31 mL) was added. This solution was heated at 60 °C for 6 hours. After this period, the solution was cooled to room temperature, poured onto hexane (10 mL), and washed sequentially with HCl (1 M), NaHCO3 (1 M), and brine. The mixture was then dried over anhydrous MgSO4. After evaporating the solvent, the crude mixture was purified by column chromatography (silica gel, hexane:AcOEt 9:1) to obtain 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl acetate I as a pale yellow oil (282 mg, yield 91%). 1 1H NMR (500 MHz, CDCl3) δ H 6.14 (1H, d, J 5Hz), 5.95 (1H, d, J 5Hz), 4.84 (1H, d, J 3Hz), 4.65 (1H, d, J 3Hz), 4.1-3.94 (2H, m), 2.38 (1H, m), 2.01 (3H, s), 1.65-1.54 (2H, m), 1.12 (3H, s), 1.07 (1H, d, J 7.1 Hz); 13 ¹³C NMR (125 MHz) δ C 171.1, 157.9, 145.1, 132.0, 102.6, 62.2, 49.1, 48.7, 35.9, 25.8, 21.2, 11.8. MS (70eV) m / z: 43 (6), 53 (1), 65 (1), 79 (5), 91 (12), 107 (15), 119 (15), 134 (11), 194 (2, M+).

[0086] Example 3: Synthesis of 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethylpropionate [ka] Compound Ia (100 mg, 0.51 mmol) was dissolved in MeOH (5 mL), and K2CO3 (207 mg, 3 equivalents) was added to this solution. After continuous stirring for 2 hours, the suspension was filtered, and the solution was poured into ethyl acetate and washed sequentially with HCl (0.1 M), NaHCO3 (5%), and brine, and dried over anhydrous MgSO4. After evaporating the solvent, the crude alcohol was dissolved in anhydrous DCM (5 mL) and Et3N (0.2 mL, 3 equivalents), and 4-dimethylaminopyridine (0.01 equivalents) and propionic anhydride (0.14 mL, 1.1 equivalents) were added sequentially. After continuous stirring for 3 hours, the solution was transferred to a separation funnel, washed with HCl (0.1 M), NaHCO3 (5%), and brine, and dried over anhydrous MgSO4. After evaporating the solvent, the crude material was purified using column chromatography (silica gel, hexane:AcOEt 95:5) to obtain compound Ib 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethylpropionate as a pale yellow oil (100 mg, yield 95%). δ H (400 MHz, C6D6) 6.03 (1H, d, J 5.6 Hz), 5.71 (1H, d, J 5.6 Hz), 4.85 (1H, m), 4.67 (1H, m), 4.15-3.94 (2H, m), 2.26 (1H, m), 2.04 (2H, MS (70eV) m / z: 57 (5), 65 (1), 79 (4), 91 (10), 107 (16), 119 (16), 134 (11), 208 (1, M+).

[0087] Example 4: Field attraction response test of male long-tailed mealybugs The response of male long-spotted mealybugs to 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl acetate was evaluated in a field trial conducted in a persimmon orchard in Alginet, Valencia, Spain. Six blocks of three types of apparatus were set up: (A) an apparatus containing a carrier but no attractant, and including a trap made of white adhesive cardboard (95 × 150 mm); (B) an apparatus containing a carrier to which 250 μg of a substance described by Miller et al. in 2009 (e.g., 2-(1,5,5-trimethylcyclopenta-2-en-1-yl)ethyl acetate) was added, and a trap made of white adhesive cardboard; and (C) a carrier apparatus to which 250 μg of 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl acetate was added, and a trap made of white adhesive cardboard. Within each block, devices were placed at a distance of 10m from each other, and the distance between blocks was at least 30m. The carrier containing the added substance was a rubber partition type and was inserted into the center of the trap.

[0088] The captured specimens from each trap were checked every two weeks, and the captured individuals were brought to the laboratory for identification and counting.

[0089] The number of males captured in each trap each day was compared using analysis of variance (ANOVA; LSD test for mean comparison, P<0.05), after pre-transforming the data (ln(x+1)) to equalize the variance.

[0090] The results showed that the apparatus using 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl acetate as a decoy (C) had significantly higher attractiveness than the apparatus without the attractant (A) and the pheromone (B) described by Millar et al. (Table 1).

[0091] Analysis of the content of the attractant composition after 21 days shows that the final content of the substance was 134 μg. Therefore, the average release over 21 days was 5.52 ± 1.20 μg / day.

[0092] [Table 1]

[0093] The second field trial was conducted in a persimmon orchard in L'Arcudia (Valencia, Spain) to evaluate the attracting activity of 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethylpropionate. Four blocks of three types of apparatus were set up: (A) an apparatus containing a carrier but no attractant, and a trap made of white adhesive cardboard (95 × 150 mm); (B) an apparatus containing a carrier with 250 μg of 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethylpropionate added, and a trap made of white adhesive cardboard; and (C) a carrier apparatus with 250 μg of 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl acetate added, and a trap made of white adhesive cardboard. Other test conditions were the same as described above.

[0094] The results showed that the device (B) using 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethylpropionate as decoy had significant attracting activity and captured significantly more males than the trap (A) without the attractant (Table 2). Similarly, the device using 2-(1,5-dimethyl-4-methylenecyclopenta-2-en-1-yl)ethyl acetate (C) as decoy achieved the highest level of capture.

[0095] [Table 2]

Claims

1. Compound of formula I: 【Chemistry 1】 , its stereoisomers: 【Chemistry 2】 and mixtures thereof: [wherein R is the group -C(=O)R'; R' is selected from C1-C6 alkyl or C3-C6 cycloalkyl groups].

2. A compound of formula I according to claim 1, wherein R is the group -C(=O)R'; and R' is selected from methyl or ethyl.

3. A composition comprising the compound described in any one of claims 1 to 2 for controlling and / or monitoring a population of the long-tailed mealybug.

4. The composition according to claim 3, comprising at least one additional component.

5. The composition according to claim 4, wherein the additional component is selected from attractants, antioxidants, radiation protectants, insecticides, pheromones, kairomones, and mixtures thereof.

6. The composition according to any one of claims 3 to 5, comprising at least one agriculturally acceptable excipient.

7. The composition according to claim 6, wherein the agriculturally acceptable excipient is selected from binders, diluents, disintegrants, lubricants, colorants, sweeteners, flavorings, preservatives, and mixtures thereof.

8. The composition according to any one of claims 1 to 7, which is formulated as an emulsion, solution, dispersant, aerosol, liquid, gel, powder, granule, paste, or tablet; preferably, formulated as an emulsion, solution, aerosol, or tablet.

9. A carrier containing a compound of the formula described in any one of claims 1 or 2, or a composition described in any one of claims 3 to 8.

10. An insect attractant for the long-tailed mealybug species, comprising the carrier described in claim 9.

11. The attraction device according to claim 10, wherein the effective average release amount of the compound of formula I contained in the composition defined in claim 1 or 2, or in any one of claims 3 to 8, or in the carrier according to claim 9 is 0.1 to 250 μg / day, preferably 0.1 to 100 μg / day, more preferably 0.1 to 50 μg / day.

12. A method for controlling and / or monitoring a population of the long-tailed mealybug, comprising using a compound according to any one of claims 1 to 2, a composition according to any one of claims 3 to 8, or an apparatus according to any one of claims 10 or 11.

13. A method for controlling and / or monitoring a population of the long-tailed mealybug according to claim 12, wherein control is carried out by attracting, capturing, preventing mating, and / or killing male individuals belonging to the species of the long-tailed mealybug.

14. Use of the compound according to any one of claims 1 to 2, the composition according to any one of claims 3 to 8, the carrier according to claim 9, or the apparatus according to any one of claims 10 or 11 for the control and / or monitoring of populations of the long-tailed mealybug.

15. A method for synthesizing the compound described in claim 1, i. Compound of formula 1: 【Transformation 3】 The compound of formula 2 is formed by the aldol condensation of p-formaldehyde: 【Chemistry 4】 The process of obtaining; ii. Protect the hydroxyl group of compound 2 with the hydroxyl protecting group PG. １ The process of protecting with; iii. Reduce the carbonyl group of the product from step ii and protect the resulting -OH group with a hydroxyl protecting group PG. ２ Protected by the compound of formula 3: 【Transformation 5】 The process of obtaining; iv. Rearrange compound 3 to form compound 4: 【Transformation 6】 The process of obtaining; v. Reduce the carboxyl group of compound 4 and protect the resulting hydroxyl group with an acetyl group to obtain compound 5: 【Transformation 7】 The process of obtaining; vi. PG of compound 5 １ The protected hydroxyl group is deprotected and iodized to form compound 6: 【Transformation 8】 The process of obtaining; vii. Dehalogenation of compound 6 yields a compound of formula I where R is Ac, or dehalogenation of compound 6 is followed by hydrolysis of the acetyl group to obtain a compound of formula: 【Chemistry 9】 The process involves reacting the compound with an anhydride [wherein R' is selected from C2-C6 alkyl or C3-C6 cycloalkyl] to obtain a compound of formula I in which R is different from Ac. A method that includes the following:

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