Limonene derivative-based aphid repellent, preparation method therefor and use thereof

Abstract

The present invention relates to a limonene derivative-based aphid repellent, a preparation method therefor and the use thereof. Specifically, disclosed in the present invention is a compound of formula I, wherein the groups and substituents are as defined in the description and claims. The compound exhibits an excellent aphid-repellent effect. Further provided in the present invention are a method for preparing the compound and the use thereof for controlling and / or preventing damage to useful plants caused by pest infestation.

Description

A Limonene-Based Aphid Repellent, Its Preparation Method and Application Technical Field

[0001] This invention relates to the field of pesticides, specifically to an aphid repellent based on limonene derivatives, its preparation method, and its application. Background Technology

[0002] Aphids are among the most threatening pests in global agriculture, causing severe damage to crops and further exacerbating agricultural losses by spreading plant viruses. Currently, the main method of aphid control relies on chemical pesticides. However, traditional pesticide control strategies face a series of problems, including toxic risks to human health and the environment, as well as the rapid development of insect resistance. To overcome these problems, the scientific community is gradually turning to the use of pheromones and their analogues as a more sustainable and environmentally friendly means of aphid control.

[0003] Pheromones, as important biological signaling molecules in insects, play a crucial role in their behavior and life cycle. Compared with traditional chemical pesticides, pheromones and their analogues have lower resistance risks, faster degradation rates, and higher specificity, thus reducing negative impacts on non-target insects and the environment. In particular, developing pheromone analogues by mimicking the structure of natural pheromones has become a current research hotspot.

[0004] Currently, known aphid pheromones mainly include alarm pheromones (whose main component is (E)-β-farnesene) and sex pheromones (whose main components are nepetalol and nepetalactone). Although (E)-β-farnesene has a significant repellent effect on aphids, its application is limited by factors such as easy oxidation and poor stability. While nepetalactone shows some repellent effect, its effect is still weaker than that of (E)-β-farnesene. Therefore, finding aphid pheromone analogs with better stability and higher repellent efficiency has become an important research goal.

[0005] Plant volatiles, as a natural source of aphid repellent signals, have been extensively studied. While these volatiles have shown potential in aphid control, the effectiveness of most is limited by their release rate, timing, and structural characteristics. For example, many plant volatiles are released after aphid infestation, while repellents focus more on preventative effects. Furthermore, the repellent activity of plant volatiles is structurally constrained, making it difficult to meet the needs of large-scale applications. Therefore, modifying plant volatiles to enhance their repellent effects has become an important way to improve their application value.

[0006] In recent years, significant progress has been made in enhancing the repellent activity of plant volatiles against aphids by modifying them. For example, based on the binding affinity of jasmonic acid ester derivatives to aphid odorant-binding proteins, researchers have developed compounds with significant repellent activity (Li H et al., 2022). Furthermore, β-ionone derivatives have also shown enhanced repellent effects while attracting ladybugs, providing a new approach for integrated pest management (Pan S et al., 2024). These studies on modifying plant volatiles offer important insights for improving their repellent activity. In previous studies, the carbonyl group in nepeta lactone was identified as a key aphid-repelling group (Lu Y et al., 2024).

[0007] Therefore, there is an urgent need in this field to develop a novel aphid pheromone analog with excellent repellent activity to overcome the shortcomings of existing technologies. Summary of the Invention

[0008] The purpose of this invention is to provide a novel aphid pheromone analog with excellent activity, which can effectively control aphid behavior and has a significant repellent effect.

[0009] In a first aspect, the present invention provides a compound of Formula I, or a geometrical isomer thereof, a stereoisomer thereof, or a pesticide-acceptable salt thereof.

[0010] in,

[0011] R 1 The group consisting of H or a substituted or unsubstituted group selected from the group consisting of: C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C10 cycloalkyl, C3-C10 cycloalkoxy, C3-C8 heterocyclic alkyl containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, 5-7 membered heteroaryl containing 1-3 heteroatoms selected from N, O and S, -O (C6-C10 aryl), -O (containing 1-3... -O (containing 1-3 C3-C8 heterocyclic alkyl groups selected from N, O, and S heteroatoms), -NH (C1-C10 alkyl), -NH (C3-C10 cycloalkyl), -NH (C6-C10 aryl), -NH (containing 1-3 5-7 heterocyclic alkyl groups selected from N, O, and S heteroatoms), -NH (containing 1-3 C3-C8 heterocyclic groups selected from N, O, and S heteroatoms);

[0012] R 2The group is H or a substituted or unsubstituted group selected from the group consisting of: halogen, OH, NO2, NH2, CN, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, saturated or unsaturated C3-C8 cycloalkyl, C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O and S, C2-C6 alkenyloxy, C2-C6 alkynyl, C6-C10 aryl, 5-7 membered heteroaryl containing 1-3 heteroatoms selected from N, O and S, C1- C6 aldehyde, -C(=O)(C1-C6 alkyl), -OC(=O)(C6-C10 aryl), -OC(=O)(C6-C10 aryl)(C2-C6 alkenyl), -OC(=O)(C1-C8 alkylene)(C6-C10 aryl), -OC(=O)(C1-C8 alkylene)phenyl(C2-C6 alkenyl), -(C1-C8 alkylene)NHC(=O) (containing 1-3 5-7 heteroaryl groups selected from N, O and S heteroatoms);

[0013] The substitution refers to substitution by one or more groups selected from the group consisting of: halogen, CN, NO2, OH, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 thioalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C8 cycloalkyl, C3-C8 heterocyclic group containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, and 5-7 membered heteroaryl group containing 1-3 heteroatoms selected from N, O and S.

[0014] In another preferred embodiment, R 1 The group is H or is substituted or unsubstituted and selected from the group consisting of: C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C8 cycloalkyl, C3-C10 cycloalkoxy, C3-C8 heterocyclic alkyl containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, 5-7 heteroaryl containing 1-3 heteroatoms selected from N, O and S, -O (C6-C10 aryl), -O (5-7 heteroaryl containing 1-3 heteroatoms selected from N, O and S), -O (C3-C8 heterocyclic alkyl containing 1-3 heteroatoms selected from N, O and S);

[0015] R 2 The group is H or is substituted or unsubstituted and selected from the group consisting of: halogen, OH, NO2, NH2, CN, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, saturated or unsaturated C3-C8 cycloalkyl, C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, 5-7 membered heteroaryl containing 1-3 heteroatoms selected from N, O and S, carbonyl, and C1-C6 aldehyde.

[0016] In another preferred embodiment, R 1 The group is H or is substituted or unsubstituted and selected from the group consisting of: C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C10 cycloalkyl, C3-C10 cycloalkoxy, C3-C8 heterocyclic alkyl containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, and 5-7 heteroaryl containing 1-3 heteroatoms selected from N, O and S.

[0017] In another preferred embodiment, R 2 The group selected from the group consisting of substituted or unsubstituted groups: halogen, NO2, NH2, CN, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, saturated or unsaturated C3-C8 cycloalkyl, C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, 5-7 heteroaryl containing 1-3 heteroatoms selected from N, O and S, and C1-C6 aldehyde.

[0018] In another preferred embodiment, the compound of formula I is the compound of formula II.

[0019] in,

[0020] R 2 H or a substituted or unsubstituted group selected from the group consisting of: halogens, OH, NO2, NH2, CN, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, saturated or unsaturated C3-C8 cycloalkyl, C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O and S, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C6-C10 aryl, and groups containing 1-3 heteroatoms. Selected from 5-7 membered heteroaryl, C1-C6 aldehyde, -C(=O)(C1-C6 alkyl), -OC(=O)(C6-C10 aryl), -OC(=O)(C6-C10 aryl)(C2-C6 alkenyl), -OC(=O)(C1-C8 alkylene)(C6-C10 aryl), -OC(=O)(C1-C8 alkylene)phenyl(C2-C6 alkenyl);

[0021] The substitution refers to substitution by one or more groups selected from the group consisting of: halogen, CN, NO2, OH, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 thioalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C8 cycloalkyl, C3-C8 heterocyclic group containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, and 5-7 membered heteroaryl group containing 1-3 heteroatoms selected from N, O and S.

[0022] In another preferred embodiment, R 2 The group selected from the group consisting of substituted or unsubstituted groups: C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, saturated or unsaturated C3-C8 cycloalkyl, C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O and S, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C6-C10 aryl, and 5-7 heteroaryl containing 1-3 heteroatoms selected from N, O and S.

[0023] In another preferred embodiment, the compound of formula I is the compound of formula III.

[0024] in,

[0025] R 1 As defined above;

[0026] R 3 The group is H or is substituted or unsubstituted and selected from the group consisting of: halogen, OH, NH2, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C8 cycloalkyl, C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, and 5-7 heteroaryl containing 1-3 heteroatoms selected from N, O and S.

[0027] The substitution refers to substitution by one or more groups selected from the group consisting of: halogen, CN, NO2, OH, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 thioalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C8 cycloalkyl, C3-C8 heterocyclic group containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, and 5-7 membered heteroaryl group containing 1-3 heteroatoms selected from N, O and S.

[0028] n is 0, 1, or 2.

[0029] In another preferred embodiment, the compound of formula I is the compound of formula IV.

[0030] in,

[0031] R 1 As defined above;

[0032] R 3The group is H or is substituted or unsubstituted and selected from the group consisting of: halogen, OH, NH2, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C8 cycloalkyl, C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, and 5-7 heteroaryl containing 1-3 heteroatoms selected from N, O and S.

[0033] The substitution refers to substitution by one or more groups selected from the group consisting of: halogen, CN, NO2, OH, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 thioalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C8 cycloalkyl, C3-C8 heterocyclic group containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, and 5-7 membered heteroaryl group containing 1-3 heteroatoms selected from N, O and S.

[0034] In another preferred embodiment, the compound is selected from the group consisting of:

[0035] A second aspect of the present invention provides a composition comprising:

[0036] (i) the compound as described in the first aspect of the invention, or its geometric isomers, or its stereoisomers, or its pesticide-acceptable salts; and

[0037] (ii) A pesticide-acceptable carrier.

[0038] A third aspect of the invention provides the use of the compound as described in the first aspect of the invention for preparing an insect repellent.

[0039] In another preferred embodiment, the pest repellent is used for:

[0040] (a) Regulating pest behavior;

[0041] (b) Control and / or prevent pest infestations that damage useful plants.

[0042] A fourth aspect of the invention provides a method for controlling and / or preventing damage to useful plants caused by pest infestation, comprising the steps of applying an insecticidal effective dose of a compound of formula I, or a geometrical isomer thereof, a stereoisomer thereof, an agronomically acceptable salt thereof, or a composition as described in the second aspect of the invention, to a pest, a pest-infested area, or a plant susceptible to pest infestation.

[0043] It should be understood that, within the scope of this invention, the above-described technical features of this invention and the technical features specifically described below (such as in the embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, they will not be described in detail here. Attached Figure Description

[0044] Figure 1 shows the experimental results of antennal potentials for compounds 1, 2, 3 and 4 of this application.

[0045] Figure 2 shows the stability test results of compounds 1, 2, 3 and 4 of this application.

[0046] Figure 3 shows the results of the pot experiment for the preferred compound 2.

[0047] Figure 4 shows the calculated analysis of the saturated vapor pressure and logP values ​​for compounds 1, 2, 3, and 4. Detailed Implementation

[0048] Through extensive and in-depth research, the inventors have unexpectedly developed a series of novel aphid pheromone analogs. These compounds retain the carbonyl functional group of nepeta lactone and introduce phytovolatile components on the other side to achieve a stronger repellent effect against aphids. The invention also provides a method for preparing these compounds and their use in controlling and / or preventing damage to beneficial plants caused by pest infestations. Based on this, the inventors completed this invention.

[0049] the term

[0050] In this invention, unless otherwise specified, the terms used have the general meanings known to those skilled in the art.

[0051] In this invention, the term "halogen" refers to F, Cl, Br, or I.

[0052] In this invention, "C1-C6 alkyl" refers to a straight-chain or branched alkyl group comprising 1-6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, pteropentyl, or similar groups. The similar term "C1-C4 alkyl" has a similar definition.

[0053] In this invention, the term "C1-C6 alkoxy" refers to a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, including but not limited to methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, etc. Similar terms such as "C1-C4 alkoxy" have similar definitions.

[0054] In this invention, the term "C2-C6 alkenyl" refers to a straight-chain or branched alkenyl group having 2 to 6 carbon atoms and containing at least one double bond, including but not limited to vinyl, propenyl, butenyl, isobutenyl, pentenyl, and hexenyl.

[0055] In this invention, the term "C2-C6 ynyl" refers to a straight-chain or branched ynyl group having 2 to 6 carbon atoms and containing at least one triple bond, including but not limited to ethynyl, propynyl, butynyl, isobutynyl, pentynyl, and hexynyl.

[0056] In this invention, the term "C3-C8 cycloalkyl" represents a cyclic aliphatic hydrocarbon group consisting of 3 to 8 cyclic carbon atoms, and so on. It should be understood that "cycloalkyl" as used in this invention includes not only monocyclic aliphatic hydrocarbon groups, but also fused ring, spiro ring, and bridged ring systems composed of multiple cyclic aliphatic hydrocarbons. "Cycloalkyl" as used in this invention includes not only aliphatic hydrocarbon groups with fully saturated carbon atoms, but also aliphatic hydrocarbon groups with some carbon atoms having unsaturated bonds. Examples of "cycloalkyl" as used in this invention include, but are not limited to: When "cycloalkyl" is used as a substituent, the connection site with the main molecule can occur at any position allowed by the chemical bonds on the "cycloalkyl". Terms such as "C3-C6 cycloalkyl" have similar definitions.

[0057] In this invention, the term "aryl" refers to a monocyclic or bicyclic system consisting of a specific number of carbon atoms that obeys Hückel's rule. It should be understood that when "aryl" in this invention refers to a bicyclic system, it includes not only the case where all rings are aromatic rings, but also the case where only one ring is an aromatic ring and the other ring is a non-aromatic aliphatic ring.

[0058] In this invention, the term "C6-C10 aryl" refers to a cyclic system having 6 to 10 carbon atoms, and at least one ring being an aromatic ring; examples of "aryl" in this invention include, but are not limited to, those described in this invention. When "aryl" is used as a substituent, the connection site with the main molecule occurs on the aromatic ring.

[0059] In this invention, the term "heterocyclic alkyl" refers to a non-aromatic cyclic group that indicates a specific number of cyclic atoms, contains at least one cyclic heteroatom (N, O, or S), and is saturated or partially unsaturated. It should be understood that the "heterocyclic group" described in this invention includes not only monocyclic heterocyclic systems but also polycyclic heterocyclic systems, such as fused rings, spirocyclic rings, and bridged rings. When the "heterocyclic group" is a polycyclic system, at least one ring contains a cyclic heteroatom, and the other rings may contain cyclic heteroatoms or be cyclic alkyl groups. For example, the term "4-8 membered heterocyclic alkyl" refers to a monocyclic or polycyclic system having 4 to 8 cyclic atoms, at least one of which is a heteroatom, and is saturated or partially unsaturated. The definitions of other similar terms follow the same pattern. More preferably, the number of heteroatoms is 1 to 3. This includes (but is not limited to) the following groups: It is important to understand that when a "heterocyclic group" is used as a substituent, the connection site with the main body of the molecule can occur at any position allowed by the chemical bonds on the "heterocyclic group".

[0060] In this invention, the term "heteroaryl" refers to a cyclic group with a specific number of cyclic atoms, containing at least one cyclic heteroatom (N, O, or S), and possessing aromaticity. Unless otherwise defined, the "heteroaryl" in this invention includes not only monocyclic heteroaryl systems but also polycyclic heteroaryl systems, such as bicyclic, tricyclic, and tetracyclic heteroaryl systems. When the "heteroaryl" is a polycyclic heteroaryl system, at least one ring is aromatic, and the other rings can be aromatic or non-aromatic. The heteroatom can be located in an aromatic ring or a non-aromatic ring. Polycyclic heteroaryl systems include not only fused ring systems but also bridged and spirocyclic systems. The term "5-7 membered heteroaryl" refers to a cyclic group having 5 to 7 cyclic atoms, at least one of which is a heteroatom, and possessing aromaticity. The definitions of other similar terms follow the same pattern.

[0061] In this invention, the term "halogenated" refers to being replaced by a halogen.

[0062] In this invention, the term "optionally" means that when there is a series of candidate groups to choose from, some of them can be selected, or none can be selected.

[0063] In this invention, "each independently" means that when several substituents defined at the same time are selected from the same series of candidate groups, they do not affect each other, and they may be the same or different.

[0064] In this invention, the term "substitution" refers to the replacement of one or more hydrogen atoms on a specific group by a specific substituent. The specific substituent is either the substituent described accordingly above or the substituent appearing in the various embodiments. Unless otherwise specified, a substituted group may have a substituent selected from a specific group at any substituted site of that group, and the substituents at each position may be the same or different. Those skilled in the art will understand that the combinations of substituents contemplated in this invention are those that are stable or chemically feasible.

[0065] In this invention, the term "1-6" refers to having 1, 2, 3, 4, 5 or 6, and other similar terms each have a similar meaning independently.

[0066] It should be understood that when a group exists simultaneously at multiple different positions in a compound, its definition at each position is independent and can be the same or different. That is, the term "selected from the following group:" and the term "each independently selected from the following group:" have the same meaning.

[0067] Compound of Formula I of the present invention

[0068] This invention provides a compound of formula I.

[0069] The groups are defined as above.

[0070] In another preferred embodiment, R 1 Substituted or unsubstituted groups selected from the group consisting of C1-C6 alkyl and C1-C6 cycloalkyl groups;

[0071] The substitution refers to substitution by one or more substituents selected from the group consisting of: halogen, CN, OH, C1-C3 alkyl, and C1-C3 haloalkyl.

[0072] In another preferred embodiment, R 1 The group selected from the group consisting of substituted or unsubstituted groups: methyl, ethyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl;

[0073] The substitution refers to substitution by one or more substituents selected from the group consisting of: F, OH, methyl, trifluoromethyl.

[0074] In another preferred embodiment, R 2 Substituted or unsubstituted groups selected from the group consisting of: OH, -C(=O)(C1-C6 alkyl), C1-C6 aldehyde, and C2-C6 alkenyl.

[0075] The substitution refers to substitution by one or more substituents selected from the group consisting of: halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, and C1-C6 haloalkoxy.

[0076] In another preferred embodiment, R 2 The group selected from the group consisting of substituted or unsubstituted groups: C1-C6 aldehydes and C2-C6 alkenes.

[0077] In another preferred embodiment, the compound has the following structure:

[0078] In another preferred embodiment, in the compound, R 1 R 2 and R 3 Each of the above can be independently a group corresponding to the specific compound described in this invention.

[0079] To better understand the objectives, techniques, and advantages of this invention, the invention will be further explained in detail based on the above-described embodiments. It should be understood that the specific embodiments described are for illustrative purposes only and are not intended to limit the scope of the invention.

[0080] This invention provides aphid pheromone analogs for repelling aphids, including pheromone analog 1 (4-(1-oxopropan-2-yl)cyclohex-1-en-1-yl) methyl acetate, analog 2 (4-(but-3-en-2-yl)cyclohex-1-en-1-yl) methyl acetate, analog 3 (4-(1-oxopropan-2-yl)cyclohex-1-en-1-yl) methyl propionate, and analog 4 (4-(1-oxopropan-2-yl)cyclohex-1-en-1-yl) methyl isobutyrate. The structures of these four pheromone analogs are shown above.

[0081] In one embodiment, the aphid pheromone analogue may be selected from compound 1, compound 2, compound 3 and compound 4.

[0082] As used herein, the term "pesticide-acceptable salt" means that the anion of the salt is known and acceptable in forming an insecticide-pesticide-acceptable salt. Preferably, the salt is water-soluble. Suitable acid addition salts formed from compounds of formula (I) include salts formed from inorganic acids, such as hydrochlorides, phosphates, sulfates, and nitrates; and salts formed from organic acids, such as acetates, benzoates, etc.

[0083] The preparation methods of the compounds of Formula I of the present invention are described in more detail below, but these specific methods do not constitute any limitation on the present invention. The compounds of the present invention can also be conveniently prepared by optionally combining various synthetic methods described in this specification or known in the art, such combinations being readily performed by those skilled in the art.

[0084] Typically, the raw materials and reagents used in the preparation process of the compounds of the present invention can be purchased commercially unless otherwise specified.

[0085] Combinations containing the compounds of the present invention and uses of the compounds and compositions thereof.

[0086] In one embodiment, the pheromone analog is dissolved in a hexane solution. The concentration of the solution can be in the range of 0.1 mg / mL to 10 mg / mL.

[0087] Not limited to any specific theory, the aphid sex pheromone analogs used in this invention may have a repellent effect on a variety of aphid species.

[0088] In one embodiment of the invention, the composition may also be supplemented with other excipients according to the intended formulation to be prepared. These excipients may be selected from emulsifiers, diluents, gelling agents, stabilizers or any other excipients, or mixtures thereof.

[0089] In one embodiment of the invention, the emulsifier or diluent may be a suitable organic solvent, and non-limiting examples of emulsifiers or diluents include one or more of acetone, ethanol and methanol, isopropanol, methyl ethyl ketone, etc.

[0090] In one embodiment of the invention, additional adjuvants may be present in appropriate amounts to achieve their intended purpose.

[0091] In one embodiment of the invention, the content of aphid sex pheromone analogues according to the composition and formulation of the invention is within a specific range, while the concentration and amount of additional adjuvants can be varied according to the formulation and amount of the active ingredient.

[0092] Based on laboratory studies (details provided in the examples below), the aphid sex pheromone analogues of the present invention have a certain repellent effect on aphids, thereby expanding the potential of the composition in integrated pest management (IPM), control and eradication programs for aphids.

[0093] In one embodiment of the invention, the useful plant is selected from the group consisting of: maize, cotton, cereals (including winter wheat, spring wheat, spelt wheat, durum wheat, rye, barley, oats, millet, and triticale); rapeseed (including Brassica napus subsp. napus, i.e., Argentine rapeseed, rapeseed, or rapeseed and certain varieties of low-erucic acid rapeseed; Brassica rapa, i.e., Polish rapeseed; Brassica Juncea (high-quality brown mustard); perennial plants (including coffee and fruit trees such as yellow fruit, almond, Indian gooseberry, apple, apricot, avocado, wood apple, Indian date, star fruit, cashew, cherry, citrus (including Clementine, lemon, lime, sweet orange, etc.), coconut, crabapple, Damson plum, durian, elderberry, fig, grapefruit, guava, jackfruit, date, loquat, lychee, mango, hawthorn, sour cherry, mulberry, olive, papaya (including tropical and North American papaya), peach and nectarine, pear, pecan, persimmon, plum, pomelo, wood pear, pomegranate, rambutan, sapodilla, custard apple, sweet chestnut, tree tomato, ugly orange, walnut and rose apple); grapes; rice; sorghum; soybeans; turfgrass; and vegetables, including Brassica oleracea. *Oleracea*, such as cabbage, Brussels sprouts, cauliflower, broccoli, kale, turnip, red cabbage, crème brûlée, Chinese kale, mustard greens; *Brassica rapa*, such as turnip, Chinese cabbage, bok choy; *Raphanus sativus*, such as radish, white radish, seed radish; *Daucus carota*, such as carrot; *Pastinaca sativa*, such as parsnip; *Beta vulgaris*, such as beet, sea beet, Swiss chard, sugar beet; *Lactuca sativa*, such as lettuce, asparagus; *Asparagus officinalis*, such as asparagus; *Phaseolus vulgaris*, *Phaseolus coccineus*, and *Phaseolus lunatus*, such as green beans, French beans, pole beans, lima beans; *Vicia*, *Vicia*. (e.g., faba, broad bean); (e.g., Pisum sativum, pea, snow pea, dried pea); (e.g., Solanum tuberosum, potato; Solanum melongena, eggplant; Solanum lycopersicum, tomato); (e.g., Cucumis sativus, cucumber); (e.g., cucumber); (e.g., Cucurbita spp.)Examples of common plant genera include: pumpkin, zucchini, winter melon, and winter squash; Allium cepa (e.g., onion, scallion, green onion, shallot); Allium sativum (e.g., garlic); Allium ampeloprasum (e.g., leek, garlic chive); Capsicum annuum (e.g., chili pepper, bell pepper, bell pepper); Spinacia oleracea (e.g., spinach); Dioscorea spp. (e.g., yam); Ipomoea batatas (e.g., sweet potato); and Manihot esculenta (e.g., cassava).

[0094] The compositions provided by this invention comprise a compound of formula 1, a liquid or solid carrier, and optionally one or more conventional formulation adjuvants, which may be liquid or solid, such as surfactants, defoamers (e.g., silicone oils), preservatives, clays, inorganic compounds, viscosity modifiers, adhesives, and / or thickeners. Furthermore, the compositions may further comprise fertilizers, micronutrient donors, or other formulations that influence plant growth.

[0095] In another embodiment of the invention, the pest is an aphid (Aphis spp.), preferably a citrus aphid (Aphis citricola), bean aphid (Aphis craccivora), broad bean aphid (Aphis fabae), forbes aphid (Aphis forbesi), soybean aphid (Aphis glycines), cotton aphid (Aphis gossypii), ivy aphid (Aphis hederae), Illinois aphid (Aphis illinoisensis), Middleton aphid (Aphis middletoni), watercress aphid (Aphis nasturtii), oleander aphid (Aphis nerii), apple aphid (Aphis pomi), apple spiraecola (Aphis spiraecola), or viburnum aphid (Aphis vibumiphila); more preferably a bean aphid (Aphis craccivora), broad bean aphid (Aphis fabae), soybean aphid (Aphis glycines), or cotton aphid (Aphis spp.). The useful plants are selected from cotton, soybean, Cucurbita spp., Phaseolus spp., broad bean (Vicia faba), and pea (Pisum sativum).

[0096] In another embodiment of the invention, the use of the Formula I compound for controlling or preventing aphid (Aphis spp.) damage to useful plants is provided, as well as a method for controlling or preventing aphid damage by applying the Formula I compound, the method comprising applying an insecticidal effective dose of the Formula I compound to the useful plant. The useful plant is selected from cotton, soybean, Cucurbita spp., Phaseolus spp., Vicia faba, and Pisum sativum. The aphid species include citrus aphid (Aphis citricola), bean aphid (Aphis craccivora), broad bean aphid (Aphis fabae), yellow apple aphid (Aphis forbesi), soybean aphid (Aphis glycines), cotton aphid (Aphis gossypii), ivy aphid (Aphis hederae), grape aphid (Aphis illinoisensis), middle aphid (Aphis middletoni), water celery aphid (Aphis nasturtii), milkweed aphid (Aphis nerii), apple aphid (Aphis pomi), pear aphid (Aphis spiraecola), and lotus aphid (Aphis vibumiphila).

[0097] In another embodiment of the invention, the use of the compound of formula I for controlling or preventing damage to useful plants by the peach aphid (Myzus persicae) is provided, as well as a method for controlling or preventing peach aphid damage by applying the compound of formula I, the method comprising applying the compound of formula I to the useful plants at an insecticidal effective dose when the peach aphid appears, wherein the useful plants are selected from cotton, rapeseed, and vegetables, the vegetables including tomato (Solanum lycopersicum, preferably tomato), pepper (Capsicum annuum, preferably pepper, bell pepper), eggplant (Solanum melongena, preferably eggplant), Brassica oleracea, spinach (Spinacia oleracea, preferably spinach), Lactuca sativa (Lactuca sativa, preferably lettuce), carrot (Daucus carota, preferably carrot), and potato (Solanum tuberosum, preferably potato).

[0098] The compounds of this invention can be used alone or in combination with other aphid repellents.

[0099] The other aphid repellents have the following structure:

[0100] The foregoing description of the invention and the following appendices should not be construed as limiting the invention, as those skilled in the art will be able to conceive of other forms of the invention within the scope defined in the drawings.

[0101] In one embodiment, the present invention relates to the application and use of novel aphid pheromone analogs, such as compounds 1, 2, 3, and 4, as novel pest control agents. These analogs offer improved properties in terms of human and environmental safety compared to standard aphid control chemicals and solutions.

[0102] Compared with the prior art, the main advantages of the present invention are:

[0103] (a) The compounds of the present invention have excellent pest repellency capabilities.

[0104] (b) The compounds of the present invention can effectively regulate aphid behavior.

[0105] (c) The compounds of the present invention have simple synthesis steps, high yield and good purity.

[0106] (d) The compounds of this invention have significant structural innovation.

[0107] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. Unless otherwise stated, percentages and parts are weight percentages and parts by weight.

[0108] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as are familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to the methods of this invention. The preferred embodiments and materials described herein are for illustrative purposes only.

[0109] Compound preparation examples

[0110] Example 1: Synthesis of Compound 1 (4-(1-oxopropan-2-yl)cyclohex-1-en-1-yl)methyl acetate

[0111] Perillyl alcohol (300 mg, 1.97 mmol) and acetic acid (142 mg, 2.37 mmol) were dissolved in dichloromethane (10 mL) and stirred in an ice bath. Then, N,N'-dicyclohexylcarbodiimide (DCC, 488 mg, 2.37 mmol) and 4-dimethylaminopyridine (DMAP, 29 mg, 0.24 mmol) were added, and stirring was continued for 10 minutes. The ice bath was then removed, and stirring was continued at room temperature for 3 hours until the product was detected by thin-layer chromatography (TLC). After the reaction was complete, the reaction mixture was washed sequentially with saturated sodium bicarbonate aqueous solution, followed by extraction with dichloromethane (10 mL × 3). The organic phase was dried over anhydrous sodium sulfate, filtered, rotary evaporated, and purified by silica gel column chromatography (gradient: 0-10% petroleum ether / ethyl acetate) to obtain (4-(prop-1-en-2-yl)cyclohex-1-en-1-yl)methyl acetate (367 mg, yield 96%), which was a colorless oil. 1 H NMR(400MHz, CDCl3)δ5.75(br s,1H),4.71(d,J=6.8Hz,2H),4.45(s,2H),2.20–2.11(m,2H),2.10–2.07(m,2H),2 .06(s,3H),2.02–1.91(m,1H),1.88–1.80(m,1H),1.73(s,3H),1.55–1.42(m,1H).

[0112] Under argon protection, 2.4 mL (1.13 mmol) of 9-boronbicyclo[3.3.1]nonane in 0.5 M tetrahydrofuran solution was added dropwise to compound 1 (200 mg, 1.03 mmol) at 0 °C. After the addition was complete, stirring was continued for 10 minutes, then the ice bath was removed, and the reaction was stirred at room temperature for 3 hours. Subsequently, the reaction solution was cooled to 0 °C, and 10 mL of sodium perborate aqueous solution (788 mg, 5.15 mmol) was slowly added, followed by stirring for 2 hours. Then, 20 mL of saturated ammonium chloride solution and 20 mL of ethyl acetate were added to the reaction system, and the mixture was allowed to stand for phase separation. The aqueous phase was extracted with ethyl acetate (20 mL × 2), and the organic phases were combined, washed successively with saturated brine, dried over anhydrous sodium sulfate, and then rotary evaporated. Finally, the compound (4-(1-hydroxypropyl-2-yl)cyclohex-1-en-1-yl)methyl acetate (148 mg, yield 68%) was purified by silica gel column chromatography (gradient: 10-30% petroleum ether / ethyl acetate) as a colorless oil. 1H NMR(400MHz,CDCl3)δ5.70(br s,1H),4.41(s,2H),3.65–3.56(m,1H),3.51–3.43(m,1H),2.06–1.99(m,5H),1.92–1.79(m,2 H),1.81–1.69(m,3H),1.65–1.53(m,2H),1.28–1.18(m,1H),0.91(d,J=6.4Hz,1.69H,isomer 1),0.88(d,J=6.4Hz,1.69H,isomer 2).

[0113] Under argon protection, compound (4-(1-hydroxypropan-2-yl)cyclohexyl-1-en-1-yl)methyl acetate (203 mg, 0.96 mmol) was dissolved in dichloromethane (5 mL), followed by the sequential addition of N-methylmorpholine oxide (168 mg, 1.44 mmol) and tetrapropylammonium perruthenate (17 mg, 0.05 mmol, 5 mol%). After stirring the reaction solution for 2 hours, the mixture was filtered through diatomaceous earth and then rotary evaporated. Finally, the compound (4-(1-oxopropan-2-yl)cyclohexyl-1-en-1-yl)methyl acetate (138 mg, yield 68%) was purified by silica gel column chromatography (gradient: 0-30% petroleum ether / ethyl acetate) as a colorless oil. 1 H NMR (400MHz, CDCl3) δ9.65 (d, J=2.4Hz, 0.47H, isomer 1), 9.64 (d, J=2.4Hz, 0.44H, isomer 2), 5.69 (br s,1H),4.42(s,2H),2.33–2.24(m,1H),2.04(s,6H),1.92–1.67(m,2H),1.44–1.29(m,1H),1.07(t,J=4.6Hz,1.50H,isomer 1),1.05(t,J=4.6Hz,1.48H,isomer 2).

[0114] Example 2: Synthesis of Compound 2 (4-(but-3-en-2-yl)cyclohex-1-en-1-yl)methyl acetate

[0115] Methyltriphenylphosphine bromide (207 mg, 0.58 mmol) was dissolved in 5 mL of tetrahydrofuran and stirred at -78 °C. Then, a solution of n-butyllithium (1.6 M, 360 μL, 0.58 mmol) was added dropwise. After stirring for 30 minutes, the mixture was heated to room temperature and stirred for 2 hours. Subsequently, the reaction solution was cooled again to -78 °C, and compound (4-(1-oxopropan-2-yl)cyclohex-1-en-1-yl)methyl acetate (100 mg, 0.48 mmol) was added. The reaction solution was heated to room temperature and stirred for 18 hours. After the reaction was complete, the reaction solution was rotary evaporated and purified by silica gel column chromatography (gradient: 0-15% petroleum ether / ethyl acetate) to give compound (4-(but-3-en-2-yl)cyclohex-1-en-1-yl)methyl acetate (75 mg, yield 76%) as a colorless, transparent oil. 1 H NMR (400MHz, CDCl3) δ5.77–5.63(m,2H),5.00–4.95(m,1H),4.95–4.91(m,1H),4.43(s,2H),2.15–1. 92(m,7H),1.86–1.71(m,1H),1.70–1.58(m,1H),1.48–1.13(m,2H),1.00(d,J=4.4Hz,1.45H,isomer 1),0.99(d,J=4.4Hz,1.59H,isomer 2).

[0116] Example 3 Synthesis of Compound 3 (4-(1-oxopropan-2-yl)cyclohex-1-en-1-yl)methylpropionate The specific synthesis operation of Compound 3 is similar to that of Compound 1.

[0117] (4-(prop-1-en-2-yl)cyclohex-1-en-1-yl)methylpropionate: colorless, transparent oil, yield 94%; 1 H NMR(400MHz,CDCl3)δ5.74(br s,1H),4.75–4.67(m,2H),4.46(s,2H),2.34(q,J=7.6Hz,2H),2.20–2.10(m,2H),2.10–2.04(m,2 H),2.02–1.90(m,1H),1.88–1.80(m,1H),1.73(s,3H),1.54–1.42(m,1H),1.14(t,J=7.6Hz,3H).

[0118] (4-(1-hydroxypropan-2-yl)cyclohex-1-en-1-yl)methylpropionate: colorless, transparent oil, yield 73%; 1H NMR(400MHz,CDCl3)δ5.70(br s,1H),4.43(s,2H),3.66–3.56(m,1H),3.52–3.36(m,2H),2.32(q,J=7.6Hz,2H),2.07–1.96(m,2H),1.93– 1.69(m,3H),1.70–1.46(m,2H),1.42–1.17(m,1H),1.12(t,J=7.6Hz,3H),0.91(d,J=6.6Hz,1.64H,isomer 1),0.89(d,J=6.6Hz,1.31H,isomer 2).

[0119] (4-(1-oxopropan-2-yl)cyclohex-1-en-1-yl)propyl formate: colorless, transparent oil, yield 70%; 1 H NMR (400MHz, CDCl3) δ9.68 (d, J=2.4Hz, 0.46H, isomer 1), 9.66 (d, J=2.4Hz, 0.45H, isomer 2), 5.71 (br s,1H),4.45(s,2H),2.43–2.26(m,3H),2.12–2.02(m,3H),2.01–1.94(m,1H),1.91–1.84(m,1H ),1.83–1.70(m,1H),1.44–1.33(m,1H),1.14(t,J=7.6Hz,3H),1.09(d,J=4.8Hz,1.46H,isomer 1), 1.07 (d, J=4.8Hz, 1.48H, isomer 2).

[0120] Example 4: Synthesis of compound 4 (4-(1-oxopropan-2-yl)cyclohex-1-en-1-yl)methyl isobutyrate

[0121] The specific synthetic procedure for compound 4 is similar to that for compound 1.

[0122] (4-(prop-1-en-2-yl)cyclohex-1-en-1-yl)methyl isobutyrate: colorless, transparent oil, yield 72%; 1H NMR(400MHz,CDCl3)δ5.74(br s,1H),4.76–4.67(m,2H),4.45(s,2H),2.56(hept,J=7.0Hz,1H),2.20–2.10(m,2H),2.10–2.03(m ,2H),2.03–1.90(m,1H),1.89–1.80(m,1H),1.73(s,3H),1.55–1.42(m,1H),1.17(d,J=7.0Hz,6H).

[0123] (4-(1-hydroxypropan-2-yl)cyclohex-1-en-1-yl)methyl isobutyrate: colorless, transparent oil, yield 69%; 1 H NMR(400MHz,CDCl3)δ5.70(br s,1H),4.43(s,2H),3.67–3.57(m,1H),3.53–3.45(m,1H),2.54(hept,J=7.0Hz,1H),2.13–1.98(m,2H),1.9 3–1.74(m,2H),1.72–1.48(m,3H),1.39–1.26(m,1H),1.16(d,J=7.0Hz,6H),0.92(d,J=6.6Hz,1.65H,isomer 1),0.90(d,J=6.6Hz,1.72H,isomer 2).

[0124] Synthesis of target compound V-27

[0125] (4-(1-oxopropan-2-yl)cyclohex-1-enyl)carboxylate: colorless, transparent oil, yield 72%; 1 H NMR (400MHz, CDCl3) δ9.66 (d, J=2.4Hz, 0.44H, isomer 1), 9.64 (d, J=2.4Hz, 0.47H, isomer 2), 5.68 (br s,1H),4.43(s,2H),2.54(hept,J=7.0Hz,1H),2.35–2.22(m,1H),2.14–2.00(m,3H),1.99–1.90(m,1H),1.8 9–1.81(m,1H),1.81–1.68(m,1H),1.42–1.31(m,1H),1.15(d,J=7.0Hz,6H),1.07(d,J=4.8Hz,1.38H,isomer 1),1.05(d,J=4.8Hz,1.58H,isomer 2).

[0126] Test Experiment Implementation Examples

[0127] Test Example 1 Solution Formulation

[0128] When preparing pheromone analog solutions, an appropriate amount of pheromone analog was dissolved in n-hexane solution to prepare experimental group solutions with concentrations of 0.1 mg / mL, 1 mg / mL, and 10 mg / mL, respectively.

[0129] Test Example 2: Biological Testing of Pheromone Analogs

[0130] Experimental Methods: The biological tests were performed using a T-tube olfactometer. 10 μL of the appropriate concentration of solution was sprayed evenly onto a 1 cm × 1 cm filter paper and allowed to stand for 1 minute to allow the solvent to evaporate completely. The treated filter paper was then fixed to one side of the T-tube olfactometer as the experimental group, while filter paper sprayed with an equal volume of n-hexane solvent was placed on the other side as the control group.

[0131] Twenty aphids were placed in the center of a T-tube, and the insects' choice of different arms was recorded over 15 minutes. The repulsion value (RV) was determined using the following formula: RV = [(CT) / (C+T)] × 100%, where C and T represent the number of aphids observed in the control group and the treatment group, respectively.

[0132] Experimental results: The repellency rates of the compounds of the present invention against aphids at concentrations of 10 mg / mL, 1 mg / mL and 0.1 mg / mL are shown in Table 1.

[0133] Table 1

[0134] Experimental Conclusions: As shown in the table above, the compounds of this invention exhibit a repellency rate of over 45% against aphids at a concentration of 10 mg / mL, indicating that these compounds possess excellent pest-repelling capabilities. Specifically, compounds I-44, I-51, I-101, and I-102 all show a repellency rate exceeding 70% at a concentration of 1 mg / mL; compounds I-51 and I-102 still demonstrate a repellency rate exceeding 70% at a concentration of 0.1 mg / mL. This demonstrates that by extending the distance between the double bond and the cyclohexene structure based on the known structural framework, the repellency rate of the compounds of this invention can be effectively improved.

[0135] Test Example 3: Antennae Potential Experiment

[0136] Experimental methods: To further explore the effects of the compounds, antennal potential experiments were conducted on representative compounds 1, 2, 3 and 4, with EBF used as a control compound.

[0137] Experimental results: As shown in Figure 1, aphids can sense these four derivatives, but the antennal potential responses they elicit are all less than those EBF, and the EAG response shows a decreasing trend as the concentration decreases.

[0138] Compound 2 exhibited the highest potential response at all concentrations (second only to EBF), indicating its effective stimulation of aphid antennal receptors, consistent with its good repellent activity demonstrated in behavioral experiments. In contrast, compounds 1, 3, and 4 showed lower EAG responses, particularly at a concentration of 0.1 mg / mL, suggesting weaker binding affinity to aphid olfactory receptors. This result further indicates that, during compound structure optimization, the introduction of alkenyl groups may play a greater role than aldehyde groups in enhancing olfactory receptor recognition and repellent activity, providing a new direction for subsequent molecular optimization.

[0139] Test Example 4 Stability Test

[0140] Experimental Methods: Given the structural instability of EBF, which limits its practical application, stability tests were conducted on representative compounds 1, 2, 3, and 4. Their half-lives were estimated by measuring their content change curves to assess their feasibility in pesticide development.

[0141] Experimental Results: The results in Figure 2 show that the stability of these compounds is significantly improved compared to EBF. Among them, compound 2 has the longest half-life (44.1 days), exhibiting the best stability; while the half-lives of compounds 1, 3, and 4 are 18.1 days, 17.4 days, and 18.7 days, respectively, all meeting the stability requirements for pesticide development and demonstrating good application potential.

[0142] Test Example 5: Potted Plant Experiment

[0143] Experimental Methods: Given that compound 2 exhibits optimal stability and repellent activity, a pot experiment was conducted to evaluate its practical application. In this experiment, broad bean seedlings (Vicia faba) were planted in small pots. Each pot contained five seedlings, with one seedling in the center inoculated with 15 aphids (Aphis craccivora), and the remaining four seedlings arranged diagonally around it. Compound 2 was prepared into three concentrations (0.1, 1, and 10 mg / mL) of distilled aqueous solution containing 2% acetone. The treatment group was sprayed with the corresponding solution on the plants along one diagonal line in the pot, while the control group was not sprayed. The plants in each pot were arranged in a mixed order to avoid interference from light or temperature gradients on aphid migration. Each pot was placed in a separate mesh cage to prevent aphid escape or cross-infestation, and then placed in an artificial climate chamber. On days 4, 6, 8 and 12 after the start of the experiment, the number of surviving aphids on each plant was recorded. By comparing the changes in the number of aphids in the treatment group and the control group, the persistence and control efficiency of the compound were analyzed.

[0144] Experimental results: As shown in Figure 3, at concentrations of 10 mg / mL and 0.1 mg / mL, the number of aphids in the treatment group was similar to that in the control group, and even slightly higher at some time points. This indicates that at these concentrations, compound V-24 did not show a significant repellent effect.

[0145] At a concentration of 1 mg / mL, the number of aphids in the treatment group was significantly lower than that in the control group on days 4 and 6, indicating that compound 2 at this concentration could effectively reduce aphid infestation and provide some protection for crops. This result suggests that compound 2 has good application prospects within a suitable concentration range and warrants further optimization and research to determine the optimal application method and field application strategy, thereby improving its actual repellency effect.

[0146] Test Example 6 Calculation Analysis

[0147] Experimental Methods: To further investigate the relationship between the physicochemical properties of the compounds and their repellency activity, the saturated vapor pressure and logP were calculated for representative compounds 1, 2, 3, and 4. The saturated vapor pressure was predicted using the CompTox Chemicals Dashboard, and the logP values ​​were calculated using the ALOGPS2.1 program.

[0148] Experimental results: The physicochemical properties of compounds 1, 2, 3 and 4 are shown in Table 2.

[0149] Table 2 Physicochemical properties of compounds 1, 2, 3 and 4

[0150] The data show a correlation between saturated vapor pressure and the repellent activity of compounds. Compound 2 has the highest saturated vapor pressure and also exhibits the best repellent activity; the methyl group on its left-hand ester group enhances volatility while maintaining activity. This trend suggests that, with the same active skeleton, compounds with higher volatility generally have better repellent activity. This may be because higher volatility allows the compound to diffuse into the air more quickly, thus affecting aphid behavior over a wider area.

[0151] Furthermore, logP reflects the lipophilicity of the compound, which may have some influence on its penetration through insect antennae. Compound 2 has the highest clogP value, indicating that it has strong lipophilicity and can effectively penetrate the insect antennal lymph, promoting its interaction with odorant-binding proteins, thereby regulating insect behavior.

[0152] By comparing the electrostatic potential diagrams of compound 2 and EBF (Figure 4), it can be found that compound 2 is not only highly similar to EBF in configuration, but also shows significant similarity in electron distribution. In particular, the right-hand region of its molecule exhibits an electron-rich characteristic, with a charge distribution similar to the corresponding region of EBF. This similarity in electronic properties may play a key role in the molecular recognition process, enabling compound 2 to effectively mimic the mechanism of action of EBF, thus exhibiting good repellency activity.

[0153] All documents mentioned in this invention are incorporated herein by reference as if each document were individually incorporated by reference. Furthermore, it should be understood that after reading the foregoing teachings of this invention, those skilled in the art can make various alterations or modifications to this invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. A compound of Formula I, or a geometrical isomer thereof, a stereoisomer thereof, or a pesticide-acceptable salt thereof, in, R 1 The group consisting of H or a substituted or unsubstituted group selected from the group consisting of: C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C10 cycloalkyl, C3-C10 cycloalkoxy, C3-C8 heterocyclic alkyl containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, 5-7 membered heteroaryl containing 1-3 heteroatoms selected from N, O and S, -O (C6-C10 aryl), -O (containing 1-3... -O (containing 1-3 C3-C8 heterocyclic alkyl groups selected from N, O, and S heteroatoms), -NH (C1-C10 alkyl), -NH (C3-C10 cycloalkyl), -NH (C6-C10 aryl), -NH (containing 1-3 5-7 heterocyclic alkyl groups selected from N, O, and S heteroatoms), -NH (containing 1-3 C3-C8 heterocyclic groups selected from N, O, and S heteroatoms); R 2 The group is H or a substituted or unsubstituted group selected from the group consisting of: halogen, OH, NO2, NH2, CN, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, saturated or unsaturated C3-C8 cycloalkyl, C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O and S, C2-C6 alkenyloxy, C2-C6 alkynyl, C6-C10 aryl, 5-7 membered heteroaryl containing 1-3 heteroatoms selected from N, O and S, C1- C6 aldehyde, -C(=O)(C1-C6 alkyl), -OC(=O)(C6-C10 aryl), -OC(=O)(C6-C10 aryl)(C2-C6 alkenyl), -OC(=O)(C1-C8 alkylene)(C6-C10 aryl), -OC(=O)(C1-C8 alkylene)phenyl(C2-C6 alkenyl), -(C1-C8 alkylene)NHC(=O) (containing 1-3 5-7 heteroaryl groups selected from N, O and S heteroatoms); The substitution refers to substitution by one or more groups selected from the group consisting of: halogen, CN, NO2, OH, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 thioalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C8 cycloalkyl, C3-C8 heterocyclic group containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, and 5-7 membered heteroaryl group containing 1-3 heteroatoms selected from N, O and S.

2. The compound of claim 1, wherein R 1 The group is H or is substituted or unsubstituted and selected from the group consisting of: C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C8 cycloalkyl, C3-C10 cycloalkoxy, C3-C8 heterocyclic alkyl containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, 5-7 heteroaryl containing 1-3 heteroatoms selected from N, O and S, -O (C6-C10 aryl), -O (5-7 heteroaryl containing 1-3 heteroatoms selected from N, O and S), -O (C3-C8 heterocyclic alkyl containing 1-3 heteroatoms selected from N, O and S); R 2 The group is H or is substituted or unsubstituted and selected from the group consisting of: halogen, OH, NO2, NH2, CN, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, saturated or unsaturated C3-C8 cycloalkyl, C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, 5-7 membered heteroaryl containing 1-3 heteroatoms selected from N, O and S, carbonyl, and C1-C6 aldehyde.

3. The compound as claimed in claim 3, characterized in that, R 1 The group is H or is substituted or unsubstituted and selected from the group consisting of: C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C10 cycloalkyl, C3-C10 cycloalkoxy, C3-C8 heterocyclic alkyl containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, and 5-7 heteroaryl containing 1-3 heteroatoms selected from N, O and S.

4. The compound of claim 3, wherein R 2 The group selected from the group consisting of substituted or unsubstituted groups: halogen, NO2, NH2, CN, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, saturated or unsaturated C3-C8 cycloalkyl, C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, 5-7 heteroaryl containing 1-3 heteroatoms selected from N, O and S, and C1-C6 aldehyde.

5. The compound according to claim 1, characterized in that, Compound I is a compound of formula II. in, R 2 H or a substituted or unsubstituted group selected from the group consisting of: halogens, OH, NO2, NH2, CN, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, saturated or unsaturated C3-C8 cycloalkyl, C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O and S, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C6-C10 aryl, and groups containing 1-3 heteroatoms. Selected from 5-7 membered heteroaryl, C1-C6 aldehyde, -C(=O)(C1-C6 alkyl), -OC(=O)(C6-C10 aryl), -OC(=O)(C6-C10 aryl)(C2-C6 alkenyl), -OC(=O)(C1-C8 alkylene)(C6-C10 aryl), -OC(=O)(C1-C8 alkylene)phenyl(C2-C6 alkenyl); The substitution refers to substitution by one or more groups selected from the group consisting of: halogen, CN, NO2, OH, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 thioalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C8 cycloalkyl, C3-C8 heterocyclic group containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, and 5-7 membered heteroaryl group containing 1-3 heteroatoms selected from N, O and S.

6. The compound according to claim 1, characterized in that, Compound I is a compound of formula III. in, R 1 As defined in claim 1 ; R 3 The group is H or is substituted or unsubstituted and selected from the group consisting of: halogen, OH, NH2, C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C8 cycloalkyl, C3-C8 heterocycloalkyl containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, and 5-7 heteroaryl containing 1-3 heteroatoms selected from N, O and S. The substitution refers to substitution by one or more groups selected from the group consisting of: halogen, CN, NO2, OH, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 thioalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C8 cycloalkyl, C3-C8 heterocyclic group containing 1-3 heteroatoms selected from N, O and S, C6-C10 aryl, and 5-7 membered heteroaryl group containing 1-3 heteroatoms selected from N, O and S. n is 0, 1, or 2.

7. The compound according to claim 1, characterized in that, The compounds are selected from the group consisting of:

8. A composition, characterized in that, Include: (i) the compound of claim 1, or its geometric isomer, or its stereoisomer, or its pesticide-acceptable salt; and (ii) A pesticide-acceptable carrier.

9. Use of the compound as claimed in claim 1, characterized in that, Used to prepare insect repellents.

10. A method for controlling and / or preventing damage to useful plants caused by pest infestation, characterized in that, The steps include: applying an insecticidal effective dose of a compound of formula I, or a geometric isomer thereof, a stereoisomer thereof, an agronomically acceptable salt thereof, or the composition as described in claim 8, to pests, pest-infested areas, or pest-vulnerable plants.

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