Ester group-containing pinene analogue as well as preparation and application thereof

Abstract

The invention discloses an ester group-containing pinene analogue as well as preparation and application thereof, and belongs to the field of agricultural chemicals. The structural formula of the ester group-containing pinene analogue provided by the invention is as shown in formula I: # imgabs0. According to the invention, aphid alarm pheromone pinene is subjected to esterification modification to obtain the ester group-containing pinene analogue; bioactivity research shows that the compound has double functions of repelling aphids and luring natural enemies of the aphids, and has a good application prospect in the aspect of green prevention and control of the aphids.

Description

Technical Field

[0001] The invention relates to the field of agricultural chemicals, and in particular to an ester-containing pinene analogue and a preparation method thereof, as well as application of the compound in aphid control and natural enemy attraction. Background Art

[0002] Aphids are worldwide agricultural pests with the characteristics of many species, fast reproduction, overlapping generations, and multiple hosts. At present, the prevention and control of aphids still relies on chemical pesticides. However, the long-term use of traditional pesticides has led to increasingly serious resistance of aphids. As of 2024, peach aphids (Myzus persicae) have become resistant to more than 80 active ingredients of insecticides, ranking in the top 10 of the most resistant invertebrates in the world. Therefore, it is urgent to develop new green, safe and efficient aphid control agents. In recent years, the use of aphid natural enemies for biological control of aphids has been favored by people because of its environmental friendliness and safety to non-target organisms.

[0003] Diaeretiella rapae is a gregarious, polyphagous endoparasitic wasp of the order Hymenoptera, family Aphididae, genus Diaeretiella. As an important natural enemy of biological control, it has a very wide host range. It mainly parasitizes various aphids of the superfamily Aphidoidea, such as peach aphid, radish aphid and cabbage aphid, which harm cruciferous crops. It plays a very important role in controlling the aphid population.

[0004] When aphids are attacked or stimulated by external factors, their abdominal tubes will secrete small droplets containing volatile gases with alarm activity - alarm pheromones. Other aphids can receive the alarm signal, produce behavioral responses such as repellent, and quickly flee the scene. In addition to playing a repellent or anti-feeding role to directly resist pests, it can also play an indirect role by attracting natural enemies of pests. It is an important component of aphid alarm pheromone, which can not only effectively repel peach aphids, but also has good fumigation toxicity to peach aphids. When mixed with other terpenoid compounds, it can enhance its repellent activity against aphids. In addition, pinene has attractant activity against many natural enemies of aphids, such as Chinese lacewings, big lacewings, thirteen-spotted ladybirds, multicolored ladybirds and black-banded aphid flies. However, the biological activity of pinene and its analogs against natural enemies of the Aphididae family is still unclear, so its behavioral activity against aphid parasitic wasps deserves further study, in order to develop aphid control agents with dual activities of aphid repellent and parasitic wasp attraction.

[0005] Although aphid alarm pheromone components have the advantages of strong specificity, trace amount and eco-friendly, they also have the disadvantages of being volatile, unstable in structure and difficult to apply in the field. Therefore, it is of great significance to develop aphid control agents with both activity and stability by taking aphid alarm pheromone components as active guides for green prevention and control of aphids. Summary of the invention

[0006] The purpose of the present invention is to provide an ester-containing pinene analogue and its preparation and application. The present invention uses aphid alarm pheromone components as the lead to synthesize the ester-containing pinene analogue. The compound not only has obvious repellent activity against aphids but also has obvious attractant activity against natural enemies of aphids. It has dual activity and can be used for the prevention and treatment of aphids in crops, fruit trees, Chinese herbal medicines and flowers.

[0007] The ester-containing pinene analog provided by the present invention has a structural formula as shown in Formula I:

[0008]

[0009] In Formula I:

[0010] R represents a substituent on the benzene ring, which may be monosubstituted or polysubstituted;

[0011] R can be independently selected from hydrogen, halogen, nitro, cyano, alkenyl (such as allyl -CH2CHCH2), amino, C1-C 10 Alkoxy, acyl (specifically formyl-CHO, acetyl-COCH3), aromatic heterocyclic group, heterocyclic group, carboxyl, ester group (specifically COOCH3), C1-C 10 Straight chain or branched alkyl, halogen substituted C1-C 10 Straight chain or branched alkyl, halogen substituted C1-C 10 At least one of the alkoxy groups.

[0012] When R is a ring structure, R is connected to the benzene ring by a single bond or a benzophenone ring;

[0013] Specifically, R is monosubstituted or polysubstituted, and R is independently selected from at least one of methyl, isopropyl, formyl (-CHO), ester (-COOCH3), methoxy, allyl-CH2CHCH2, 3,4-methylenedioxy, 3,4-pyrrolyl, acetyl-COCH3, Cl, F, -NO2, -CF3, -OCF3, ethoxy, Br, H and carbonyltrifluoromethyl.

[0014] The compound represented by the above formula I, wherein R is monosubstituted;

[0015] R is selected from H, C1-C 10 Alkyl, C1-C 10Any of alkoxy, halogen, nitro, amino and trifluoromethyl;

[0016] Preferably, R is selected from methyl, propyl, isopropyl, methoxy, fluoro, chloro, bromo, amino, trifluoromethyl or nitro.

[0017] The compound represented by the above formula I can be specifically selected from any one of the following:

[0018]

[0019] The compound represented by the above formula I is an α-pinene analogue containing an ester group.

[0020] The present invention provides a method for preparing the compound represented by the above formula I.

[0021] The preparation method of the compound of formula I provided by the present invention comprises the following steps: in the presence of a dehydrating agent and a catalyst, subjecting myrtenol (formula III) and substituted phenylacetic acid (formula IV) to an esterification condensation reaction to obtain the compound of formula I;

[0022]

[0023] In formula IV, the definition of R is the same as that of R in formula I.

[0024] In the above preparation method, the esterification condensation reaction is carried out in an organic solvent; specifically, the organic solvent can be selected from at least one of cyclohexane, hexane, tetrahydrofuran, dichloromethane, 1,4-dioxane, ethyl acetate, petroleum ether, methanol, ethanol, n-propanol, carbon tetrachloride, DMF, chloroform, diethyl ether and acetonitrile;

[0025] The condensation reagent activates the carboxyl group in the compound represented by formula IV;

[0026] The molar ratio of myrtenol, substituted phenylacetic acid, dehydrating agent and catalyst is 1:1-10:1-10:0.1-10, specifically 1:1.4:1.4:0.28, 1:1.4-10:1.4-10:0.28-10, 1:1-1.4:1-1.4:0.05-0.1, 1:1-5:1-5:0.1-5 or 1:1-7.5:1-7.5:0.1-7.5;

[0027] The dehydrating agent may be at least one of N,N-diisopropylcarbodiimide (DIC), N,N-diisopropylethylamine (DIEA), dicyclohexylcarbodiimide (DCC) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDCI);

[0028] The catalyst may be selected from at least one of 4-dimethylaminopyridine (DMAP) and 1-hydroxybenzotriazole (HOBt);

[0029] The molar ratio of the myrtenol to the substituted phenylacetic acid may be 1:1-10, specifically 1:1.4, 1:1.4-10, 1:1-1.4, 1:1-5 or 1:1-7.5.

[0030] In the above preparation method, the temperature range of the esterification condensation reaction is relatively wide, which is -50°C to 200°C, and the preferred temperature of the esterification condensation reaction is 10°C to 50°C; the time can be 2 to 24 hours; the preferred reaction time can be 8 hours, 4 to 8 hours, 8-12 hours or 10-20 hours.

[0031] In the above preparation method, the reaction product is purified by silica gel column chromatography.

[0032] In the above-mentioned preparation method, the myrtenol can be purchased from commercial sources or prepared by the following steps: α-pinene is oxidized to myrtenal using an oxidant, selenium dioxide, and then reduced to obtain the myrtenol.

[0033] The use of the compound represented by the above formula I in aphid control, aphid behavior control and aphid natural enemy behavior control also falls within the protection scope of the present invention.

[0034] The aphid behavior control refers to the control of aphid repellent behavior;

[0035] The aphid may specifically be at least one of green peach aphid, soybean aphid, onion aphid, pea aphid, vetch aphid and cereal aphid.

[0036] The compound represented by the above formula I can repel aphids and / or lure natural enemies of aphids in aphid control; specifically, the natural enemies of aphids can be Aphididae rapae and / or Harmonia axyridis.

[0037] The medicines with the ester-containing pinene analogs shown in formula I as active ingredients are also within the protection scope of the present invention.

[0038] The drug can specifically be an aphid control agent, an aphid behavior control agent or a natural enemy behavior control agent.

[0039] The ester-containing pinene analogue of the present invention has been confirmed by experiments to have not only obvious repellent activity against aphids but also obvious attractant activity against natural enemies of aphids, that is, it has the activity of regulating the behavior of aphids, can be used as an aphid control agent for preventing and controlling aphids on crops, fruit trees, Chinese herbal medicines and flowers; it can also regulate the behavior of natural enemies of aphids and attract natural enemies of aphids, and has dual activity.

[0040] The raw materials of the invention are derived from natural substances, the preparation method is simple and easy, the product is easy to purify, the cost is low, and it is eco-friendly. Some compounds have excellent activity of repelling aphids and attracting natural enemies of aphids, and have good application prospects in the green prevention and control of aphids.

[0041] The present invention obtains a class of ester-containing pinene analogs by esterification modification of pinene, a component of aphid alarm pheromone. Biological activity studies have shown that the present invention provides green agricultural chemicals with the dual functions of repelling aphids and attracting aphid natural enemies. DETAILED DESCRIPTION

[0042] The present invention is further described in detail below in conjunction with specific embodiments. The given examples are only for illustrating the present invention, but not for limiting the scope of the present invention.

[0043] The experimental methods in the following examples are all conventional methods unless otherwise specified.

[0044] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0045] Example 1. Preparation of (6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)methyl 2-(4-isopropylphenyl)acetate (I-a)

[0046] 4-Isopropylphenylacetic acid (1.51 g, 8.4 mmol) was placed in a 100 mL single-necked bottle, 4-dimethylaminopyridine (0.2 g, 1.68 mmol) was added and dissolved in 20 mL of dichloromethane, then dicyclohexylcarbodiimide (1.73 g, 8.4 mmol) was weighed and added to the single-necked bottle, and stirred at room temperature for 0.5 h, myrtenol (0.91 g, 6 mmol) was weighed and added dropwise to the single-necked bottle, and the reaction was allowed to proceed overnight at room temperature for 8 h. After the reaction was completed by monitoring by TLC, the byproduct 1,3-dicyclohexylurea was filtered out with a funnel, the crude product was collected, concentrated, and subjected to silica gel column chromatography to obtain product Ⅰ-a with a yield of 43.0%.

[0047] The H NMR spectrum data are as follows:

[0048] 1H NMR(500MHz,Chloroform-d)δ(ppm):7.17(q,J=8.3Hz,4H),5.50(tt,J=3.1,1.5Hz,1H),4.50-4.40(m,2H),3.56(s,2H),2.87(p,J=6.9H z,1H),2.34(dt,J=8.7,5.7Hz,1H),2.23(q,J=17.9Hz,2H),2.08-2.00(m,2H),1.22(d,J=7.3Hz,9H),1.12(d,J=8.7Hz,1H),0.74(s,3H).

[0049] Example 2. Preparation of (6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)methyl 2-(p-methyl)acetate (I-c)

[0050] 4-Methylphenylacetic acid (1.51 g, 8.4 mmol) was placed in a 100 mL single-necked bottle, 4-dimethylaminopyridine (0.2 g, 1.68 mmol) was added and dissolved in 20 mL of dichloromethane, then dicyclohexylcarbodiimide (1.73 g, 8.4 mmol) was weighed and added to the single-necked bottle, and stirred at room temperature for 0.5 h, and myrtenol (0.91 g, 6 mmol) was weighed and added dropwise to the single-necked bottle, and the reaction was allowed to proceed overnight at room temperature for 8 h. After the reaction was completed by monitoring by TLC, the byproduct 1,3-dicyclohexylurea was filtered out with a funnel, and the crude product was collected, concentrated, and subjected to silica gel column chromatography to obtain product Ⅰ-c with a yield of 64.2%.

[0051] The H NMR spectrum data are as follows:

[0052] 1 H NMR (500MHz, Chloroform-d) δ (ppm): 7.18-7.09 (m, 4H), 5.55-5.50 (m, 1H), 4.46 (d, J = 1.5Hz, 2H), 3.57 (s, 2H), 2.3 7-2.34(m,1H),2.32(s,3H),2.29-2.18(m,2H),2.11-2.03(m,2H),1.25(s,3H),1.14(d,J=8.7Hz,1H),0.77(s,3H).

[0053] Example 3. Preparation of (6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)methyl 2-(4-aminophenyl)acetate (I-k)

[0054] 4-Aminophenylacetic acid (1.51 g, 8.4 mmol) was placed in a 100 mL single-necked bottle, 4-dimethylaminopyridine (0.2 g, 1.68 mmol) was added and dissolved in 20 mL of dichloromethane, then dicyclohexylcarbodiimide (1.73 g, 8.4 mmol) was weighed and added to the single-necked bottle, stirred at room temperature for 0.5 h, myrtenol (0.91 g, 6 mmol) was weighed and added dropwise to the single-necked bottle, and the reaction was allowed to proceed overnight at room temperature for 8 h. After the reaction was completed by monitoring by TLC, the byproduct 1,3-dicyclohexylurea was filtered out with a funnel, the crude product was collected, concentrated, and subjected to silica gel column chromatography to obtain product Ⅰ-k with a yield of 17.9%.

[0055] The H NMR spectrum data are as follows:

[0056] 1 H NMR (500MHz, Chloroform-d) δ (ppm): 7.04 (d, J = 8.4Hz, 2H), 6.62 (d, J = 8.4Hz, 2H), 5.53-5.50 (m, 1H), 4.45 (d, J = 1.7Hz, 2H), 3.61 (s, 2H),3.49(s,2H),2.36(dt,J=8.7,5.6Hz,1H),2.31-2.19(m,2H),2.09-2.04(m,2H),1.26(s,3H),1.14(d,J=8.7Hz,1H),0.78(s,3H).

[0057] With reference to the preparation methods of Ia, Ic and Ik above, a series of compounds of formula I can be prepared.

[0058] Table 1 below lists the structure and basic physicochemical data of the compound of formula I, and Table 2 lists the H NMR spectrum data of the compound of formula I. They are all prepared according to methods similar to those shown in the aforementioned Examples 1-3.

[0059] Table 1 Properties, appearance and yield of the compound of formula I

[0060] serial number Characteristics Yield (%) <![CDATA[I- a ]]> Colorless transparent liquid 43.0％ Ib Colorless transparent liquid 20.4％ <![CDATA[I- c ]]> Colorless transparent liquid 64.2％ Id Colorless transparent liquid 83.5％ <![CDATA[I- e ]]> Colorless transparent liquid 75.3％ If Colorless transparent liquid 58.7％ Ig Colorless transparent liquid 64.3％ Ih Colorless transparent liquid 58.5％ Ii Colorless transparent liquid 53.6％ Ij Colorless transparent liquid 45.7％ I Brown liquid 17.9％ I-1 Colorless transparent liquid 24.4％ Im Colorless transparent liquid 39.5％ In Colorless transparent liquid 66.7％ Io Colorless transparent liquid 53.9％ Ip Colorless transparent liquid 60.7％ Iq Light yellow transparent liquid 26.9％ I-r Light yellow transparent liquid 11.3％ Is Light yellow transparent liquid 35.3％ It Colorless transparent liquid 46.7％

[0061] Table 2 H NMR data of compounds of formula I

[0062]

[0063]

[0064] The structural formulas of Formula I-a to Formula I-t are as follows:

[0065]

[0066]

[0067] Example 4: Attraction activity of the compounds of the present invention against Aphididae

[0068] The method reported in the reference (Qin YG, et al. Insects. 2022, 13 (11): 1105) was used to test the attraction activity of the compounds of the present invention as representatives of the embodiments (as shown in Table 3), and 60 heads (12 groups, 5 heads in each group) were used for each sample. The test equipment was a T-type olfactometer, and 5 newly emerged aphid wasps were released from the release port. Air was passed into each arm at 0.4 L / min through a vacuum pump. The air introduced into the test arm first passed through 10 μg of the sample flavor source, and the other arm was used as a solvent control arm. The number of aphid wasps in each arm was recorded 15 minutes after the sample was introduced. The experiment for each sample was repeated at least three times. The aphid wasps that crossed the center of the olfactometer were counted as the treatment group or the control group, and the aphid wasps that did not cross were recorded as the unresponsive group.

[0069] To calculate the preference index, the formula is as follows:

[0070] Preference index (%) = (number of insects in the treatment group - number of insects in the control group) / (number of insects in the treatment group + number of insects in the control group) * 100%

[0071] The test results of the attraction activity of Aphididae are shown in Table 3.

[0072] Table 3 The attraction activity of the compounds of formula I to Aphididae

[0073] serial number Preference index (%) Ia 12.3 Ib 14.8 Ic 46.5 Id 42.8 Ie 10.8 If 38.2 Ig 35.3 Ih 11.5 Ii 2.5 Ij 2.2 I 10.0 I-l 25.2 Im 24.3 In 1.3 Io 11.5 Ip 10.7 Iq 18.7 I-r 11.7 Is 8.1 It 2.7 Pinene 33.6 Myrtenol 5.5

[0074] As can be seen from Table 3, the lead pinene and some compounds of formula I provided by the present invention have good attraction activity to Aphididae, among which compounds Ic, Id and If have a better preference index to Aphididae at a dose of 10 μg than the aphid alarm pheromone pinene and its oxidized product myrtene alcohol, among which Ic and Id have the most outstanding activity, and the preference index of Aphididae is above 40%. They can be used as candidate attractants of Aphididae for green control of aphids.

[0075] Example 5: Repellent activity against aphids

[0076] The method reported in the reference (Yang ZK, et al. Pest Manag Sci. 2023, 79: 760-770) was used to test the repellent activity against aphids using the compounds of the present invention as representatives of the embodiments (as shown in Table 4). The test equipment is a T-type olfactometer, and more than 20 wingless adult aphids are released from the release port, and air is introduced into each arm at 0.2 L / min through a vacuum pump. The air introduced into the test arm first passes through 5 μg of the sample odor source, and the other arm serves as a solvent control arm. Record the number of aphids in each arm when the sample is introduced for 15 minutes. Each sample experiment was repeated at least three times. Aphids that crossed the center of the olfactometer were counted as the treatment group or the control group, and aphids that did not cross were recorded as the unresponsive group.

[0077] Calculate the repellency rate, the formula is as follows

[0078] Repellency rate (%) = (number of insects in the control group minus number of insects in the treatment group) / (number of insects in the control group + number of insects in the treatment group) * 100%

[0079] The results of the aphid repellent activity test are shown in Tables 4 and 5.

[0080] Table 4 Repellent activity of some compounds of formula I against peach aphid

[0081] serial number Repellency rate (%) Ia 73.9 Ib 61.4 Ic 40.6 Id 59.9 Ie 50.4 If 33.9 Ig 27.4 Ih 71.7 Ij 69.9 It 66.5 Pinene 46.7 Myrtenol 41.4

[0082] Table 5 Repellent activity of some compounds of formula I against soybean aphids

[0083] serial number Repellency rate (%) Ic 50.8 Id 37.4 Pinene 15.9 Myrtenol 23.3

[0084] The results in Table 4 and Table 5 show that the compounds of the present invention have repellent activity against peach aphids at low concentrations, among which compounds Ia, Ib, Id, Ie, Ih, Ij and It have repellent rates of more than 50% against peach aphids at a dose of 5 μg. Further studies have found that the repellent rates of Ic and Id against soybean aphids at a dose of 5 μg are more than 37%, which is significantly better than the aphid alarm pheromone pinene and its oxidized product myrtenol. The above compounds are simple and feasible to synthesize, and the raw material sources are green and safe. They are worth further development as aphid behavior control agents and have good application prospects.

[0085] Example 6: Attraction activity against Harmonia axyridis

[0086] The method reported in the reference (Pan SX, et al. JAgr Food Chem. 2024, 72 (40): 22035-22044) uses some compounds of the present invention as representatives of the examples to test their biological activity against Harmonia axyridis. The test equipment is a Y-shaped olfactometer, in which a Y-shaped wire is placed to facilitate the crawling of the ladybug. The two sides of the Y-shaped olfactometer are connected to the flavor source and the blank, respectively, and a blank and 100 μg of flavor source are introduced from both sides of the Y-shaped olfactometer at a wind speed of 0.6 L / min. A ladybug is placed at the bottom of the Y-shaped tube, and the choice of the ladybug is observed after 5 minutes. It is effective only after crossing the bifurcation of the Y-shaped olfactometer by 7 cm. Every 5 ladybugs form a group. After each group, the Y-shaped olfactometer is cleaned with clean water and anhydrous ethanol, and the directions of the two ends of the Y-shaped olfactometer are reversed to carry out the next group of experiments. The test does not distinguish between male and female insects, and 60 effective Harmonia axyridis need to be counted.

[0087] Calculate the selection rate, the formula is as follows

[0088] Selection rate (%) = number of effective ladybugs in treatment / (number of effective ladybugs in treatment + number of effective ladybugs in blank)*100%

[0089] The test results of the attraction activity of Harmonia axyridis are shown in Table 6.

[0090] Table 6 The attraction activity of some compounds of formula I to Harmonia axyridis

[0091] serial number Attraction rate (%) Ic 60.0 Id 71.7 Pinene 66.7 Myrtenol 55.0

[0092] As can be seen from Table 6, the lead pinene and some compounds of formula I provided by the present invention have good attraction activity to Harmonia axyridis. The attraction activity of compounds Id and Ic is better than that of the raw material myrtene alcohol. Among them, compound Id has the most outstanding activity, with an attraction rate of more than 70% for Harmonia axyridis, which is better than lead pinene and myrtene alcohol, and can be used as a ladybug attractant for green control of aphids.

[0093] The present invention has been described in detail above. For those skilled in the art, without departing from the purpose and scope of the present invention, and without the need to carry out unnecessary experimental conditions, the present invention can be implemented in a wide range under equivalent parameters, concentrations and conditions. Although the present invention provides specific embodiments, it should be understood that the present invention can be further improved. In a word, according to the principles of the present invention, the application is intended to include any changes, uses or improvements to the present invention, including departure from the disclosed scope in the application, and changes made with conventional techniques known in the art.

Claims

1. Compounds represented by formula I: In Formula I: R is a substituent on the benzene ring, which can be monosubstituted or polysubstituted; R is independently selected from hydrogen, halogen, nitro, cyano, alkenyl, amino, C1-C 10 Alkoxy, acyl, aromatic hetero, heterocyclic, carboxyl, ester, C1-C 10 Straight chain or branched alkyl, halogen substituted C1-C 10 Straight chain or branched alkyl and halogen substituted C1-C 10 at least one of alkoxy groups; When R is a ring structure, R is connected to the benzene ring via a single bond or a paraben ring.

2. The compound of formula I according to claim 1, characterized in that: The R is monosubstituted; R is selected from H, C1-C 10 Alkyl, C1-C 10 Any of alkoxy, halogen, nitro, amino and trifluoromethyl; Preferably, R is selected from methyl, propyl, isopropyl, methoxy, fluoro, chloro, bromo, amino, trifluoromethyl or nitro.

3. The compound of formula I according to claim 1, characterized in that: The compound represented by formula I is selected from any one of the following:

4. A method for preparing the compound of formula I as claimed in any one of claims 1 to 3, comprising the following steps: In the presence of a dehydrating agent and a catalyst, myrtenol (Formula III) and substituted phenylacetic acid (Formula IV) are subjected to an esterification condensation reaction to obtain a compound represented by Formula I; In formula IV, the definition of R is the same as that of R in formula I in any one of claims 1-3.

5. The preparation method according to claim 4, characterized in that: The molar ratio of myrtenol, substituted phenylacetic acid, dehydrating agent and catalyst is 1:1-10:1-10:0.1-10, specifically 1:1.4:1.4:0.28, 1:1.4-10:1.4-10:0.28-10, 1:1-1.4:1-1.4:0.05-0.1, 1:1-5:1-5:0.1-5 or 1:1-7.5:1-7.5:0.1-7.5; The dehydrating agent is at least one of N,N-diisopropylcarbodiimide, N,N-diisopropylethylamine, dicyclohexylcarbodiimide and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide; The catalyst is selected from at least one of 4-dimethylaminopyridine and 1-hydroxybenzotriazole; The esterification condensation reaction is carried out in an organic solvent; specifically, the organic solvent is selected from at least one of cyclohexane, hexane, tetrahydrofuran, dichloromethane, 1,4-dioxane, ethyl acetate, petroleum ether, methanol, ethanol, n-propanol, carbon tetrachloride, DMF, chloroform, diethyl ether and acetonitrile.

6. The preparation method according to claim 4 or 5, characterized in that: The condensation reaction temperature is -50°C to 200°C, and the reaction time is 2 to 24 hours.

7. Use of the compound of formula I according to any one of claims 1 to 3 in controlling aphids, controlling aphid behavior and controlling the behavior of aphid natural enemies.

8. The use according to claim 7, characterized in that: The aphid is at least one of green peach aphid, soybean aphid, onion aphid, pea aphid, vetch aphid and cereal aphid; The natural enemies of aphids are Aphididae rapae and / or Harmonia axyridis.

9. An aphid control agent, wherein the active ingredient is the compound represented by formula I as claimed in any one of claims 1 to 3; An aphid behavior control agent, the active ingredient of which is the compound represented by formula I as described in any one of claims 1 to 3; A natural enemy behavior control agent for aphids, the active ingredient of which is the compound represented by formula I as claimed in any one of claims 1 to 3.

10. The preparation according to claim 9, characterized in that: The aphid control agent has dual activities of repelling aphids and attracting natural enemies of aphids; The aphid is at least one of green peach aphid, soybean aphid, onion aphid, pea aphid, vetch aphid and cereal aphid; The natural enemies of aphids are Aphididae rapae and / or Harmonia axyridis.

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