Ester group-containing pinene analogues, preparation and application thereof

Abstract

The application discloses a pinene analogue containing an ester group and preparation and application thereof, and belongs to the field of agricultural chemicals. The pinene analogue containing the ester group provided by the application has a structural formula as shown in formula I: the application obtains a pinene analogue containing an ester group by esterification modification of an aphid alarm pheromone pinene; through biological activity research, it is found that the compound has double functions of repelling aphids and attracting natural enemies of the aphids, and has a good application prospect in green prevention and control of the aphids.

Description

Technical Field

[0001] This invention relates to the field of agricultural chemicals, specifically to an ester-containing pinene analogue and its preparation method, as well as the application of this type of compound in aphid control and attraction of natural enemies of aphids. Background Technology

[0002] Aphids are global agricultural pests, characterized by their diversity, rapid reproduction, overlapping generations, and multiple host types. Currently, aphid control still relies heavily on chemical pesticides; however, the long-term use of traditional pesticides has led to increasingly serious resistance in aphids. As of 2024, the peach aphid (Myzus persicae) had developed resistance to more than 80 active insecticide ingredients, ranking among the top 10 most resistant invertebrates globally. Therefore, the development of green, safe, and highly effective new aphid control agents is urgently needed. In recent years, utilizing aphid natural enemies for biological control has gained popularity due to its environmental friendliness and safety for non-target organisms.

[0003] The cabbage aphid wasp (Diaeretiella rapae) is a gregarious, polyphagous endoparasitic wasp belonging to the order Hymenoptera, family Diaretiella, and genus Diaretiella. As an important biocontrol enemy, it has a very wide host range, mainly parasitizing various aphids in the superfamily Aphidae, such as the peach aphid, turnip aphid, and cabbage aphid, which damage cruciferous crops. It plays a very important role in controlling aphid populations.

[0004] When aphids are attacked or stimulated, their septostomes secrete small droplets containing volatile gases with alarm activity—alarm pheromones. Other aphids can receive this alarm signal, exhibiting avoidance behaviors and quickly fleeing the area. Besides directly repelling or refusing food from pests, aphids can also indirectly exert their effect by attracting natural enemies of pests. Pinene Pinene is an important aphid alarm pheromone component, effectively repelling peach aphids and exhibiting good fumigation toxicity. Its repellent activity against aphids is enhanced when mixed with other terpenoid compounds. In addition, pinene attracts various aphid natural enemies, such as the Chinese lacewing, the large lacewing, the thirteen-spotted ladybug, the multicolored ladybug, and the black-banded hoverfly. However, the biological activity of pinene and its analogues against aphid parasitic wasps remains unclear. Therefore, its behavioral activity against aphid parasitic wasps warrants further investigation in order to develop aphid control agents with both aphid repellent and parasitic wasp attractant activities.

[0005] While aphid alarm pheromones possess advantages such as high specificity, trace amounts, and eco-friendliness, they also have disadvantages including volatility, structural instability, and difficulty in field application. Therefore, developing aphid control agents that combine activity and stability, using aphid alarm pheromones as activity leaders, is of great significance for the green control of aphids. Summary of the Invention

[0006] The purpose of this invention is to provide an ester-containing pinene analogue and its preparation and application. This invention synthesizes an ester-containing pinene analogue by using aphid alarm pheromone components as a guide. This type of compound not only has significant repellent activity against aphids but also significant attraction activity against aphid natural enemies, exhibiting dual activity. It can be used for the control of aphids on crops, fruit trees, Chinese herbal medicines, and flowers.

[0007] The ester-containing pinene analogues provided by this invention have the structural formula shown in Formula I:

[0008]

[0009] In Formula I:

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

[0011] R can be independently selected from hydrogen, halogen, nitro, cyano, alkenyl (e.g., allyl-CH2CHCH2), amino, C1-C 10 Alkoxy, acyl (specifically formyl-CHO, acetyl-COCH3), aromatic heteroyl, heterocyclic, carboxyl, ester (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 fused benzene 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-pyrrole, acetyl-COCH3, Cl, F, -NO2, -CF3, -OCF3, ethoxy, Br, H and carbonyl trifluoromethyl.

[0014] In the compounds represented by Formula I above, R is a monosubstituted compound;

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

[0016] Preferably, R is selected from methyl, propyl, isopropyl, methoxy, fluorine, chlorine, bromine, amino, trifluoromethyl, or nitro.

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

[0018]

[0019] The compound shown in Formula I above is an α-pinene analog containing an ester group.

[0020] This invention provides a method for preparing the compound shown in Formula I above.

[0021] The method for preparing the compound shown in Formula I provided by the present invention includes the following steps: in the presence of a dehydrating agent and a catalyst, myrtol (Formula III) is subjected to an esterification condensation reaction with substituted phenylacetic acid (Formula IV) to obtain the compound shown in Formula I;

[0022]

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

[0024] In the above preparation method, the esterification condensation reaction is carried out in an organic solvent; specifically, the organic solvent may 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 condensing agent activates the carboxyl group in the compound shown in Formula IV;

[0026] The molar ratio of myrtleenol, substituted phenylacetic acid, dehydrating agent, and catalyst is 1:1 to 10:1 to 10:0.1 to 10, specifically 1:1.4:1.4:0.28, 1:1.4 to 10:1.4 to 10:0.28 to 10, 1:1 to 1.4:1 to 1.4:0.05 to 0.1, 1:1 to 5:1 to 5:0.1 to 5, or 1:1 to 7.5:1 to 7.5:0.1 to 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 myrtol to the substituted phenylacetic acid can be 1:1 to 10, specifically 1:1.4, 1:1.4 to 10, 1:1 to 1.4, 1:1 to 5, or 1:1 to 7.5.

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

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

[0032] In the above preparation method, the myrtol can be purchased commercially or prepared by the following steps: oxidizing α-pinene with selenium dioxide to myrtol, and then reducing it to obtain the myrtol.

[0033] The application of the compound shown in Formula I above in aphid control, aphid behavior control, and aphid natural enemy behavior control also falls within the scope of protection of this invention.

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

[0035] The aphids may specifically be at least one of the following: peach aphid, soybean aphid, onion aphid, pea aphid, vetch aphid, and cereal constrictor aphid.

[0036] The compound shown in Formula I above can repel aphids and / or attract aphid natural enemies in aphid control; specifically, the aphid natural enemies can be cabbage aphid parasitoids and / or ladybugs.

[0037] Drugs containing pinene analogs with ester groups as shown in Formula I as active ingredients are also within the scope of protection of this invention.

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

[0039] The pinene analogues containing ester groups of the present invention have been experimentally proven to have significant repellent activity against aphids and significant attraction activity against aphid natural enemies, that is, they have the activity of regulating aphid behavior and can be used as aphid control agents to prevent and control aphids on crops, fruit trees, Chinese herbal medicines and flowers; they can also regulate the behavior of aphid natural enemies and attract aphid natural enemies, thus having dual activity.

[0040] The raw materials of this 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 aphid-repelling activity and aphid-attracting activity, showing good application prospects in the green control of aphids.

[0041] This invention modifies pinene, a component of aphid alarm pheromones, by esterification to obtain a class of pinene analogs containing ester groups. Bioactivity studies have demonstrated that this invention provides a green agricultural chemical with the dual functions of repelling aphids and attracting aphid natural enemies. Detailed Implementation

[0042] The present invention will be further described in detail below with reference to specific embodiments. The embodiments given are only for illustrating the present invention and are not intended to limit the scope of the present invention.

[0043] Unless otherwise specified, the experimental methods described in the following examples are conventional methods.

[0044] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0045] Example 1: Preparation of (6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl)methyl 2-(4-isopropylphenyl)acetic acid ester (I-a)

[0046] 4-Isopropylphenylacetic acid (1.51 g, 8.4 mmol) was placed in a 100 mL single-necked flask. 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 flask. After stirring at room temperature for 0.5 h, myrtol (0.91 g, 6 mmol) was weighed and added dropwise to the single-necked flask. The reaction was allowed to proceed overnight at room temperature for 8 h. After the reaction was completed as monitored by TLC, the byproduct 1,3-dicyclohexylurea was filtered out using 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 1H NMR 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] 1.51 g (8.4 mmol) of 4-methylphenylacetic acid was added to a 100 mL single-necked flask, followed by the addition of 0.2 g (1.68 mmol) of 4-dimethylaminopyridine in 20 mL of dichloromethane. Then, 1.73 g (8.4 mmol) of dicyclohexylcarbodiimide was weighed and added to the flask. After stirring at room temperature for 0.5 h, 0.91 g (6 mmol) of myrtol was weighed and added dropwise to the flask. The reaction was allowed to proceed overnight at room temperature for 8 h. After the reaction was completed as monitored by TLC, the byproduct 1,3-dicyclohexylurea was filtered out using a funnel. 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 1H NMR 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] 1.51 g (8.4 mmol) of 4-aminophenylacetic acid was added to a 100 mL single-necked flask, followed by the addition of 0.2 g (1.68 mmol) of 4-dimethylaminopyridine in 20 mL of dichloromethane. Then, 1.73 g (8.4 mmol) of dicyclohexylcarbodiimide was weighed and added to the flask. After stirring at room temperature for 0.5 h, 0.91 g (6 mmol) of myrtol was weighed and added dropwise to the flask. The reaction was allowed to proceed overnight at room temperature for 8 h. After the reaction was completed as monitored by TLC, the byproduct 1,3-dicyclohexylurea was filtered out using 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 1H NMR 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] By referring to the preparation methods of Ia, Ic and Ik described above, 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 shows the 1H NMR spectrum data of the compound of formula I. They were all prepared according to methods similar to those shown in Examples 1-3 above.

[0059] Table 1. Properties, appearance, and yield of compounds of formula I.

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

[0061] Table 2. 1H NMR spectral data of compounds of formula I

[0062]

[0063]

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

[0065]

[0066]

[0067] Example 4: Attraction activity of the compound of the present invention on the cabbage aphid wasp

[0068] The method reported in reference (Qin YG, et al. Insects. 2022, 13(11):1105) was used to test the attraction activity of the compounds of the present invention on the aphid parasitic wasps as representative examples (as shown in Table 3). Each sample used 60 wasps (12 groups, 5 wasps per group). The testing equipment was a T-type olfactometer. Five newly emerged aphid parasitic wasps were released from the release port, and air was introduced into each arm at a rate of 0.4 L / min via a vacuum pump. The air introduced into the test arm first passed through 10 μg of the sample flavoring agent, and the other arm served as a solvent control arm. The number of aphid parasitic wasps in each arm was recorded 15 min after the sample was introduced. Each sample experiment was repeated at least three times. Wasps that crossed the center of the olfactometer were counted as either the treatment or control group; those that did not cross the center were recorded as the unreacted group.

[0069] The preference index is calculated using the formula shown below:

[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 results of the attraction activity test of the cabbage aphid wasp are shown in Table 3.

[0072] Table 3 shows the attraction activity of compound I to the cabbage aphid wasp.

[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 Ik 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 Myrtol 5.5

[0074] As shown in Table 3, the lead pinene and some of the compounds of formula I provided in this invention exhibit good attraction activity for *Aphidius simonii*. Among them, compounds Ic, Id, and If, at a dose of 10 μg, showed better preference indices for *Aphidius simonii* than the aphid alarm pheromone pinene and its oxidation product myrtol. Ic and Id showed the most outstanding activity, with preference indices for *Aphidius simonii* exceeding 40%. These compounds can be used as candidate attractants for the green control of aphids.

[0075] Example 5: Repellent activity against aphids

[0076] The repellent activity against aphids was tested using the compounds of this invention as representative examples (as shown in Table 4), according to the method reported in the reference (Yang ZK, et al. Pest Manag Sci. 2023, 79: 760-770). The testing equipment was a T-type olfactometer, through which more than 20 wingless adult aphids were released. Air was introduced into each arm via a vacuum pump at 0.2 L / min. The air introduced into the test arm first passed through 5 μg of the sample odorant, while the other arm served as a solvent control arm. The number of aphids in each arm was recorded 15 min after the sample was introduced. Each sample experiment was repeated at least three times. Aphids that crossed the center of the olfactometer were counted as either the treatment or control group; those that did not cross the center were recorded as the non-reactive group.

[0077] The formula for calculating the avoidance rate is as follows:

[0078] Repellency rate (%) = (Number of insects in control group - Number of insects in treatment group) / (Number of insects in control group + Number of insects in treatment group) * 100%

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

[0080] Table 4 shows the repellent activity of some compounds in Formula I against peach aphids.

[0081] serial number Avoidance 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 Myrtol 41.4

[0082] Table 5 shows the repellent activity of some compounds in Formula I against soybean aphids.

[0083] serial number Avoidance rate (%) Ic 50.8 Id 37.4 pinene 15.9 Myrtol 23.3

[0084] Tables 4 and 5 show that the compounds of this invention exhibit repellent activity against peach aphids at low concentrations. Compounds Ia, Ib, Id, Ie, Ih, Ij, and It all showed repellency rates exceeding 50% against peach aphids at a dose of 5 μg. Further studies revealed that Ic and Id achieved repellency rates exceeding 37% against soybean aphids at a dose of 5 μg, significantly superior to the aphid alarm pheromone pinene and its oxidation product, myrtol. The above compounds are simple and feasible to synthesize, with green and safe raw material sources, and possess value for further development as aphid behavior control agents, showing promising application prospects.

[0085] Example 6: Attraction activity against ladybugs

[0086] The method reported in reference (Pan SX, et al. JAgr Food Chem. 2024, 72(40): 22035-22044) was used to test the bioactivity of some compounds of the present invention as representatives of the examples on ladybugs. The testing device was a Y-shaped olfactometer, in which a Y-shaped wire was placed to facilitate ladybug crawling. The two sides of the Y-shaped olfactometer were connected to the flavor source and the blank, respectively. The blank and 100 μg of flavor source were introduced from the two sides of the Y-shaped olfactometer at a wind speed of 0.6 L / min. A ladybug was placed at the bottom of the Y-shaped tube, and the ladybug selection was observed after 5 minutes. It was considered effective if it crossed 7 cm past the bifurcation of the Y-shaped olfactometer. Each group consisted of 5 ladybugs. After each group, the Y-shaped olfactometer was cleaned with water and anhydrous ethanol, and the two ends of the Y-shaped olfactometer were reversed to conduct the next group of experiments. The test did not distinguish between male and female ladybugs, and 60 effective ladybugs were counted.

[0087] The selection rate is calculated using the formula shown below.

[0088] Selection rate (%) = (Number of effective ladybugs treated / (Number of effective ladybugs treated + Number of effective ladybugs in the blank)) * 100%

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

[0090] Table 6 shows the attraction activities of some compounds from Formula I to ladybugs.

[0091] serial number Seduction rate (%) Ic 60.0 Id 71.7 pinene 66.7 Myrtol 55.0

[0092] As shown in Table 6, the lead pinene and some of the compounds of formula I provided by this invention have good attraction activity for ladybugs. The attraction activity of compounds Id and Ic is superior to that of the raw material myrtol. Among them, compound Id shows the most outstanding activity, with an attraction rate of over 70% for ladybugs, which is better than that of lead pinene and myrtol, and can be used as a ladybug attractant for the green control of aphids.

[0093] The present invention has been described in detail above. Those skilled in the art will recognize that the invention can be practiced in a wide range of ways with equivalent parameters, concentrations, and conditions without departing from its spirit and scope, and without requiring unnecessary experiments. While specific embodiments have been provided, it should be understood that further modifications can be made to the invention. In summary, according to the principles of the invention, this application is intended to include any changes, uses, or improvements to the invention, including changes made using conventional techniques known in the art that depart from the scope disclosed herein.

Claims

1. The compound shown in Formula I: In Formula I: R is a substituent on the benzene ring, which is a monosubstituted group; R is independently selected from halogen, nitro, amino, C1-C 10 Alkoxy, C1-C 10 C1-C chains with straight or branched alkyl groups and halogen substitution 10 Any one of straight-chain or branched alkyl groups.

2. The compound of formula I according to claim 1, characterized in that: R is selected from halogen, C1-C 10 Straight-chain or branched alkyl groups, C1-C 10 Any one of alkoxy, nitro, amino, and trifluoromethyl.

3. The compound of formula I according to claim 2, characterized in that: R is selected from methyl, propyl, isopropyl, methoxy, fluorine, chlorine, bromine, amino, trifluoromethyl, or nitro.

4. The compound of formula I according to claim 1, characterized in that: The compound represented by Formula I is selected from any of the following: 。 5. A method for preparing the compound of formula I according to any one of claims 1-3, comprising the following steps: In the presence of a dehydrating agent and a catalyst, Formula III and Formula IV are subjected to an esterification condensation reaction to obtain the compound shown in Formula I; In Formula IV, the definition of R is the same as the definition of R in Formula I of any one of claims 1-3.

6. The preparation method according to claim 5, characterized in that: The molar ratio of Formula III, Formula IV, dehydrating agent, and catalyst is 1:1~10:1~10:0.1~10; The dehydrating agent is at least one of N,N-diisopropylcarbodiimide, 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.

7. The preparation method according to claim 6, characterized in that: 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.

8. The preparation method according to claim 5 or 6, characterized in that: The condensation reaction is carried out at a temperature of -50℃ to 200℃ for 2 to 24 hours.

9. Application of the compound shown in Formula I in the control of aphid behavior; In Formula I: R is a substituent on the benzene ring, which is a monosubstituted group; R is independently selected from halogens, C1-C 10 Alkoxy and C1-C 10 Any one of straight-chain or branched alkyl groups.

10. The application according to claim 9, characterized in that: The aphids are at least one of the following: peach aphid, soybean aphid, onion aphid, pea aphid, vetch aphid, and cereal constrictor aphid.

11. Application of the compound shown in Formula I in the control of the behavior of aphid natural enemies; In Formula I: R is a substituent on the benzene ring, which is a monosubstituted group; R is independently selected from amino, C1-C 10 Alkoxy, C1-C 10 C1-C chains with straight or branched alkyl groups and halogen substitution 10 Any one of straight-chain or branched alkyl groups.

12. The application according to claim 11, characterized in that: The aphid's natural enemies are cabbage aphid parasitoids and / or ladybugs.

13. An aphid behavior control agent, the active ingredient of which is the compound shown in Formula I; In Formula I: R is a substituent on the benzene ring, which is a monosubstituted group; R is independently selected from halogens, C1-C 10 Alkoxy and C1-C 10 Any one of straight-chain or branched alkyl groups.

14. A behavior control agent for aphid natural enemies, the active ingredient of which is the compound shown in Formula I; In Formula I: R is a substituent on the benzene ring, which is a monosubstituted group; R is independently selected from amino, C1-C 10 Alkoxy, C1-C 10 C1-C chains with straight or branched alkyl groups and halogen substitution 10 Any one of straight-chain or branched alkyl groups.

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