S-methoprene ester and amide derivative as well as preparation method and application thereof

Abstract

The invention discloses ester and amide derivatives of S-methoprene and a preparation method of the ester and amide derivatives. The compounds shown in the formula (1) comprise structures shown in a formula (I) and a formula (II). The preparation method of the esters and amide derivatives of the S-methoprene comprises the following step of: reacting (2E, 4E, 7S)-11-methoxy-3, 7, 11-trimethyl-2, 4-dodecadienoic acid with various alcohols (amines) under different esterification or amidation conditions to form the corresponding esters and amide derivatives of the S-methoprene. The compound has good inhibitory activity on targets such as plutella xylostella and aphis medicaginis. The compound and the preparation method thereof have a wide application prospect. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of the development of biochemical pesticides, and relates to a class of ester and amide derivatives of S-methoprene and their synthesis methods and applications. Background Art

[0002] Chemical pesticides are an important means for preventing and controlling agricultural pests and diseases. With the extensive and frequent use of chemical pesticides, problems such as food residues, environmental pollution, and ecological hazards have become increasingly prominent. At the same time, the resistance of pests has also been continuously increasing. Currently, the resistance of agricultural pests such as Lepidoptera and aphids that affect crop yields, quality, and even cause crop failures is very serious. For example, the diamondback moth has developed varying degrees of resistance to nearly a hundred kinds of insecticides and is one of the most resistant agricultural pests globally; the armyworm, alfalfa aphid, etc. have all developed resistance to most insecticides. Therefore, there is an urgent need to develop new, highly efficient, safe, and green control agents for agricultural pests.

[0003] S-methoprene ((2E,4E,7S)-isopropyl 11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate) is an artificially synthesized juvenile hormone analogue of insects, belonging to biochemical pesticides. It can mimic the activity of natural hormones, interfere with the normal growth process of insects, and affect the development from larvae to adults, thereby achieving the effect of controlling pests. As one of the most successful biochemical pesticides in the world, S-methoprene has the advantages of specificity, high efficiency, etc., low environmental residue levels, low toxicity or non-toxicity to non-target organisms, and is not prone to developing resistance. It has been widely used in multiple fields such as mosquito and fly control, storage pest control, and increasing silk production in silkworms. Taking S-methoprene as a lead compound, carrying out multi-system structural modification and optimization to synthesize a series of S-methoprene analogues is expected to create highly efficient and safe new chiral biochemical pesticides and provide new methods for the control of agricultural pests. Summary of the Invention

[0004] To solve the problems existing in the current technology, the present invention has innovatively developed a class of ester and amide derivatives of S-methoprene, and their structural formula is shown in formula (1):

[0005]

[0006] In the formula (1), R is selected from alkyl, aryl, and heteroaryl groups with 1 to 20 carbon atoms; among them, the heteroaryl groups include thiophene, furan, pyridine, pyrrole, pyrazole, pyrimidine, pyrazine, pyridazine, and thiazole; X is selected from oxygen (O), NH, and a nitrogen atom with a substituent (NR1); the chiral configuration of the compound shown in the formula (1) is the (S) configuration, and the double bond configuration is the (E) form.

[0007] Specifically, the present invention provides a class of (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate compounds, and their structural formula is shown as formula (I):

[0008]

[0009] Wherein, R is selected from C1-C20 alkyl, aryl, heteroaryl; wherein, the heteroaryl includes thiophene, furan, pyridine, pyrrole, pyrazole, pyrimidine, pyrazine, pyridazine, thiazole; the chiral configuration of the compound shown in formula (I) is the (S) configuration, and the double bond configuration is the (E) form.

[0010] Specifically, the present invention also provides a class of (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienamide compounds, and their structural formula is shown as formula (II):

[0011]

[0012] Wherein, R is selected from C1-C20 alkyl, aryl, heteroaryl; wherein, the heteroaryl includes thiophene, furan, pyridine, pyrrole, pyrazole, pyrimidine, pyrazine, pyridazine, thiazole; R1 is selected from hydrogen, C1-C20 alkyl, aryl; the chiral configuration of the compound shown in formula (II) is the (S) configuration, and the double bond configuration is the (E) form.

[0013] Preferably, the ester and amide derivatives of S-methoprene are optically pure ester and amide derivative compounds of S-methoprene.

[0014] Specifically, the ester and amide derivatives of S-methoprene include but are not limited to the following structures:

[0015]

[0016] The present invention also provides a method for preparing esters and amide derivatives of the S-methoprene, including: a method for preparing (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid esters represented by formula (I) and (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid amides represented by formula (II); in a solvent, (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid and an alcohol or an amine undergo an esterification or amidation reaction under the action of an activator and a base, and the (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid esters represented by formula (I) or the (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid amides represented by formula (II) can be obtained by separation and purification. The preparation method is shown in the following reaction formula (A):

[0017]

[0018] In the reaction formula (A), R is selected from C1-C20 alkyl, aryl, heteroaryl; wherein, the heteroaryl includes thiophene, furan, pyridine, pyrrole, pyrazole, pyrimidine, pyrazine, pyridazine, thiazole; wherein, X is selected from oxygen (O), NH, a nitrogen atom with a substituent (NR1). Among them, the chiral configuration of (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid in the reactants and the chiral configuration of the (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid esters (or amides) in the products are both in the (S) configuration, and the double bond configuration is in the (E) form; the activator includes acyl chloride, condensing agent.

[0019] The acyl chloride includes but is not limited to one or more selected from acetyl chloride, thionyl chloride, oxalyl chloride, etc. The amount of the acyl chloride used is 1.0 to 15 mmol per mmol of (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid, that is, 0.5 to 15 equivalents; preferably, the acyl chloride is selected from one of acetyl chloride, thionyl chloride, etc., and the amount of the acyl chloride used is 1.5 equivalents;

[0020] In the present invention, the condensing agent includes but is not limited to one or more selected from DIC (N,N - diisopropylcarbodiimide), DCC (N,N - dicyclohexylcarbodiimide), HOBt (hydroxybenzotriazole), HOAt (N - hydroxy - 7 - azabenzotriazole), HATU (N,N,N’,N’ - tetramethyl - O - (7 - azabenzotriazol - 1 - yl)uronium hexafluorophosphate), HBTU (benzotriazole - N,N,N',N' - tetramethylurea hexafluorophosphate), HCTU (6 - chlorobenzotriazole - 1,1,3,3 - tetramethylurea hexafluorophosphate), or EDC·HCl (1 - ethyl - (3 - dimethylaminopropyl)carbodiimide hydrochloride), etc. The amount of the condensing agent used is 0.5 to 5 millimoles, that is, 0.5 to 5 equivalents, corresponding to each millimole of (2E,4E,7S) - 11 - methoxy - 3,7,11 - trimethyl - 2,4 - dodecadienoic acid. Preferably, the condensing agent is one of DIC (N,N - diisopropylcarbodiimide), EDC·HCl (1 - ethyl - (3 - dimethylaminopropyl)carbodiimide hydrochloride), etc.; the amount of the condensing agent used is 1.0 to 5.0 equivalents; more preferably, the amount of the condensing agent used is 1.5 equivalents.

[0021] In the present invention, the base includes but is not limited to one or more selected from triethylamine, diisopropylethylamine, DMAP, pyridine, tributylamine, N,N - dimethylaniline, N - methylpyrrolidine, N - methylpiperidine, DABCO, etc. The amount of the base used is 0.1 to 5 millimoles, that is, 0.1 to 5 equivalents, corresponding to each millimole of (2E,4E,7S) - 11 - methoxy - 3,7,11 - trimethyl - 2,4 - dodecadienoic acid. Preferably, the base is one of triethylamine, diisopropylethylamine, DMAP, etc.; the amount of the base used is 1.5 equivalents.

[0022] In the present invention, the solvent includes but is not limited to one or more selected from toluene, dichloromethane, ethyl acetate, tetrahydrofuran, acetone, acetonitrile, DMF, DMSO, ethanol, methanol, etc. The amount of the solvent used is 0.1 mL to 50 mL corresponding to each millimole of (2E,4E,7S) - 11 - methoxy - 3,7,11 - trimethyl - 2,4 - dodecadienoic acid. Preferably, the solvent is dichloromethane; the amount of the solvent used is 5 mL.

[0023] In the present invention, the reaction temperature is - 10°C to 100°C, and the reaction time is 0.5 - 100 hours. Preferably, the reaction temperature is 0°C. The reaction time is 12 h.

[0024] In a specific embodiment, in Solvent 1, (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid undergoes an esterification reaction with alcohols of different structures under the action of Acyl Chloride 1 and Base 1, and the ester derivatives of S-methoprene of formula (I), namely (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid ester compounds, can be obtained by separation and purification. The method is shown in Reaction Scheme (B) as follows:

[0025]

[0026] Among them, R is selected from C1-C20 alkyl groups, aryl groups, and heteroaryl groups; among them, the heteroaryl groups include thiophene, furan, pyridine, pyrrole, pyrazole, pyrimidine, pyrazine, pyridazine, and thiazole; the chiral configurations of both (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid and (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid ester compounds are in the (S) configuration, and the double bond configurations are all in the (E) form.

[0027] The Acyl Chloride 1 includes but is not limited to one or more selected from acetyl chloride, thionyl chloride, oxalyl chloride, etc. The dosage of the Acyl Chloride 1 is 1.0 to 15 mmol, that is, 0.5 to 15 equivalents, corresponding to each mmol of (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid; preferably, the Acyl Chloride 1 is selected from one of acetyl chloride, thionyl chloride, etc., and the dosage of the Acyl Chloride 1 is 1.5 equivalents;

[0028] The Base 1 includes but is not limited to one or more selected from triethylamine, diisopropylethylamine, DMAP (4-dimethylaminopyridine), pyridine, tributylamine, N,N-dimethylaniline, N-methylpyrrolidine, N-methylpiperidine, DABCO, etc.; the dosage of the Base 1 is 0.1 to 5 mmol, that is, 0.1 to 5 equivalents, corresponding to each mmol of (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid; preferably, the Base 1 is selected from one of triethylamine, DMAP, etc., and the dosage of the Base 1 is 1.5 equivalents;

[0029] The Solvent 1 includes but is not limited to one or more selected from toluene, dichloromethane, ethyl acetate, tetrahydrofuran, acetone, acetonitrile, DMF, DMSO, ethanol, methanol, etc. The dosage of the Solvent 1 is 0.1 mL to 50 mL corresponding to each mmol of (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid. Preferably, the Solvent 1 is dichloromethane; the dosage of the Solvent 1 is 5 mL.

[0030] The reaction temperature is -10°C to 100°C, and the reaction time is 0.5 - 100 hours. Preferably, the reaction temperature is 0°C and the reaction time is 12 h.

[0031] In a specific embodiment, in Solvent 2, (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid undergoes a condensation reaction with amines of different structures in the presence of Condensing Agent 1 and Base 2, and the S-methoprene amide derivatives of formula (II), namely (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid amide compounds, can be obtained by separation and purification. The method is shown in Reaction Scheme (C) as follows:

[0032]

[0033] Among them, R is selected from C1-C20 alkyl, aryl, and heteroaryl; among them, the heteroaryl includes thiophene, furan, pyridine, pyrrole, pyrazole, pyrimidine, pyrazine, pyridazine, and thiazole; R1 is selected from hydrogen, C1-C20 alkyl, and aryl; the chiral configurations of both (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid and (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid amide compounds are in the (S) configuration, and the double bond configurations are all in the (E) form.

[0034] The Condensing Agent 1 includes but is not limited to one or several selected from DIC (N,N-diisopropylcarbodiimide), DCC (N,N-dicyclohexylcarbodiimide), HOBt (hydroxybenzotriazole), HOAt (N-hydroxy-7-azabenzotriazole), HATU (N,N,N',N'-tetramethyl-O-(7-azabenzotriazol-1-yl)uronium hexafluorophosphate), HBTU (benzotriazole-N,N,N',N'-tetramethyluronium hexafluorophosphate), HCTU (6-chlorobenzotriazole-1,1,3,3-tetramethyluronium hexafluorophosphate), or EDC·HCl (1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride), etc. The amount of Condensing Agent 1 used is 0.5 to 5 millimoles, i.e., 0.5 to 5 equivalents, corresponding to each millimole of (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid. Preferably, the Condensing Agent 1 is one of DIC (N,N-diisopropylcarbodiimide), EDC·HCl (1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride), etc., and the amount of Condensing Agent 1 used is 1.0 to 5.0 equivalents; more preferably, the amount of Condensing Agent 1 used is 1.5 equivalents.

[0035] The base 2 includes, but is not limited to, one or more selected from triethylamine, diisopropylethylamine, DMAP (4-dimethylaminopyridine), N,N-dimethylaniline, pyridine, tributylamine, N-methylpyrrolidine, N-methylpiperidine, etc. The amount of the base 2 used is 0.1 to 4 millimoles, i.e., 0.1 to 4 equivalents, corresponding to each millimole of (2E,4E,7S)-11-methoxy-3,7,11-trimethyldodeca-2,4-dienoic acid. Preferably, the base 2 is triethylamine or diisopropylethylamine, and the amount of the base 2 used is 1.5 equivalents.

[0036] The solvent 2 includes, but is not limited to, one or more selected from toluene, dichloromethane, ethyl acetate, tetrahydrofuran, acetone, acetonitrile, DMF, DMSO, ethanol, methanol, etc. The amount of the solvent 2 used is 0.1 mL to 50 mL corresponding to each millimole of (2E,4E,7S)-11-methoxy-3,7,11-trimethyldodeca-2,4-dienoic acid. Preferably, the solvent 2 is dichloromethane, and the amount of the solvent 2 used is 5 mL.

[0037] The reaction temperature is -10°C to 100°C, and the reaction time is 0.5 - 100 hours. Preferably, the reaction temperature is 0°C, and the reaction time is 12 h.

[0038] The present invention also provides the ester and amide derivatives of S-methoprene shown by formula (1) prepared by the above preparation method, which include the compounds shown by formula (I) and formula (II).

[0039] The beneficial effects of the present invention include, but are not limited to: providing a class of ester and amide derivatives of S-methoprene with new structures and their preparation methods, and simultaneously providing the ester and amide compounds of S-methoprene and their synthesis methods. The present invention also provides the application of the ester and amide derivatives of S-methoprene in the control of agricultural pests including, but not limited to, Plutella xylostella and Aphis medicaginis. The new structure compounds provided by the present invention have good activity in the inhibition of specific pests, and preferably have good activity in inhibiting the growth of Plutella xylostella larvae and Aphis medicaginis nymphs. The compounds and their manufacturing methods of the present invention have broad application prospects. Specific Embodiments

[0040] Combined with the following specific embodiments, the present invention will be further described in detail. The processes, conditions, experimental methods, etc. for implementing the present invention, except for the specifically mentioned content below, are all common knowledge and well-known common sense in the art, and the present invention has no particularly limited content.

[0041] Example 1:

[0042]

[0043] In a 100 mL three-necked flask, (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid (2.69 g, 10 mmol) and CH2Cl2 (10 mL) were added under nitrogen protection and stirred at room temperature. Then 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride EDCI (5.7 g, 15 mmol) was slowly added and stirred. Subsequently, isopropanol (0.90 g, 15 mmol) and 1-hydroxybenzotriazole HOBT (1.35 g, 10 mmol) were added in sequence and stirred for 3 h. After the raw materials were completely converted, water was added to quench the reaction system, and it was extracted three times with dichloromethane, 10 mL each time. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10 / 1 - 5 / 1) to obtain the target product as a colorless oily liquid (2.76 g, 89% yield, NMR and gas phase purity: 98%). When 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI) was replaced with similar condensation reagents such as N,N-diisopropylcarbodiimide (DIC) and N,N-dicyclohexylcarbodiimide (DCC), similar yields could also be obtained.

[0044] Colorless liquid, 89%yield, [α] D 20 = 1.80 (c = 1.000, CHCl3). 1 H NMR (300 MHz, CDCl3): δ6.15–6.03 (m, 2H), 5.67 (d, J = 1.0 Hz, 1H), 5.05 (hept, J = 6.3 Hz, 1H), 3.17 (s, 3H), 2.27 (s, 3H), 2.22–2.14 (m, 1H), 2.04–1.95 (m, 1H), 1.62–1.54 (m, 1H), 1.48–1.40 (m, 12H), 1.37–1.30 (m, 12H), 1.26 (d, J = 8.4 Hz, 6H), 1.14 (s, 6H), 0.88 (d, J = 6.7 Hz, 3H); 13 C NMR (100 MHz, CDCl3): δ166.9, 152.2, 136.0, 134.9, 118.2, 74.6, 66.7, 49.1, 40.6, 40.1, 37.2, 33.2, 25.0, 22.0, 21.3, 19.6, 13.9; IR (neat): 2973, 1708, 1614, 1363, 1239, 1159, 1079, 967, 879 cm -1 ; HRMS (ESI): Exact mass calcd for C 19 H34 O3Na[M+Na]+: 333.2400, Found: 333.2390.

[0045] Example 2:

[0046]

[0047] In a 100 mL three-necked flask, under nitrogen protection, (2E,4E,7S)-11-methoxy-3,7,11-trimethyldodeca-2,4-dienoic acid (2.69 g, 10 mmol), cyclopropanol (0.87 g, 15 mmol) and dichloromethane (20 mL) were added and stirred at room temperature. Then, N,N-diisopropylcarbodiimide DIC (1.89 g, 15 mmol) was slowly added and stirred, and then 4-dimethylaminopyridine DMAP (122 mg, 1 mmol) was added and stirred for 4 h. After the raw materials were completely converted, water was added to quench the reaction system, and the mixture was extracted with dichloromethane three times, 10 mL each time. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10 / 1 - 5 / 1) to obtain the target product as a colorless oily liquid (1.54 g, 50% yield, NMR and gas phase purity: 98%). When DIC (N,N-diisopropylcarbodiimide) was replaced with similar condensation reagents such as benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (HBTU), N,N'-dicyclohexylcarbodiimide (DCC), 6-chloro-1H-benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (HCTU), etc., similar yields could also be obtained.

[0048] Colorless liquid, 50% yield, [α] D 20 = 4.35 (c = 0.230, CHCl3). 1 1H NMR (400 MHz, CDCl3): δ 6.17 - 6.03 (m, 2H), 5.62 (s, 1H), 4.16 - 4.09 (m, 1H), 3.17 (s, 3H), 2.27 (d, J = 1.2 Hz, 3H), 2.20 - 2.13 (m, 1H), 2.04 - 1.95 (m, 1H), 1.60 - 1.54 (m, 1H), 1.44 - 1.27 (m, 6H), 1.13 (s, 6H), 0.88 (d, J = 6.6 Hz, 3H), 0.73 - 0.69 (m, 4H); 1313C NMR(100MHz,CDCl3):δ168.1,153.1,136.5,134.7,117.1,74.6,49.1,48.1,40.5,40.1,37.2,33.2,24.9,21.3,19.6,13.9,5.1; IR(neat):2970,1716,1610,1363,1235,1153,1084,966,871cm -1 ; HRMS(ESI):Exact mass calcd for C 19 H 32 O3Na[M+Na] + :331.2244,Found:331.2230.

[0049] Example 3:

[0050]

[0051] (2E,4E,7S)-11-Methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid (2.69 g, 10 mmol), allyl alcohol (0.87 g, 15 mmol) and dichloromethane (20 mL) were added to a 100 mL three-necked flask under nitrogen protection and stirred at room temperature. Then DCC (N,N'-dicyclohexylcarbodiimide) (3.09 g, 15 mmol) was slowly added and stirred, and then 4-dimethylaminopyridine DMAP (122 mg, 1 mmol) was added and stirred for 10 h. After the raw materials were completely converted, water was added to quench the reaction system, and the mixture was extracted with dichloromethane three times, 10 mL each time; the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10 / 1 - 5 / 1) to obtain the target product as a colorless oily liquid (1.69 g, 55% yield, NMR and gas phase purity: 98%). When DCC (N,N'-dicyclohexylcarbodiimide) is replaced with similar condensation reagents such as DIC (N,N-diisopropylcarbodiimide), N,N,N′,N′-tetramethyl-O-(7-azabenzotriazol-1-yl)uronium hexafluorophosphate (HATU), benzotriazole-N,N,N',N'-tetramethylurea hexafluorophosphate (HBTU), 6-chlorobenzotriazole-1,1,3,3-tetramethyluronium hexafluorophosphate (HCTU), etc., similar yields can be obtained.

[0052] Colorless liquid, 55% yield. [α] D 20 = 4.17 (c = 0.563, CHCl3). 11H NMR (400 MHz, CDCl3): δ 6.12 - 6.10 (m, 2H), 6.00 - 5.90 (m, 1H), 5.73 (s, 1H), 5.33 (d, J = 17.2 Hz, 1H), 5.23 (d, J = 10.0 Hz, 1H), 4.62 (d, J = 5.6 Hz, 2H), 3.17 (s, 3H), 2.28 (s, 3H), 2.20–2.15 (m, 1H), 2.02–1.97 (m, 1H), 1.56 (s, 1H), 1.43–1.41 (m, 2H), 1.39–1.25 (m, 4H), 1.14 (s, 6H), 0.89 (d, J = 6.8 Hz, 3H); 13 13C NMR (100 MHz, CDCl3): δ 166.8, 153.2, 136.4, 134.7, 132.7, 117.8, 117.2, 74.6, 64.4, 49.1, 40.6, 40.1, 37.2, 33.2, 25.0, 21.3, 19.6, 14.0; IR (neat): 2937, 1732, 1609, 1354, 1227, 1126, 1085, 967, 870 cm -1 ; HRMS (ESI): Exact mass calcd for C 19 H 32 O3Na [M+Na] + : 331.2244, Found: 331.2226.

[0053] Example 4:

[0054]

[0055] In a 100 mL three-necked flask, under nitrogen protection, (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid (2.69 g, 10 mmol), sec-butanol (1.11 g, 15 mmol) and dichloromethane (20 mL) were added and stirred at room temperature. Then, DCC (N,N'-dicyclohexylcarbodiimide) (3.09 g, 15 mmol) was slowly added and stirred, and then 4-dimethylaminopyridine D MAP (122 mg, 1 mmol) was added and stirred for 10 h. After the raw materials were completely converted, water was added to quench the reaction system, and the mixture was extracted with dichloromethane three times, 10 mL each time; the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10 / 1 - 5 / 1) to obtain the target product as a colorless oily liquid (1.62 g, 50% yield, NMR and gas phase purity: 98%). When DCC (N,N'-dicyclohexylcarbodiimide) is replaced with similar condensation reagents such as DIC (N,N-diisopropylcarbodiimide), N,N,N′,N′-tetramethyl-O-(7-azabenzotriazol-1-yl)uronium hexafluorophosphate (HATU), benzotriazole-N,N,N',N'-tetramethylurea hexafluorophosphate (HBTU), 6-chlorobenzotriazole-1,1,3,3-tetramethyluronium hexafluorophosphate (HC TU), etc., similar yields can also be obtained.

[0056] Colorless liquid, 50% yield. [α] D 20 = 3.79 (c = 0.203, CHCl3). 1 1H NMR (400 MHz, CDCl3): δ 6.13–6.05 (m, 2H), 5.68 (s, 1H), 4.92–4.84 (m, 1H), 3.17 (s, 3H), 2.27 (s, 3H), 2.19–2.14 (m, 1H), 2.02–1.96 (m, 1H), 1.64–1.53 (m, 3H), 1.45–1.41 (m, 2H), 1.37–1.25 (m, 4H), 1.22 (d, J = 6.4 Hz, 3H), 1.13 (s, 6H), 0.92–0.87 (m, 6H); 13 13C NMR (100 MHz, CDCl3): δ 167.0, 152.1, 135.8, 134.9, 118.2, 74.5, 71.3, 53.4, 49.1, 40.6, 40.1, 37.2, 33.2, 28.9, 25.0, 21.3, 19.6, 13.9, 9.7; IR (neat): 2971, 1709, 1613, 1363, 1238, 1158, 1085, 966, 871 cm-1 ; HRMS(ESI): Exact mass calcd for C 20 H 36 O3Na[M+Na] + : 347.2557, Found: 347.2538.

[0057] Example 5:

[0058]

[0059] In a 100 mL three-necked flask, (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid (2.69 g, 10 mmol) and DMF (10 mL) were added under nitrogen protection and stirred at room temperature. Triethylamine (1.5 g, 15 mmol) and anhydrous dichloromethane (20 mL) were stirred at room temperature, and then 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI, 2.8 g, 15 mmol) was slowly added and stirred for 4 h. After the raw materials were completely converted, water was added to quench the reaction system, and the mixture was extracted three times with dichloromethane, 10 mL each time; the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10 / 1 - 5 / 1) to obtain the target product as a colorless oily liquid (2.38 g, 78% yield, NMR and gas phase purity: 98%). When EDCI (1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride) was replaced with similar condensation reagents such as benzotriazol-N,N,N',N'-tetramethyluronium hexafluorophosphate (HBTU), 6-chlorobenzotriazol-1,1,3,3-tetramethyluronium hexafluorophosphate (HCTU), etc., similar yields could also be obtained.

[0060] Colorless liquid, 78% yield, [α] D 20 = 5.74 (c = 0.190, CHCl3). 1 1H NMR (300 MHz, CDCl3): δ 6.21 - 6.06 (m, 2H), 5.73 (s, 1H), 4.71 (d, J = 2.7 Hz, 2H), 3.17 (s, 3H), 2.46 (t, J = 2.7 Hz, 1H), 2.29 (s, 3H), 2.23 - 2.15 (m, 1H), 2.06 - 1.97 (m, 1H), 1.61 - 1.55 (m, 2H), 1.45 - 1.40 (m, 2H), 1.34 - 1.26 (m, 3H), 1.14 (s, 6H), 0.89 (d, J = 6.6 Hz, 3H); 1313C NMR (100 MHz, CDCl3): δ 166.2, 154.3, 137.1, 134.6, 116.2, 78.2, 74.6, 74.4, 51.2, 49.1, 40.6, 40.1, 37.2, 33.2, 25.0, 21.3, 19.6, 14.1; IR (neat): 2970, 2939, 1717, 1610, 1365, 1234, 1142, 1081, 967, 870 cm -1 ; HRMS (ESI): Exact mass calcd for C 19 H 30 O3Na [M+Na] + : 329.2087, Found: 329.2079.

[0061] Example 6:

[0062]

[0063] In a 100 mL three-necked flask, (2E,4E,7S)-11-methoxy-3,7,11-trimethyldodeca-2,4-dienoic acid (2.69 g, 10 mmol) and DMF (10 mL) were added under nitrogen protection and stirred at room temperature. Then, N,N,N′,N′-tetramethyl-O-(7-azabenzotriazol-1-yl)uronium hexafluorophosphate HATU (5.7 g, 15 mmol) was slowly added and stirred. Subsequently, isobutanol (1.48 g, 20 mmol) and triethylamine (3.0 g, 30 mmol) were added in sequence and stirred for 6 h. After complete conversion of the starting materials, the reaction system was quenched with water and extracted three times with 10 mL of dichloromethane each time; the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10 / 1 - 5 / 1) to obtain the target product as a colorless oily liquid (1.29 g, 40% yield, NMR and gas phase purity: 98%). When N,N,N′,N′-tetramethyl-O-(7-azabenzotriazol-1-yl)uronium hexafluorophosphate (HATU) was replaced with similar condensation reagents such as benzotriazol-N,N,N',N'-tetramethyluronium hexafluorophosphate (HBTU) and 6-chloro-1,1,3,3-tetramethyluronium hexafluorophosphate (HCTU), similar yields could be obtained. Colorless liquid, 40% yield. [α] D 20 = 4.35 (c = 0.170, CHCl3). 11H NMR (400 MHz, CDCl3): δ 6.09 (s, 2H), 5.71 (s, 1H), 3.89 (d, J = 6.8 Hz, 2H), 3.17 (s, 3H), 2.26 (s, 3H), 2.17–2.15 (m, 1H), 2.02–1.93 (m, 2H), 1.63–1.54 (m, 1H), 1.43–1.40 (m, 2H), 1.37–1.29 (m, 4H), 1.13 (s, 6H), 0.94 (d, J = 6.4 Hz, 6H), 0.88 (d, J = 6.8 Hz, 3H); 13 13C NMR (100 MHz, CDCl3): δ 167.4, 152.4, 136.0, 134.8, 117.7, 74.5, 69.9, 49.1, 40.6, 40.1, 37.2, 33.2, 27.8, 25.0, 21.3, 19.6, 19.2, 13.9; IR (neat): 2965, 1711, 1611, 1363, 1235, 1147, 1084, 966, 871 cm -1 ; HRMS (ESI): Exact mass calcd for C 20 H 36 O3Na [M+Na] + : 347.2557, Found: 347.2541. (CHP-CB-64)

[0064] Example 7:

[0065]

[0066] In a 100 mL three-necked flask, under nitrogen protection, (2E,4E,7S)-11-methoxy-3,7,11-trimethyldodeca-2,4-dienoic acid (2.69 g, 10 mmol), N,N'-carbonyldiimidazole CDI (1.78 g, 11 mmol), benzyl alcohol (1.29 g, 12 mmol), and anhydrous acetonitrile (20 mL) were successively added and stirred at room temperature for 4 h. After the raw materials were completely converted, saturated sodium bicarbonate was added, and the mixture was extracted with dichloromethane three times, 10 mL each time; the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10 / 1 - 5 / 1) to obtain the target product as a colorless oily liquid (2.36 g, 66% yield, NMR and gas phase purity: 98%). Among them, N,N'-carbonyldiimidazole CDI can be replaced with reagents such as HATU (N,N,N’,N’-tetramethyl-O-(7-azabenzotriazol-1-yl)uronium hexafluorophosphate), HBTU (benzotriazole-N,N,N',N'-tetramethyluronium hexafluorophosphate), etc., and similar yields can also be obtained.

[0067] Colorless liquid, 66% yield, [α] D 20 =5.39 (c=0.775, CHCl3). 1 1H NMR (300 MHz, CDCl3): δ 7.38 - 7.29 (m, 5H), 6.13 - 6.05 (m, 2H), 5.75 (s, 1H), 5.16 (s, 2H), 3.17 (s, 3H), 2.29 (d, J=0.9 Hz, 3H), 2.22 - 2.14 (m, 1H), 2.04 - 1.96 (m, 1H), 1.57 (m, 2H), 1.44 - 1.37 (m, 2H), 1.33 - 1.26 (m, 3H), 1.13 (s, 6H), 0.88 (d, J=6.6 Hz, 3H); 13 13C NMR (100 MHz, CDCl3): δ 167.0, 153.3, 136.5, 134.7, 128.5, 128.1, 128.0, 117.2, 74.6, 65.5, 49.1, 40.6, 40.1, 37.2, 33.2, 25.0, 21.3, 19.6, 14.0; IR (neat): 2970, 1716, 1456, 1380, 1233, 1146, 1077, 966, 871 cm−1; -1 ; HRMS (ESI): Exact mass calcd for C 23 21 34 H31O3Na [M + Na]+ + : 381.2400, Found: 381.2396. (YZT - YB - 13)

[0068] Example 8:

[0069]

[0070] In a 100 mL three-necked flask, under nitrogen protection, (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid (2.69 g, 10 mmol), diethylamine (1.54 mL, 15 mmol), triethylamine (1.54 mL, 30 mmol) and anhydrous dichloromethane (20 mL) were successively added and stirred at room temperature. Then, HATU (N,N,N’,N’-tetramethyl-O-(7-azabenzotriazol-1-yl)uronium hexafluorophosphate) (5.7 g, 15 mmol) was slowly added and stirred for 4 h. After the raw materials were completely converted, saturated sodium bicarbonate was added, and the mixture was extracted three times with 10 mL of dichloromethane each time. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10 / 1 - 5 / 1) to obtain the target product as a yellow oily liquid (2.73 g, 92% yield, NMR and gas phase purity: 98%). Among them, HATU (N,N,N’,N’-tetramethyl-O-(7-azabenzotriazol-1-yl)uronium hexafluorophosphate) can be replaced by reagents such as CDI (N,N'-carbonyldiimidazole), HBTU (benzotriazol-N,N,N',N'-tetramethylurea hexafluorophosphate), HCTU (6-chlorobenzotriazol-1,1,3,3-tetramethylurea hexafluorophosphate), etc. The triethylamine can be replaced by reagents such as diisopropylethylamine, pyridine, tributylamine, etc. to obtain a similar yield.

[0071] Yellow liquid, 56% yield, [α] D 20 = 1.28 (c = 0.290, CHCl3). 1 H NMR (300 MHz, CDCl3): δ 6.08 (d, J = 15.7 Hz, 1H), 5.93–5.83 (m, 2H), 3.34 (q, J = 9.2 Hz, 2H), 3.33 (q, J = 9.2 Hz, 2H), 3.18 (s, 3H), 2.20–2.11 (m, 1H), 2.05–1.95 (m, 4H), 1.56–1.47 (m, 1H), 1.46–1.22 (m, 6H), 1.17 - 1.14 (m, 12H), 0.89 (d, J = 6.6 Hz, 3H); 13 C NMR (100 MHz, CDCl3): δ 167.7, 143.9, 134.6, 132.7, 120.6, 74.6, 49.1, 42.5, 40.4, 40.1, 39.5, 37.2, 33.3, 25.0, 21.3, 19.6, 14.4, 13.2; IR (neat): 2970, 1716, 1627, 1363, 1219, 1148, 1080 cm -1; HRMS(ESI): Exact mass calcd for C 20 H 37 NO2Na [M+Na] + : 346.2717, Found: 346.2706. (WZW-WA-141)

[0072] Example 9:

[0073]

[0074] In a 100 mL three-necked flask, under nitrogen protection, (2E,4E,7S)-11-methoxy-3,7,11-trimethyldodeca-2,4-dienoic acid (2.69 g, 10 mmol), N,N'-carbonyldiimidazole CDI (1.78 g, 11 mmol), p-methoxyaniline PMPN H2 (1.47 g, 12 mmol), and anhydrous tetrahydrofuran (20 mL) were successively added and stirred at room temperature for 4 h. After the raw materials were completely converted, saturated sodium bicarbonate was added, and the mixture was extracted three times with dichloromethane, 10 mL each time; the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 10 / 1 - 5 / 1) to obtain the target product as a yellow solid (1.04 g, 28% yield, NMR and gas phase purity: 98%). Among them, N,N'-carbonyldiimidazole CDI can be replaced by reagents such as HATU (N,N,N’,N’-tetramethyl-O-(7-azabenzotriazol-1-yl)uronium hexafluorophosphate), HBTU (benzotriazole-N,N,N',N'-tetramethylurea hexafluorophosphate), etc., and similar yields can also be obtained.

[0075] Yellow solid, 28% yield, m.p. = 58.5–60.2 °C; [α] D 20 = 5.07 (c = 0.655, CHCl3). 1 H NMR (400 MHz, CDCl3): δ 7.45 (d, J = 8.4 Hz, 2H), 7.25 (s, br, 1H), 6.84 (d, J = 8.8 Hz, 2H), 6.06 (s, 2H), 5.71 (s, 2H), 3.78 (s, 3H), 3.17 (s, 3H), 2.32 (s, 3H), 2.19–2.16 (m, 1H), 2.04–1.98 (m, 1H), 1.59–1.55 (m, 1H), 1.44–1.25 (m, 6H), 1.14 (s, 6H), 0.89 (d, J = 6.6 Hz, 3H); 13CNMR (100 MHz, CDCl3): δ 165.2, 156.2, 149.7, 135.1, 134.9, 131.4, 121.6, 120.4, 114.1, 74.6, 55.5, 49.1, 40.5, 40.1, 37.2, 33.2, 25.0, 21.3, 19.6, 13.8; IR (neat): 2969, 1651, 1609, 1509, 1363, 1242, 1167, 1081, 966, 830 cm -1 ; HRMS (ESI): Exact mass calcd for C 23 H 35 NO3Na [M+Na] + : 396.2509, Found: 396.2514.

[0076] Example 10

[0077] Growth inhibition experiment on Plutella xylostella larvae: Using chromatographically pure N,N-dimethylformamide as a co-solvent, dilute the compound of the present invention (see Table 1) to 0.002 - 20 mg / L with pure water containing 0.05% Tween-80. The content of N,N-dimethylformamide in the test solution does not exceed 0.1%. Wash the cabbage leaves, dry them, and make leaf discs with a diameter of 5.0 cm. Using the leaf-dipping method, immerse the leaves in 100 mL of the test solution, take them out and dry them after 10 s, and place them in a 9 cm Petri dish. Introduce 10 healthy late fourth-instar Plutella xylostella larvae of the same size into each Petri dish. The whole operation is carried out in a well-ventilated environment. There are 3 replicates for each treatment, with 20 Plutella xylostella larvae in each replicate. The control group is an aqueous solution of Tween-80 containing 0.1% N,N-dimethylformamide. After applying the drug, place the Petri dishes in an incubator at 25 ± 1 °C, 50 - 70 RH%, and a light-dark cycle of 14L:10D, and continuously observe the situation of Plutella xylostella turning into adults. The experimental results are shown in Table 1.

[0078] Table 1 Representative data on the growth inhibition of Plutella xylostella larvae by the alkyl ester (amide) compounds in the present invention

[0079]

[0080]

[0081] Example 11

[0082] Experiment on the growth inhibition of alfalfa aphid nymphs: Using chromatographically pure N,N-dimethylformamide as a cosolvent, the compound of the present invention (see Table 2) was diluted to 14.8-200 mg / L using pure water containing 0.05% Tween-80, and the N,N-dimethylformamide content in the test solution did not exceed 0.1%. Using the insect-leaf dipping method, the broad bean seedlings with 10 four-day-old alfalfa aphid nymphs were soaked in the test solution for 10 seconds, and the excess liquid was taken out and dried. The insect-infested broad bean seedlings were inserted into a glass bottle containing clean water and cultured at 25±1℃ and a light-dark cycle of 14L:10D. After 5 days, the number of surviving adult aphids and nymphs was recorded. Each treatment was repeated 3 times, with 20 alfalfa aphid nymphs in each repeat, and the control group was a Tween-80 aqueous solution containing 0.1% N,N-dimethylformamide. The experimental results are shown in Table 2.

[0083] Table 2 Representative data of the alkyl ester (amide) compounds of the present invention on the growth and reproduction inhibition of alfalfa aphids

[0084]

[0085]

[0086] According to the above data, the ester and amide derivatives of S-methoprene provided by the present invention (including the compounds of the present invention listed in Tables 1 and 2 and other compounds of the present invention) have good biological activity against Plutella xylostella and alfalfa aphid.

[0087] The protection content of the present invention is not limited to the above embodiments. Without departing from the spirit and scope of the present invention, changes and advantages that can be thought of by those skilled in the art are included in the present invention and are protected by the attached claims.

Claims

1. A class of esters and amide derivatives of S-methoprene, characterized in that, Its structural formula is shown in Formula (1): In the said Formula (1), R is selected from C1-C20 alkyl, aryl, heteroaryl; wherein, the heteroaryl includes thiophene, furan, pyridine, pyrrole, pyrazole, pyrimidine, pyrazine, pyridazine, thiazole; X is selected from oxygen, NH, a nitrogen atom with a substituent; the chiral configuration in the compound shown in Formula (1) is the (S) configuration, and the double bond configuration is the (E) form.

2. The esters and amide derivatives of S-methoprene according to claim 1, characterized in that, The derivatives include (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid esters and (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid amides, as shown in the following Formulas (I) and (II) respectively: Wherein, R is selected from C1-C20 alkyl, aryl, heteroaryl; wherein, the heteroaryl includes thiophene, furan, pyridine, pyrrole, pyrazole, pyrimidine, pyrazine, pyridazine, thiazole; R1 is selected from hydrogen, C1-C20 alkyl, aryl; the chiral configurations of the compounds shown in Formulas (I) and (II) are both the (S) configuration, and the double bond configurations are both the (E) form.

3. The ester and amide derivatives of S-methoprene as claimed in claim 1, characterized in that, It includes the following compounds:

4. The method for preparing the ester and amide derivatives of S-methoprene as claimed in claim 1 or 3, characterized in that, In a solvent, (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid and an alcohol or an amine undergo an esterification or amidation reaction under the action of an activator and a base, and after separation and purification, the ester and amide derivatives of S-methoprene shown in Formula (1) are obtained; the preparation method is shown in the following Reaction Formula (A): In the said Reaction Formula (A), R is selected from C1-C20 alkyl, aryl, heteroaryl; wherein, the heteroaryl includes thiophene, furan, pyridine, pyrrole, pyrazole, pyrimidine, pyrazine, pyridazine, thiazole; wherein, X is selected from oxygen, NH, a nitrogen atom with a substituent; the chiral configurations of (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid in the reactants and the (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid esters or amides in the products are both the (S) configuration, and the double bond configurations are both the (E) form; the activator includes acyl chloride, condensing agent.

5. The preparation method of the ester derivative of S-methoprene according to claim 4, characterized in that, In a solvent, (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid undergoes an esterification reaction with an alcohol under the action of acyl chloride and a base, and after separation and purification, the ester derivatives of S-methoprene shown in Formula (I), namely (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid esters, are obtained. The method is shown in the following Reaction Formula (B): Among them, R is selected from C1-C20 alkyl, aryl, heteroaryl; wherein, the heteroaryl includes thiophene, furan, pyridine, pyrrole, pyrazole, pyrimidine, pyrazine, pyridazine, thiazole; the chiral configurations of the (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid and the (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid ester compounds are both (S) configurations, and the double bond configurations are both (E) forms.

6. The preparation method of the amide derivative of S-methoprene as described in claim 4, characterized in that, In a solvent, (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid undergoes a condensation reaction with an amine under the action of a condensing agent and a base, and after separation and purification, an amide derivative of S-methoprene of formula (II) is obtained, namely ((2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid amide compounds, and the method is shown in reaction formula (C) as follows: Among them, R is selected from C1-C20 alkyl, aryl, heteroaryl; wherein, the heteroaryl includes thiophene, furan, pyridine, pyrrole, pyrazole, pyrimidine, pyrazine, pyridazine, thiazole; R1 is selected from hydrogen, C1-C20 alkyl, aryl; the chiral configurations of the (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid and the (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid amide compounds are both (S) configurations, and the double bond configurations are both (E) forms.

7. The method for preparing the ester and amide derivatives of S-methoprene according to claim 5, wherein the acyl chloride is selected from one or more of acetyl chloride, thionyl chloride, oxalyl chloride; the amount of the acyl chloride used is 1.0 to 15 mmol corresponding to each mmol of (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid; and / or, the base is selected from one or more of triethylamine, diisopropylethylamine, 4-dimethylaminopyridine, pyridine, tributylamine, N,N-dimethylaniline, N-methylpyrrolidine, N-methylpiperidine, DABCO; the amount of the base used is 0.1 to 5 mmol corresponding to each mmol of (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid; and / or, the solvent is selected from one or more of toluene, dichloromethane, ethyl acetate, tetrahydrofuran, acetone, acetonitrile, DMF, DMSO, ethanol, methanol; the amount of the solvent used is 0.1 mL to 50 mL corresponding to each mmol of (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid; and / or, the temperature of the reaction is -10°C to 100°C; and / or, the time of the reaction is 0.5 - 100 hours; and / or, the prepared ester derivative of S-methoprene is an optically pure ester derivative compound of S-methoprene.

8. The preparation method of the ester and amide derivatives of S-methoprene as claimed in claim 6, characterized in that, the condensing agent is selected from one or more of N,N-diisopropylcarbodiimide, N,N-dicyclohexylcarbodiimide, hydroxybenzotriazole, N-hydroxy-7-azabenzotriazole, N,N,N',N'-tetramethyl-O-(7-azabenzotriazol-1-yl)uronium hexafluorophosphate, benzotriazole-N,N,N',N'-tetramethylurea hexafluorophosphate, 6-chlorobenzotriazole-1,1,3,3-tetramethylurea hexafluorophosphate or 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride; the amount of the condensing agent used is 0.5 to 5 mmol corresponding to each mmol of (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid; and / or, the base is selected from one or more of triethylamine, diisopropylethylamine, DMAP, pyridine, tributylamine, N,N-dimethylaniline, N-methyltetrahydropyrrole, N-methylpiperidine; the amount of the base used is 0.1 to 4 mmol corresponding to each mmol of (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid; and / or, the solvent is selected from one or more of toluene, dichloromethane, ethyl acetate, tetrahydrofuran, acetone, acetonitrile, DMF, DMSO, ethanol, methanol; the amount of the solvent used is 0.1 mL to 50 mL corresponding to each mmol of (2E,4E,7S)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoic acid; and / or, the temperature of the reaction is -10°C to 100°C; and / or, the time of the reaction is 0.5 - 100 hours; and / or, the prepared amide derivative of S-methoprene is an optically pure amide derivative compound of S-methoprene.

9. The ester and amide derivatives of S-methoprene shown by formula (1) prepared by the method according to claim 4, characterized in that, It includes the compounds shown in formula (I) and formula (II).

10. The application of the ester and amide derivatives of S-methoprene as claimed in any one of claims 1 to 3, 9, and the preparation method as claimed in any one of claims 4 to 8 in the control of agricultural pests such as Plutella xylostella and Aphis medicaginis, and in the growth inhibition of Plutella xylostella larvae and Aphis medicaginis nymphs.

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