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A kind of method for synthesizing flea beetle aggregation pheromone

A technology for gathering pheromones and flea beetles, which is applied in the field of green pesticides and can solve problems such as low total yield, difficulty in scaling up, and lengthy synthetic routes

Active Publication Date: 2022-07-26
CHINA AGRI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] Although the synthesis of flea beetle aggregation pheromone 1 has been reported in the literature, these methods have many problems such as lengthy synthetic routes, low overall yields, and difficulty in scaling up.

Method used

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  • A kind of method for synthesizing flea beetle aggregation pheromone
  • A kind of method for synthesizing flea beetle aggregation pheromone
  • A kind of method for synthesizing flea beetle aggregation pheromone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Synthesis of 2-cyclohepten-1-one (3)

[0023] Cycloheptanone (5.608 g, 50.00 mmol) was added to a 500 mL single-neck flask, and anhydrous DCM (50 mL) was added. P-toluenesulfonic acid monohydrate (85.0 mg, 0.50 mmol) was slowly added, and the reaction was carried out at room temperature for 10 min. Under ice-cooling, NBS (9.788 g, 55.00 mmol) was slowly added, the temperature was gradually raised to room temperature, and the reaction was carried out at room temperature for 16 h to stop the reaction. Under ice-cooling, saturated sodium thiosulfate solution (40 mL) was added, and the solution was separated. The aqueous phase was extracted with DCM (3 x 100 mL) and the organic phases were combined. Anhydrous Na for organic phase 2 SO 4 Dry and remove the solvent under reduced pressure. Finally, it was purified by silica gel column chromatography (petroleum ether:ethyl acetate 10:1) to obtain the crude bromocycloheptanone.

[0024] Under the protection of argon, lithi...

Embodiment 2

[0026] Synthesis of (R)-3-methylcycloheptanone (4)

[0027] Under argon, Cu(TC) (28.6 mg, 0.15 mmol), ligand L1 (307.8 mg, 0.6 mmol) and ultra-dry Et 2 O (10 mL) was added to a 100 mL Shrek bottle, and the reaction was stirred for 1 h. Cool to -30°C and add trimethylaluminum (18 mL, 1 M in ether, 18 mmol) dropwise. The reaction was carried out at -30 °C for 1 h, then 2-cyclohepten-1-one (3) (1.100 g, 10 mmol) was added dropwise within 1 h, and the reaction was carried out at -30 °C for 6 h to stop the reaction. The reaction was quenched with ice (5.00 g) and the layers were separated. Et for water phase 2 O (3 x 30 mL) extraction, combined organic phases. Anhydrous Na for organic phase 2 SO 4Dry and remove the solvent under reduced pressure. Finally, it was purified by silica gel column chromatography (petroleum ether:diethyl ether 30:1) to obtain (R)-3-methylcycloheptanone (4) as a colorless oil (1.00 g, yield 85%, optical purity 90%) .

[0028] See formula 3 for the...

Embodiment 3

[0031] Synthesis of (R)-2,2,6-trimethylcycloheptanone (5)

[0032] Under argon protection, potassium tert-butoxide (1.137 g, 10.15 mmol) and anhydrous THF (20 mL) were added to a 100 mL Shrek bottle, and stirred uniformly. Then, a solution of chiral methylcycloheptanone 4 (800 mg, 6.34 mmol) in THF (5 mL) was added dropwise, the temperature was lowered to 0° C., and the reaction was stirred for 1 h. Continue to cool down to -15°C, add iodomethane (1.800 g, 12.68 mmol) dropwise, and react at -15°C for 15 min to stop the reaction. Saturated aqueous ammonium chloride solution (10 mL) was added to quench the reaction, the layers were separated, and the aqueous phase was treated with Et 2 Extract with O (3 x 20 mL) and combine the organic phases. Anhydrous Na for organic phase 2 SO 4 Dry and remove the solvent under reduced pressure. Finally, it was purified by silica gel column chromatography (petroleum ether:diethyl ether 80:1) to obtain trimethylcycloheptanone 5 (0.780 g, 8...

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Abstract

The invention belongs to the technical field of green pesticides, and discloses a new method for synthesizing flea aggregation pheromone. In the method, cycloheptanone (2) is used as the starting material, first bromination reaction with NBS occurs, and then elimination reaction occurs under the alkaline conditions of lithium bromide and lithium carbonate to obtain cycloheptenone 3, which is then catalyzed by copper. Asymmetric Michael addition reaction to obtain chiral methylcycloheptanone 4; then react with methyl iodide to obtain trimethylcycloheptanone 5. 5 undergoes an aldol condensation reaction with trimethylsilylbutenone under the catalysis of LDA , the diketone 6 was obtained, and finally the folic acid aggregation pheromone 1 was obtained by Robinson cyclization reaction. The invention utilizes the asymmetric Michael addition reaction for the first time to construct the chiral methyl group of the condensed pheromone, and has the advantages of simple synthesis route, easy operation and the like.

Description

technical field [0001] The invention belongs to the technical field of green pesticides, and in particular relates to a new method for synthesizing flea aggregation pheromone. Background technique [0002] Flea beetles belong to the subfamily Alticinae (Alticinae) of Chrysomelidae (Coleoptera), with a wide variety of species and are widely distributed around the world (Wei, J.; Segraves, K.A.; Li, W.-Z.; Yang, X. -K.; Xue, H.-J. Microb. Ecol. 2020, 80, 946. Furth David, G. Zookeys 2013, 1.). The subfamily Fusarium includes many important pests that harm crops such as vegetables, fruits, and grains (Mason, J.; Alford, A.M.; Kuhar, T.P.J.Econ.Entomol. 2020, 113, 887.). Flea beetle aggregation pheromone is a trace chemical substance secreted and released by male adults that can aggregate a large number of male and female insects of the same species (Peng, C.; Weiss, M.J.J.Chem.Ecol.1992,18,875.Peng,C.;Peng, C.; Bartelt, R.J.; Weiss, M.J. Physiol. Entomol. 1999, 24, 98.), whic...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C45/67C07C49/627
CPCC07C45/61C07C45/62C07C45/72C07C45/67C07B2200/07C07C49/607C07C49/413C07C49/627
Inventor 钟江春王李锋周云王敏原超楠边庆花
Owner CHINA AGRI UNIV
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