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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: 2021-12-10
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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  • Method for synthesizing flea beetle aggregation pheromone
  • Method for synthesizing flea beetle aggregation pheromone
  • 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 one-necked flask, and anhydrous DCM (50 mL) was added. Add p-toluenesulfonic acid monohydrate (85.0 mg, 0.50 mmol) slowly and react at room temperature for 10 min. Under cooling in an ice bath, NBS (9.788 g, 55.00 mmol) was added slowly, the temperature was gradually raised to room temperature, and the reaction was carried out at room temperature for 16 h, then the reaction was stopped. Under cooling in an ice bath, a saturated solution of sodium thiosulfate (40 mL) was added, and the layers were 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 solvent under reduced pressure. Finally, it was purified by silica gel column chromatography (petroleum ether: ethyl acetate 10:1) to obtain the crude product of bromocycloheptanone.

[0024] Under argon protection...

Embodiment 2

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

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

[0028] See Formula 3 for the structu...

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 evenly. Then a solution of chiral methylcycloheptanone 4 (800mg, 6.34mmol) in THF (5mL) was added dropwise, the temperature was lowered to 0°C, and the reaction was stirred for 1h. Continue to cool down to -15°C, add iodomethane (1.800g, 12.68mmol) dropwise, react at -15°C for 15min, and stop the reaction. Add saturated aqueous ammonium chloride solution (10mL) to quench the reaction, separate the layers, and wash the aqueous phase with Et 2 O (3×20 mL) was extracted, and the organic phases were combined. Anhydrous Na for organic phase 2 SO 4 Dry and remove solvent under reduced pressure. Finally, it was purified by silica gel column chromatography (petroleum ether: ether 80:1) to obtain trimethylcycloheptanone 5 (0.780 g, yield 80%) as a colorless oil.

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PUM

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Abstract

The invention belongs to the technical field of green pesticides, and discloses a novel method for synthesizing flea beetle aggregation pheromone. The method comprises the following steps of: with cycloheptanone (2) taken as an initial raw material, carrying out bromination reaction on the cycloheptanone and NBS (N-bromosuccinimide), carrying out elimination reaction under the alkaline condition of lithium bromide and lithium carbonate to obtain cycloheptenone 3, carrying out asymmetric Michael addition reaction under the catalysis of copper to prepare chiral methyl cycloheptanone 4; and making the chiral methyl cycloheptanone 4 react with methyl iodide to obtain trimethyl cycloheptanone 5. carrying out aldol condensation reaction on the trimethyl cycloheptanone 5 and trimethylsilyl ketene under the catalysis of LDA to prepare diketone 6; and finally carrying out Robinson cyclization reaction to obtain flea beetle aggregation pheromone 1. The asymmetric Michael addition reaction is utilized for the first time to construct the chiral methyl of the flea beetle aggregation pheromone, and the method has the advantages of being simple in synthetic route, easy to operate 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 beetle aggregation pheromone. Background technique [0002] Flea beetles belong to the subfamily Alticinae (Chrysomelidae) of the family Chrysomelidae (order Coleoptera), and are widely distributed all over 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.). Flea beetles include many important pests that harm vegetables, fruits, grains and other crops (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 gather 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.), can be used to...

Claims

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Application Information

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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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