Method for synthesizing (E)-7-dodecen-1-ol acetate

A technology of dodecene and alcohol acetate, applied in the field of insect pheromone synthesis, which can solve the problems of cumbersome reaction steps and harsh reaction conditions

Inactive Publication Date: 2018-12-18
CHINA AGRI UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0009] Although there are some reports in the literature about the research on the synthesis of (E)-7-dodecen-1-ol acetate, there are still problems such as harsh reaction conditions and cumbersome reaction steps.

Method used

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  • Method for synthesizing (E)-7-dodecen-1-ol acetate

Examples

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Effect test

Embodiment 1

[0024] Synthesis of 1-tetrahydropyranyloxy-6-bromohexane 2

[0025] 6-Bromohexanol 1 (1.0 g, 5.52 mmol) and 2,3-dihydropyran (0.95 g, 11.03 mmol) were added into dichloromethane (10 mL), stirred and dissolved. Then p-toluenesulfonic acid (0.1 g, 0.58 mmol) was added and the reaction was stirred overnight at room temperature. After the reaction was completed, the reaction mixture was washed with saturated Na 2 CO 3 Wash with aqueous solution (20 mL), and separate the layers. The aqueous phase was extracted with dichloromethane (3 x 20 mL), and the organic phases were combined. Anhydrous Na 2 SO 4 Dry and concentrate under reduced pressure to obtain crude product. The crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate 80:1) to obtain 1-tetrahydropyranyloxy-6-bromohexanol 2 as a light yellow liquid (1.36g, yield 93%) . 1 H NMR (300MHz, CDCl 3 )δ4.55(t,J=3.5Hz,1H),3.84–3.70(m,2H),3.41–3.35(m,4H),1.87–1.37(m,14H); 13 C NMR (75MHz...

Embodiment 2

[0027] Synthesis of 1-tetrahydropyranyloxy-7-dodecyne 3

[0028]Under the protection of argon, 1-hexyne (0.79 g, 9.6 mmol) was added into tetrahydrofuran (20 mL), stirred and dissolved at room temperature. The temperature of the mixed solution was lowered to -40°C, and n-butyllithium (4 mL, 2.4M n-hexane solution, 9.6 mmol) was slowly added dropwise. The reaction was stirred at -40°C for 2h, then 1-tetrahydropyranyloxy-6-bromohexane 2 (1.27g, 4.8mmol) was added, the reaction solution was naturally warmed to room temperature, and the reaction was continued to stir for 24h. After the reaction was completed, the temperature of the reaction solution was lowered to 0° C., the reaction was quenched with a small amount of water, the layers were separated, and the aqueous phase was extracted with diethyl ether (3×10 mL). Combined organic phases, anhydrous Na 2 SO 4 Dry and concentrate under reduced pressure to obtain crude product. The crude product was purified by silica gel colu...

Embodiment 3

[0030] Synthesis of (E)-1-tetrahydropyranyloxy-7-dodecene 4

[0031] Under the protection of argon, in the diethylene glycol dimethyl ether (40mL) solution of lithium aluminum hydride (114mg, 3mmol), add 1-tetrahydropyranyloxy-7-dodecyne 3 (266mg, 1mmol ), and stir well. The temperature of the reaction solution was raised to 150° C., and the stirring and reflux reaction was continued for 24 h. After the reaction was completed, the temperature of the reaction solution was lowered to 0° C., and the reaction was quenched with methanol (2 mL) and aqueous ammonium chloride. After suction filtration, the solid was washed with diethyl ether (30 mL), and the filtrate was washed with water (30 mL) and separated. Combined organic phases, anhydrous Na 2 SO 4 dry. Concentration under reduced pressure gave the crude product, which was purified by silica gel column chromatography (petroleum ether / ethyl acetate 110:1) to obtain (E)-1-tetrahydropyranyloxy-7-dodecene 4 as Pale yellow liq...

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Abstract

The invention belongs to the technical field of insect pheromone synthesis, and discloses a novel method for synthesizing (E)-7-dodecen-1-ol acetate. The method comprises the following steps: reactinga starting raw material 6-bromo-1-hexanol with 2,3-dihydropyran to obtain 1-tetrahydropyranyloxy-6-bromohexane, and carrying out a coupling reaction on the 1-tetrahydropyranyloxy-6-bromohexane and 1-hexyne in the presence of n-butyllithium to generate 1-tetrahydropyranyloxy-7-dodecyne; reducing the 1-tetrahydropyranyloxy-7-dodecyne by lithium aluminum hydroxide in diethylene glycol dimethyl etherto obtain (E)-tetrahydropyranyloxy-7-dodecene; and removing tetrahydropyran protecting groups by using p-toluenesulfonic acid to synthesize (E)-7-dodecen-1-ol acetate, and finally reacting the (E)-7-dodecen-1-ol acetate with acetyl chloride to obtain the target product (E)-7-dodecen-1-ol acetate. The method has the advantages of simple synthesis route, mild reaction conditions, and realization ofthe total yield reaching 49%.

Description

technical field [0001] The invention belongs to the technical field of insect pheromone synthesis, and in particular relates to a new method for synthesizing (E)-7-dodecen-1-ol acetate. Background technique [0002] (E)-7-dodecen-1-ol acetate ((E)-dodec-7-enyl acetate, formula 1) is the main component of the sex pheromone of the plant pest Argyroploce leucotreta (Meyrick), which can be used in this Biological control of pests (Read, J.S.; Warren, F.L.; Hewitt, P.H. Chem. Commun. 1968, 792-793. Read, J.S.; Hewitt, P.H.; Warren, F.L.; Myberg, A.C.J. .). (E)-7-Dodecen-1-ol acetate is also a minor component of the sex pheromone of grape vine moth (Lobesia botrana), which can significantly increase the main component (7Z,9E,11)-dodeca The ability of en-1-ol acetate to attract male moths (Witzgall, P.; Tasin, M.; Buser, H.-R.; Wegner-Kiss, G.; Mancebon, V.S.M.; Ioriatti, C.; Baeckman , A.-C.; Bengtsson, M.; Lehmann, L.; Francke, W. J. Chem. Ecol. 2005, 31, 2923-2932.). In addi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D309/12C07C29/10C07C33/025C07C67/14C07C69/145
CPCC07B2200/09C07C29/10C07C67/14C07D309/12C07C33/025C07C69/145Y02P20/55
Inventor 钟江春马思捷边庆花王敏周云侯文博李杨帆
Owner CHINA AGRI UNIV
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