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Synthesis of (Z)-7-dodecylene-1-alcohol and acetic ester thereof

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

Inactive Publication Date: 2019-01-18
CHINA AGRI UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] Although there have been some successful cases in the research on the synthesis of (Z)-7-dodecen-1-ol and its acetate, there are still problems such as the need for raw materials containing Z-type double bonds, lengthy steps, and harsh reaction conditions.

Method used

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  • Synthesis of (Z)-7-dodecylene-1-alcohol and acetic ester thereof
  • Synthesis of (Z)-7-dodecylene-1-alcohol and acetic ester thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0020] Synthesis of (Z)-7-dodecenoic acid ethyl ester (3)

[0021] Under the protection of argon, (7-ethoxy-7-oxoheptyl)-triphenylphosphonium bromide (3mmol, 1.49g) was dissolved in tetrahydrofuran (10mL), cooled to -78°C, and slowly added dropwise with Sodium methyldisilazide (3.5mmol, 2M in THF, 1.75mL), stirred for 1h. Add n-valeraldehyde (1mmol, 711mg) into the mixture, slowly warm up to room temperature, and continue to stir for 20h. After the reaction is completed, use saturated NH 4 The reaction was quenched with aqueous Cl solution, and the layers were separated. The aqueous phase was extracted with dichloromethane (2×10 mL), the layers were separated, and the organic phases were combined. Anhydrous Na for organic phase 2 SO 4 Dry, filter, and concentrate the filtrate under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate 120:1) to obtain light yellow liquid (Z)-ethyl 7-...

Embodiment 2

[0023] Synthesis of (Z)-7-dodecen-1-ol

[0024] Under the protection of argon, weigh lithium aluminum tetrahydrogen (114mg, 3mmol) into the reaction bottle, after pumping and exchanging air three times, add tetrahydrofuran (2mL), and stir well. The temperature of the mixture was lowered to 0°C, and a solution of ethyl (Z)-7-dodecenoate (3) (1 mmol, 226 mg) in tetrahydrofuran (1 mL) was slowly added dropwise, then warmed to room temperature and stirred for 8 h. After the reaction was complete, the reaction was quenched with methanol and aqueous ammonium chloride at 0 °C. Suction filtration, the solid was washed with ether, the filtrate was washed with saturated brine (5 mL), and the layers were separated. Combine the organic phases, and use anhydrous Na for the organic phase 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 20:1) to obtain (Z)-7-dodecen...

Embodiment 3

[0026] Synthesis of (Z)-7-dodecen-1-ol acetate

[0027] Under the protection of argon, (Z)-7-dodecen-1-ol (1mmol, 184mg) was dissolved in dichloromethane (5mL), triethylamine (6mmol, 607mg) was added, and stirred evenly. The temperature of the mixture was lowered to 0°C, and acetyl chloride (3 mmol, 236 mg) was slowly added dropwise. Then the stirring reaction was continued at room temperature for 8 h. After the reaction was complete, the reaction was quenched with water at 0 °C. Separation, the organic phase was washed with saturated brine (5mL), washed with 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 (Z)-7-dodecen-1-ol acetate (208 mg, yield 92%) as a light yellow liquid. 1 H NMR (300MHz, CDCl 3 )δ5.33–5.29(m,2H),4.02(t,J=6.7Hz,2H),2.00–1.97(m,7H),1.63–1.52(m,2H),1.34–1.26(m,10H) ,0.88(t,J=6.9,3H). 13 C NMR (75MHz...

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Abstract

The invention belongs to the technical field of insect pheromone synthesis, and discloses a novel method for synthesizing (Z)-7-dodecylene-1-alcohol and acetic ester thereof. The method comprises thefollowing steps: taking n-valeraldehyde as a starting material and reacting with a Wittig reagent to obtain (Z)-7-dodecenoic acid ethyl ester; then performing reduction with lithium aluminum hydroxideto obtain (Z)-dodeca-carbon-7-alkene-1-alcohol; finally taking (Z)-dodeca-carbon-7-alkene-1-alcohol to react with acetyl chloride to obtain (Z)-7-dodecylene-1-farnesyl acetate. By adopting the method, Z-shaped double bonds are directly constructed through a coupling reaction of the Wittig reagent carrying an ester group at the tail end with aldehyde. The method is simple in synthesis route, and is environmentally friendly.

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 (Z)-7-dodecen-1-ol and its acetate. Background technique [0002] (Z)-7-Dodecen-1-alcohol and its acetate (formula 1) are active components of the sex pheromone of Dendrolimns punctatus (Walker) (Zhao Chenghua; Li Qun; Guo Xingyu; Wang Xuying Acta Entomology 1993, 247-250. Su Jianwei; Xu Yanxi; Qin Xiaowei; Ge Feng Insect Knowledge 2006, 439-442.). At the same time, (Z)-7-dodecen-1-ol is also the active ingredient of the sex pheromone of forest lepidopteran pest Raphia frater Grt (Noctuidae) (Weatherson, J.; Davidson, L.M.; Simonini, D.Can. Entomol. 1974, 106, 781-782.). In addition, (Z)-7-dodecen-1-ol acetate is both the active ingredient of Trichoplusia ni (Hübner) sex pheromone (Berger, R.S.Ann.Entomol.Soc.Am.1966,59,767 -771.Green, N.; Jacobson, M.; Henneberry, T.J.; Kishaba, A.N.J.Med.Chem.1967, 10, 533-535.); a...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/343C07C67/08C07C69/533C07C29/147C07C33/025
CPCC07B2200/09C07C29/147C07C67/08C07C67/343C07C69/533C07C33/025
Inventor 钟江春马思捷边庆花王敏周云王李锋袁谷城
Owner CHINA AGRI UNIV
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