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Method for synthesizing (9Z, 12E)-9,12-tetradecadien-1-ol acetate

A technology of alcohol acetate and synthesis method, which is applied in the direction of carboxylate preparation, organic chemical method, chemical instrument and method, etc., and can solve the problems of reagent toxicity, lengthy reaction route, harsh reaction conditions, etc.

Inactive Publication Date: 2020-05-29
CHINA AGRI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] Although great progress has been made in the synthesis of (9Z,12E)-tetradec-9,12-dien-1-ol acetate, there are still many problems, such as: harsh reaction conditions, lengthy reaction routes, reagents more toxic

Method used

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  • Method for synthesizing (9Z, 12E)-9,12-tetradecadien-1-ol acetate

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Embodiment 1

[0027] Synthesis of (E)-3-pentenoic acid 2

[0028] Under argon protection, malonic acid (10.40g, 100mmol), piperidine (0.086g, 1mmol), glacial acetic acid (0.060g, 1mmol) and DMSO (40mL) were sequentially added to a 100mL three-necked flask equipped with a reflux condenser. , stirred at room temperature to dissolve, and slowly added propionaldehyde (2.90 g, 50 mmol) dropwise. After dropping, the temperature was raised to 40°C, and the reaction was stirred for 2h, then the temperature was raised to 100°C, and the reaction was continued for 8h. After the reaction, the reaction mixture was cooled to room temperature. The reaction was quenched by adding cold water (30 mL), and the layers were separated. The aqueous phase was extracted with diethyl ether (3 x 30 mL), and the organic phases were combined. The organic phase was washed successively with water (3×100 mL) and saturated aqueous sodium chloride solution (100 mL). After drying over anhydrous sodium sulfate, it was con...

Embodiment 2

[0030] Synthesis of (E)-3-penten-1-ol 3

[0031] Under the protection of argon, lithium aluminum tetrahydride (1.39 g, 36.62 mmol) was added into a 200 mL Schlenk reaction flask, and then tetrahydrofuran (60 mL) was added, and stirred evenly. A tetrahydrofuran solution (20 mL) of (E)-3-pentenoic acid 2 (2.82 g, 28.17 mmol) was slowly added dropwise under cooling in an ice bath. After dropping, the reaction mixture was gradually warmed to room temperature and stirred for 8 h. After the reaction was completed, 20% aqueous sodium hydroxide solution (3 mL) was slowly added dropwise under ice cooling to quench the reaction. The reaction mixture was suction filtered through celite, the filter cake was washed with ether (500 mL), and the filtrate was washed with water (50 mL) and saturated aqueous sodium chloride solution (100 mL) successively. After drying over anhydrous sodium sulfate, it was concentrated under reduced pressure to obtain a crude product. The crude product was pu...

Embodiment 3

[0033] Synthesis of (E)-3-pentenyltriphenylphosphine bromide 4.

[0034] Under argon protection, (E)-3-penten-1-ol 3 (2.00g, 23.22mmol), carbon tetrabromide (11.55g, 34.83mmol) and dichloromethane ( 60 mL), stirred at room temperature to dissolve. A dichloromethane solution (50 mL) of triphenylphosphine (18.27 g, 69.66 mmol) was slowly added dropwise under cooling in an ice bath. After dropping, the reaction mixture was naturally warmed to room temperature, and the stirring reaction was continued for 5 h. After the reaction, the reaction solution was concentrated to obtain a crude product. The crude product was suction filtered through diatomaceous earth, the filter cake was washed with ether (500mL), and the filtrate was concentrated under reduced pressure to obtain a light yellow liquid compound (E)-5-bromo-2-pentene crude product (2.98g, crude yield 86%).

[0035] Under argon protection, triphenylphosphine (2.64g, 10.07mmol), anhydrous acetonitrile (60mL) and crude (E)-...

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Abstract

The invention belongs to the technical field of green pesticide synthesis, and discloses a novel method for synthesizing (9Z, 12E)-9,12-tetradecadien-1-ol acetate. According to the method, malonic acid and 9-bromo-1-nonyl alcohol are used as two starting raw materials. The method comprises the following steps: carrying out a Knoevenagel condensation reaction on malonic acid and propionaldehyde inthe presence of piperidine acetate to generate (E)-3-pentenoic acid, then carrying out lithium aluminum hydride reduction to obtain (E)-3-penten-1-ol, carrying out bromination reaction, and refluxingwith triphenylphosphine in acetonitrile to obtain (E)-3-pentenyltriphenylphosphine bromide; carrying out a PCC oxidation reaction on 9-bromo-1-nonanol to obtain 9-bromononanal, and then reacting the 9-bromononanal with potassium acetate to obtain 9-acetoxynonanal; and finally, carrying out a Wittig reaction on (E)-3-pentenyltriphenylphosphine bromide and 9-acetoxynonanal so as to obtain (9Z, 12E)-9,12-tetradecadien-1-ol acetate. An E-type double bond is constructed by utilizing the Knoevenagel condensation reaction of malonic acid and propionaldehyde, and the method has the advantages of mildreaction conditions, environmental friendliness, simple synthetic route and the like.

Description

technical field [0001] The invention belongs to the technical field of green pesticide synthesis, in particular to a method for synthesizing (9Z,12E)-tetradec-9,12-dien-1-ol acetate. Background technique [0002] (9Z,12E)-Tetradeca-9,12-dien-1-ol acetate (Formula 1) is the main component of the sex pheromone of the plant pest Indian meal moth (Plodia interpunctella Hübner), and can be used for the treatment of this type of pest Integrated control (Brady, U.E.; Tumlinson, J.H., III; Brownlee, R.G.; Silverstein, R.M. Science 1971, 171, 802-804. Kuwahara, Y.; Kitamura, C.; Takahashi, S.; Hara, H.; Ishii, S. .; Fukami, H. Science 1971, 171, 801-802.). (9Z,12E)-Tetradeca-9,12-dien-1-ol acetate is also a minor component of the sex pheromone of the tobacco mealworm (Ephestiaelutella Hübner) (Brady, U.E.; Nordlund, D.A.Life Sci.1971 , 10, 797-801. Brady, U.E. Life Sci. 1973, 13, 227-235.). In addition, (9Z,12E)-tetradeca-9,12-dien-1-ol acetate is also the active ingredient of the...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/293C07C69/145C07C67/11C07C69/14C07C45/29C07C47/14C07F9/54C07C29/147C07C33/025C07C51/353C07C57/03
CPCC07B2200/09C07C29/147C07C45/292C07C51/353C07C67/11C07C67/293C07F9/5442C07C57/03C07C33/025C07C47/14C07C69/14C07C69/145
Inventor 王敏孙效钟江春原超楠袁谷城杨宇雄边庆花
Owner CHINA AGRI UNIV
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