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Simple stereoselective synthesis method of sex pheromones of hyphantria cunea

A stereoselective, white moth technology, applied in organic chemistry and other directions, can solve the problems of complex synthesis of pheromone molecules, troublesome synthesis, low efficiency, etc., and achieve simple operation and separation, high enantioselectivity, and high yield. Effect

Inactive Publication Date: 2010-08-11
XIAMEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Through the above introduction, it is not difficult to see that the synthesis of pheromone molecules IV and V is more complex than III, and the yield is low; the existing method, the whole route can only synthesize a single molecule, and the efficiency is low
In 2009, we synthesized two pheromone molecules from an intermediate with high efficiency and high enantioselectivity for the first time, but the synthesis of the raw material (Z)-2-alkyne tetradecyl alcohol was troublesome, and the hydroxyl group of the alkyne alcohol in the route still needs to be protected , the yield of some steps is low, these deficiencies need to be improved

Method used

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  • Simple stereoselective synthesis method of sex pheromones of hyphantria cunea
  • Simple stereoselective synthesis method of sex pheromones of hyphantria cunea
  • Simple stereoselective synthesis method of sex pheromones of hyphantria cunea

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0048] Step 1 Synthesis of 2-alkyne tetradecan-1-ol (2)

[0049] 2-Propargyl alcohol 1 (560mg, 10mmol) was dissolved in tetrahydrofuran (100mL) solvent, and n-butyl lithium (6.9mL, 20mmol, 2.9M in hexane) was added dropwise at -78°C under argon atmosphere. After reacting at -78°C for 60min, 1-bromoundecane (2.5mL, 11mmol) and hexamethylphosphoramide (4.5mL, 26mmol) were successively added dropwise, and then reacted at the same temperature for 5 hours. After the reaction was quenched with 20 mL of saturated sodium carbonate solution, the layers were separated, and the aqueous phase was extracted with diethyl ether (3×20 mL). The combined organic phases were dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain compound 2 (1.94 g, 92%). White solid, mp 44-45°C (n-hexane); IR(film)ν max 3342(OH), 2925, 2854, 2226(w, C≡C), 1466, 1378(w), 1137, 1015cm -1 ; 1 H-NMR (400MHz, CDCl 3 )δ0.88(t...

Embodiment 2

[0067] Step 1 Synthesis of 2-alkyne tetradecan-1-ol (2)

[0068] Under argon atmosphere, add n-butyllithium (2.9M in hexane) dropwise to the ether solution of 2-propargyl alcohol 1 at -80°C, and then add 1-bromoundecane and hexa Methylphosphoramide was reacted at the same temperature for 5 hours. After the reaction was quenched with saturated potassium carbonate aqueous solution, the layers were separated, and the aqueous phase was extracted with ether. The combined organic phases were dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 2 (90%) as a white solid.

[0069] Step 2 Synthesis of (Z)-2-entetradec-1-ol (3)

[0070] Under hydrogen atmosphere, at 0°C, add the hexane solution of compound 2 to the Lindella catalyst, and react at 0-5°C. After the reaction was completed, the catalyst was removed by filtration, and the filter cake was washed with ethyl acetate. The filtrate was concentrated...

Embodiment 3

[0086] Step 1 Synthesis of 2-alkyne tetradecan-1-ol (2)

[0087] Under argon atmosphere, at -78°C, add n-butyllithium (2.9M in hexane) dropwise to the tetrahydrofuran solution of 2-propargyl alcohol 1, and then add 1-bromoundecane and Hexamethylphosphoramide. After reacting at the same temperature for 2 hours, the temperature was gradually raised to 0°C, and the reaction was quenched with saturated sodium carbonate solution. The liquid was separated, the aqueous phase was extracted with ether, the combined organic phase was dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain a white solid 2 (94%).

[0088] Step 2 Synthesis of (Z)-2-entetradec-1-ol (3)

[0089]Hydrogen atmosphere, at 0°C, to Lindella catalyst (Pd / BaSO 4 / Pb 2+ ) was added the hexane solution of compound 2, and reacted at 0-5°C. After the reaction was completed, the catalyst was removed by filtration, the filter cake ...

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Abstract

The invention discloses a simple stereoselective synthesis method of sex pheromones of hyphantria cunea, which relates to epoxypropane compounds. The sex pheromones of hyphantria cunea III[(9S,10R)-9,10-epoxy-(3Z,6Z)-3,6-heneicosenediene] and IV[(9S,10R)-9,10-epoxy-(3Z,6Z)-3,6-heneicosenetriene] are prepared from cheap and readily available 2-propargyl alcohol serving as raw materials by eight steps with high efficiency, high enantioselectivity and high yield, wherein the total yield of (9S,10R)-III is 36 percent; the total yield of (9S,10R)-IV is 33 percent; and enantiomer excess e is more than 99 percent. The method has the advantages that: the operation and separation of each step are simple; the yield is high; all the adopted reagents are common reagents which are cheap and readily available; and the production line is short. The method is suitable for industrial production.

Description

technical field [0001] The present invention relates to a kind of propylene oxide compound, especially one end is a saturated carbon chain, one end is the synthesis method of an unsaturated carbon chain propylene oxide compound, especially a kind of synthetic white moth sex pheromone III [(9S, 10R) -9,10-epoxy-(3Z,6Z)-3,6-21 carbadiene] and IV [(9S,10R)-9,10-epoxy-(3Z,6Z)-1,3,6 -21 carbatriene] method. Background technique [0002] The American white moth, also known as the autumn curtain caterpillar, is a worldwide quarantine pest, mainly harming fruit trees, street trees, ornamental trees and other broad leaves and crops. The insect is native to North America and was introduced into my country in 1979, causing great harm to my country's agriculture, forestry production and urban afforestation. In 1990, it was listed as one of the seven major forest pests by the Ministry of Forestry. On the eve of the opening of the 2008 Beijing Olympic Games, the American white moth pest...

Claims

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Application Information

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IPC IPC(8): C07D303/04C07D301/28
Inventor 黄培强杜宇郑剑峰
Owner XIAMEN UNIV
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