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Synthesis method of laspeyresia pomonella sex pheromone intermediate (2E, 4E)-2,4-hexadienol acetate

A technology of hexadienol acetate and codling moth is applied in the field of chemical synthesis of insect sex pheromone intermediates, which can solve the problems of inconvenient industrial production and operation, difficulty in filtering aluminum salts, harsh requirements and the like, and achieve good technical results. , easy handling, mild reaction conditions

Inactive Publication Date: 2013-10-23
WATERSTONE PHARMA WUHAN
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0013] In the reduction reaction, route 1 uses LiAlH 4 / AlCl 3 system, while LiAlH4 is extremely active and decomposes explosively when it meets water, and AlCl 3 It is easy to absorb moisture and release heat to produce hydrochloric acid, so the reaction in this step requires the environment to be completely anhydrous and harsh, and AlCl 3 Need to be in N before use 2 The pretreatment of heating in the environment also causes great inconvenience to industrial production and operation.
Route 2 uses red aluminum, which will produce highly toxic ethylene glycol monomethyl ether and difficult-to-filter aluminum salts during the reaction, which are extremely difficult to handle

Method used

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  • Synthesis method of laspeyresia pomonella sex pheromone intermediate (2E, 4E)-2,4-hexadienol acetate
  • Synthesis method of laspeyresia pomonella sex pheromone intermediate (2E, 4E)-2,4-hexadienol acetate
  • Synthesis method of laspeyresia pomonella sex pheromone intermediate (2E, 4E)-2,4-hexadienol acetate

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Step (1) Synthesis of active acid anhydride:

[0039] Under nitrogen protection, 10 g (0.089 mol) of sorbic acid, 60 mL of tetrahydrofuran and 9 g (0.089 mol) of triethylamine were added to a 250 mL reaction flask, and the temperature was lowered to 20°C. Add 9.7g (0.089mol) of ethyl chloroformate dropwise at a rate of 0.01mL / s. After the feeding is completed, the reaction temperature is 35°C, and the reaction is continued for 1.5 hours. The reaction progress is tracked by HPLC, and the reaction is stopped after the reaction is complete. The white solid was removed by filtration to finally obtain 70 g of filtrate, which was directly put into the next reaction without treatment.

[0040] Step (2) reduction reaction:

[0041] Put the above 70g filtrate into a 500mL reaction flask, cool down to -20°C, add sodium borohydride / sodium hydroxide aqueous solution dropwise, wherein the preparation method of sodium borohydride / sodium hydroxide aqueous solution is: hydroboration o...

Embodiment 2

[0046] Step (1) Synthesis of active acid anhydride:

[0047] Under nitrogen protection, add 60 g (0.54 mol) of sorbic acid, 360 mL of tetrahydrofuran and 65.6 g (0.648 mol) of triethylamine into a 1 L reaction flask, and cool down to 5 °C. Add 64g (0.59mol) ethyl chloroformate dropwise at a rate of 2.0mL / s. After feeding, the reaction temperature is 35°C. Continue to react for 2 hours. HPLC tracks the reaction process, and stops the reaction after the reaction is complete. The white solid was removed by filtration to finally obtain 430 g of filtrate, which was directly put into the next step reaction without treatment.

[0048] Step (2) reduction reaction:

[0049] Put the above 430g filtrate into a 1L reaction bottle, cool down to -10°C, add potassium borohydride / potassium hydroxide aqueous solution dropwise, wherein the preparation method of potassium borohydride / potassium hydroxide aqueous solution is: hydroboration of 43.7g (0.81mol) Potassium solids were added to 180g o...

Embodiment 3

[0053] Step (1) Synthesis of active acid anhydride:

[0054] Under nitrogen protection, 120g (1.07mol) of sorbic acid, 720mL of tetrahydrofuran and 129.5g (1.28mol) of triethylamine were added to a 2L reaction flask, and the temperature was lowered to 20°C. Add 138.9g (1.28mol) ethyl chloroformate dropwise at a rate of 0.05mL / s. After the feeding is completed, the reaction temperature is 50°C, and the reaction is continued for 0.5 hours. The reaction process is tracked by HPLC, and the reaction is stopped after the reaction is complete. The white solid was removed by filtration to finally obtain 920 g of filtrate, which was directly put into the next step reaction without treatment.

[0055] Step (2) reduction reaction:

[0056] Put the above-mentioned 920g filtrate into a 2L reaction flask, cool down to -15°C, add sodium borohydride / potassium hydroxide aqueous solution dropwise, and the preparation method of sodium borohydride / potassium hydroxide aqueous solution is as follo...

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Abstract

The invention relates to the field of chemical synthesis of an insect sex pheromone intermediate, and particularly relates to a synthesis method of a laspeyresia pomonella sex pheromone intermediate (2E, 4E)-2,4-hexadienol acetate. According to the method provided by the invention, sorbic acid is used as a start material and generates an active acid anhydride with ethyl chloroformate; the active acid anhydride generates (2E, 4E)-hexadiene-1-ol in a reducing system of hydroboron anion reducing agent / inorganic aqueous alkali; and (2E, 4E)-2,4-hexadienol acetate is finally obtained through an esterification reaction. The synthesis method provided by the invention has the advantages of easily available raw materials, mild reaction conditions, convenience in operation, low requirements for equipment pipelines, high product yield and simple after-treatment, and is environment-friendly and suitable for large-scale industrial production.

Description

technical field [0001] The invention relates to the field of chemical synthesis of insect sex pheromone intermediates, in particular, the invention relates to a synthesis method of codling moth sex pheromone intermediate (2E, 4E)-2,4-hexadienol acetate. Background technique [0002] (2E,4E)-2,4-Hexadienyl acetate (CAS:57006-69-6) is a synthetic codling moth [Laspeyresia pomonella (Linnaenus)] sex pheromone (8E,10E)-8,10 -The main intermediate of dodecadien-1-ol [Wendell R, André C, Ada H, et al. Sex Attractant of the Codling Moth: Characterization with Electroantennogram Technique [J]. Science, 1971, 174: 297-299 .]. [0003] The codling moth belongs to Lepidoptera and is one of the most harmful fruit-boring pests in the world. According to reports, all apple production areas in the world except Japan are distributed, and they are quarantine objects for key prevention and control in the world [Jin Ruihua, Plant Quarantine. Beijing: Beijing Agricultural University Press, 19...

Claims

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Application Information

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IPC IPC(8): C07C69/145C07C67/08
Inventor 何伟邵言中游海军黄焜崔健
Owner WATERSTONE PHARMA WUHAN
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