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A Green and Simple Method for the Synthesis of (-)-trans-Verbenol and Its Enantiomer (+)-trans-Verbenol

A technology of verbenol and enantiomer, which is applied in the field of synthesis of α-pinene oxide, can solve the problems of human poisoning, serious environmental pollution, high catalyst cost, etc., and achieves cheap price, simple preparation method, and reduced synthesis cost Effect

Active Publication Date: 2021-11-19
INST OF FOREST ECOLOGY ENVIRONMENT & PROTECTION CHINESE ACAD OF FORESTRY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0008] The deficiencies of the method of directly utilizing α-pinene allylic oxidation to prepare trans-verbenaenol mainly include: 1. The conversion rate of α-pinene is not high, and the reaction selectivity is not ideal at the same time, and the product is mostly verbena The mixture of alcohol and verbenone increases the difficulty of separation and purification, and improves the application cost; 2, the catalyst (lead tetraacetate, etc.) and solvent (benzene, etc.) used in the reaction are costly, and the environmental pollution is serious, and the human body is relatively harmful. strong toxic effect

Method used

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  • A Green and Simple Method for the Synthesis of (-)-trans-Verbenol and Its Enantiomer (+)-trans-Verbenol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Synthesis of trans-4-nitrobenzoate verbenol of - (-) Example 1

[0022] The 4.56g (30mmol) (-) - cis-verbenol, 20.0g (120mmol) 4- nitrobenzoic acid and 31.4g (120mmol) of triphenylphosphine were dissolved in 250ml of anhydrous tetrahydrofuran at 10 ℃ the following slowly added dropwise 20.9g (120mmol) of diethyl azodicarboxylate. After completion of the dropwise addition, the temperature was raised to room temperature and stirred for 14H, the next reaction temperature was raised to 40 ℃ then stirred for 3h. After the reaction temperature was returned to room temperature, diluted with 150ml of ether. The organic phase was washed with a saturated aqueous solution (2 × 100ml) was washed with aqueous layer was repeatedly extracted again with ether (100ml). The organic phase was dried over sodium sulfate, filtered, and the solvent and low-boiling compounds using a rotary evaporator and a vacuum pump to remove. The resulting crude product was suspended in diethyl ether (60ml) and...

Embodiment 2

[0024] Synthesis of trans-verbenol is - (-) Example 2

[0025] After the above crude product, at 0 deg.] C, was slowly added 1.5g (30mmol) of lithium aluminum hydride in tetrahydrofuran at room temperature. After the addition was complete, the reaction temperature 2h, water was added sequentially, 15% NaOH, water, the residue washed with ethyl acetate was combined organic phases were washed with saturated sodium carbonate, aqueous sodium chloride solution, finally dried over anhydrous sodium sulfate, the solvent was evaporated, the resulting crude product was distilled to give 3.74 g of a light yellow liquid (yield 94%).

[0026] 1 H NMR (500MHz, CDCL 3) Δ: 0.85 [3H, s], 1.32 [3H, s], 1.67 [1H, m], 1.70 [3H, m], 2.00 [1H, m], 2.16 [1H, m], 2.23 [1H, m ], 4.25 [1H, m], 5.33 [1H, m]. 13 C NMR (125MHz, CDCl 3 ): Δ: 20.4,22.6,26.6,28.6,36.1,47.0,48.0,70.4,118.8,148.8.

Embodiment 3

[0027] Trans-4-nitrobenzoate verbenol Synthesis --3 (+) Example

[0028] The 4.56g (30mmol) (+) - cis-verbenol, 20.0g (120mmol) 4- nitrobenzoic acid and 31.4g (120mmol) of triphenylphosphine were dissolved in 250ml of anhydrous tetrahydrofuran at 10 ℃ the following slowly added dropwise 20.9g (120mmol) of diethyl azodicarboxylate. After completion of the dropwise addition, the temperature was raised to room temperature and stirred for 14h. Next, the reaction temperature was raised to 40 ℃ then stirred for 3h. After the reaction temperature was returned to room temperature, diluted with 150ml of ether. The organic phase was washed with a saturated aqueous solution (2 × 100ml) was washed with aqueous layer was repeatedly extracted again with ether (100ml). The organic phase was dried over sodium sulfate, filtered, and the solvent and low-boiling compounds using a rotary evaporator and a vacuum pump to remove. The resulting crude product was suspended in diethyl ether (60ml) and allo...

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Abstract

The invention provides a green and simple preparation method for synthesizing (-)-trans verbenol and its enantiomer (+)-trans verbenol. It is characterized in that, using (‑)‑cis verbenol and (+)‑cis verbenol, using Mitsunobu reaction, through hydroxyl configuration inversion, respectively to obtain (‑)‑trans verbenol and (+ )-trans verbenol, wherein, (-)-trans verbenol yield is 81%, (+)-trans verbenol yield is 80%. The synthetic method of the present invention includes new, effective and environmentally benign steps and procedures, and compared with the existing trans verbenol synthetic method, the use of lead tetraacetate (oxidant) and benzene toxic solvent is avoided. The raw material cis verbenol can be prepared by oxidation of α-pinene, and (‑)‑trans verbenol and (+)‑trans verbenol can be used to control bark beetles in my country.

Description

Technical field [0001] The present invention is in the synthesis method of α- pinene oxide, particularly relates to a synthetic trans-verbenol and its enantiomer (+) - - trans-verbenol green, simple method for preparing (-). Background technique [0002] Worldwide, bark beetle is one of the major pests of pine trees, which seriously affected the healthy growth of pine trees, poses a great threat to the ecological environment. In my country's Yunnan province occurred Hengkeng the beetle, the beetle cloud Nance short-haired and the beetle bark beetle species are the main hazards Yunnan pine and pine Simao, three in the beetle occurred in Yunnan Province He has 30 years, resulting in the death of a large number of pine trees, affecting forestry sustained and healthy development. [0003] At present, the beetle control methods are mainly beetles damage trees and cleaning up chemical control, but the control effect is not ideal. Insect pheromone trapping, and the sliding prevention is...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C35/28C07C29/147C07C205/57C07C201/12
CPCC07B2200/07C07C29/147C07C201/12C07C2602/42C07C205/57C07C35/28
Inventor 刘福张真孔祥波张苏芳李如华
Owner INST OF FOREST ECOLOGY ENVIRONMENT & PROTECTION CHINESE ACAD OF FORESTRY