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Synthesis method of chiral 2,3-pinanediol

A technology of pinanediol and a synthesis method, applied in the field of chirality, can solve the problems of high toxicity, serious environmental pollution, low yield and the like, and achieve the effects of mild chemical reaction conditions, stable process conditions and high chemical purity

Active Publication Date: 2014-03-19
ASYMCHEM LAB TIANJIN +4
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  • Abstract
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AI Technical Summary

Problems solved by technology

[0007] 2. Using proline boron ester as raw material, decompose it into 2,3-pinanediol with a resolving agent, or synthesize 2,3-pinanediol from α-hydroxy ketone. These two methods are used The price of raw materials is very expensive, and the synthesis cost is high
[0008] 3. Using α-pinene as raw material, 2,3-pinanediol is generated by oxidation with potassium permanganate, but the previous potassium permanganate oxidation method often has a very low yield, and the purity and enantiomeric purity of the final product are not high
[0009] The above method is not suitable for large-scale production due to the problems of expensive raw materials, high toxicity, serious environmental pollution, low yield, low product purity and enantiomeric purity.

Method used

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  • Synthesis method of chiral 2,3-pinanediol
  • Synthesis method of chiral 2,3-pinanediol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Embodiment 1: A kind of preparation (1S, 2S, 3R, 5S)-(+)-2,3-pinanediol The method is characterized in that the specific preparation steps are as follows:

[0029] Add 250kg water (1g / 2.5mL) and 975kg tert-butanol (1g / 12.5mL) in 8000L reactor, add 100kg D-α-pinene (1eq), 82.0kg ethylene glycol (1: 1.8eq), The temperature is controlled at 25±5°C, and 4290.2kg of sodium hydroxide solution (696.0kg of potassium permanganate (1:6.0eq)+35.2kg of sodium hydroxide (1: 1.2eq)+3559.0kg of water (the amount is determined by the pH)), the dropwise addition is completed, and kept at 25±5°C for 5 hours, the reaction is complete, and 610.7kg of sulfur dioxide (1:13.0eq) is introduced to terminate the reaction, liquid separation, extraction, Concentration to obtain the product (1S, 2S, 3R, 5S)-(+)-2,3-pinanediol 95.7kg. Yield 76.6%, liquid chromatography purity (HPLC): 98.8%, enantiomer ee value: 99.5%.

Embodiment 2

[0030] Embodiment 2: A kind of preparation (1S, 2S, 3R, 5S)-(+)-2,3-pinanediol The method is characterized in that the specific preparation steps are as follows:

[0031] Add 40.0kg water (1g / 0.5mL) and 189.6kg ethanol (1g / 3.0mL) to the 5000L reactor, add 80.0kg L-pinene (1eq), 27.0kg glycerol (1:0.5~3.0eq ), the temperature control is 12±2°C, and 409.7kg of potassium permanganate-containing potassium hydroxide solution (92.9kg of potassium permanganate (1:1.0eq)+3.3kg of potassium hydroxide ( 1∶0.1eq)+313.5kg water (dosage is determined by pH)), after the dropwise addition is completed, keep warm at 12±2°C for 2 hours, and the reaction is complete, then inject 188.1kg of sulfur dioxide (1:5.0eq) to terminate the reaction, and separate the liquid , extracted, and concentrated to obtain the product (1S, 2S, 3R, 5S)-(+)-2,3-pinanediol 60.7kg. Yield 60.7%, liquid chromatography purity (HPLC): 98.7%, enantiomer ee value: 99.0%.

Embodiment 3

[0032] Embodiment 3: A kind of preparation (1R, 2R, 3S, 5R)-(-)-2,3-pinanediol The method is characterized in that the specific preparation steps are as follows:

[0033] Add 325.0kg of water (1g / 5.0mL) and 1027.0kg of ethanol (1g / 20.0mL) into the 8000L reactor, add 65.0kg of L-α-pinene (1eq), 88.8kg of ethylene glycol (1:3.0eq) , temperature control is 37±3°C, add dropwise 4573.6kg sodium hydroxide solution containing sodium permanganate at pH=13.5±0.5 (677.2kg sodium permanganate (1:10.0eq)+38.2kg sodium hydroxide (1 : 2.0eq) + 3858.2kg water (the amount is determined by the pH)), the dropwise addition is completed, and kept at 37±3°C for 10h, the reaction is complete, and 611.3kg of sulfur dioxide (1:20.0eq) is added to terminate the reaction, liquid separation, extraction , concentrated to obtain the product (1R, 2R, 3S, 5R)-(-)-2,3-pinanediol 58.6kg. Yield 72.1%, liquid chromatography purity (HPLC): 98.5%, enantiomer ee value : 99.1%.

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Abstract

The invention relates to a synthesis method of chiral 2,3-pinanediol. The structural formula of chiral 2,3-pinanediol is showed in the specification. The synthesis method comprises the step of adding an oxidation inhibitor and alkali liquor containing an oxidant in alpha-pinene which is commercialized in the market and selected as a starting material for reaction so that a final product, namely chiral 2,3-pinanediol, can be obtained. According to the method, a target product with high liquid phase purity and high ee (enantiomeric excess) value of a product enantiomer can be obtained, wherein the liquid phase purity is stabilized above 98%, the ee value of the enantiomer is stabilized above 99% and the yield is 60.7-76.6%. According to the synthesis method, the materials are easy to obtain, the price is cheap, the chemical reaction condition is mild during the production process, the technical condition is stable, the operation is simple, pollution is less; the synthesis method is suitable for on-scale production, and a new idea and method can be provided for preparing chiral 2,3-pinanediol.

Description

(1) Technical field: [0001] The invention relates to a synthesis method for oxidizing olefins into cis-diols, in particular to a synthesis method for chiral 2,3-pinanediol. (two) background technology: [0002] At present, malignant tumors are still one of the major diseases that threaten people's lives. The American Cancer Society reported in "Global Cancer Facts and Figures" on December 17, 2007 that in 2007, there were 12 million new cancer patients worldwide, 7.6 million People die from cancer, which is equivalent to 20,000 people die every day. Among them, there were 5.4 million new cancer patients and 2.9 million cancer deaths in developing countries that year. According to statistics from the Ministry of Health, there are about 1.485 million new patients with malignant tumors in my country every year. In addition, the national prevalence rate of benign tumors has reached 0.93‰. Based on the total population of 1.3 billion in China, there were 1.2 million new patients...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C35/28C07C29/48
Inventor 洪浩陈朝勇蒋勇
Owner ASYMCHEM LAB TIANJIN
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