(-)-α-蒎烯选择性氧化合成(+)-2-羟基-3-蒎酮的研究

生物质化学工程 ›› 2012, Vol. 46 ›› Issue (6): 30-34.

(-)-α-蒎烯选择性氧化合成(+)-2-羟基-3-蒎酮的研究

刘兵¹, 毕中保², 王石发²

1. 南京财经大学食品科学与工程学院, 粮食储运国家工程实验室, 江苏南京 210046;2. 南京林业大学化学工程学院, 江苏南京 210037

收稿日期:2012-07-28 修回日期:1900-01-01 出版日期:2012-11-30 发布日期:2012-11-30
通讯作者: 王石发,男,教授,博士生导师,主要从事有机合成化学、天然产物化学和化学生态学方面的研究;E-mail:wangshifa65@yahoo.com.cn。

Synthesis of (+)-2-Hydroxy-3-Pinanone from (-)-α-Pinene by Selective Oxidation

LIU Bing¹, BI Zhong-bao², WANG Shi-fa²

1. Nanjing University of Finance ＆ Economics, National Engineering Lab.for Food Storage and Transportation, Nanjing 210046, China;2. College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China

Received:2012-07-28 Revised:1900-01-01 Online:2012-11-30 Published:2012-11-30

摘要/Abstract

摘要： 以(-)-α-蒎烯为原料,经过选择性氧化合成(+)-2-羟基-3-蒎酮。研究了其合成工艺条件,对不同氧化体系、氧化剂用量、反应时间以及反应温度等因素进行了探讨。结果表明, (-)-α-蒎烯选择性氧化合成(+)-2-羟基-3-蒎酮合适的工艺条件为:13.7g(纯度为93.0%)的(-)-α-蒎烯,在α-蒎烯与高锰酸钾物质的量之比为1:2,溶剂丙酮与水的用量是110:12(mL:mL),反应温度为0~5℃,反应时间为5h,α-蒎烯转化率为97.1%,(+)-2-羟基-3-蒎酮选择性为78.4%,纯度为92.1%,得率为76.1%,比旋光度为[α]_D²⁵+26°(c=0.5 mol/L, CHCl₃)。另外,采用IR、GC-MS和¹HNMR和¹³CNMR等对(+)-2-羟基-3-蒎酮结构进行了表征。

关键词: (-)-α-蒎烯, (+)-2-羟基-3-蒎酮, 选择性氧化

Abstract: (+)-2-hydroxy-3-pinanone was synthesized through selective oxidation from (-)-α-pinene. The synthetic technology was studied and affecting factors such as different oxidation systems, amount of oxidant, reaction time and temperature were investigated. The results showed that the suitable synthetic technology of (+)-2-hydroxy-3-pinanone from (-)-α-pinene were as follows: 13.7 g α-pinene (93.0% purity),α-pinene/KMnO₄ molar ratio 1:2, acetone and water used as the solvent at ratio of 110:12(mL:mL), reaction temperature 0~5℃ and reaction time 5 h. Under these conditions, the conversion of α-pinene was 97.1%, selectivity of oxidation was 78.4%, purity and yield of the product were 92.1% and 76.1%, respectively; specific rotation [α]_D²⁵+26°(c=0.5 mol/L, CHCl₃). The structure of (+)-2-hydroxy-3-pinanone was determined by IR, GC-MS and ¹HNMR, ¹³CNMR spectra.

Key words: (-)-α-pinene, (+)-2-hydroxy-3-pinanone, selective oxidation

中图分类号:

TQ35

刘兵;毕中保;王石发. (-)-α-蒎烯选择性氧化合成(+)-2-羟基-3-蒎酮的研究[J]. 生物质化学工程, 2012, 46(6): 30-34.

LIU Bing;BI Zhong-bao;WANG Shi-fa. Synthesis of (+)-2-Hydroxy-3-Pinanone from (-)-α-Pinene by Selective Oxidation[J]. , 2012, 46(6): 30-34.