(-)-α-蒎烯选择性氧化合成(＋)-2-羟基-3-蒎酮的研究

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

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:13.7 g(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5 h,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]2D5+26°(c=0.5 mol/L,CHCl3)。另外,采用IR、GC-MS和1H NMR和13C NMR等对(+)-2-羟基-3-蒎酮结构进行了表征。

（＋）-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 1H NMR, 13C NMR spectra.