异长叶烯酮的绿色合成研究

Green Synthesis of Isolongifolenone

以重质松节油为原料,经三氟化硼乙醚催化异构得到异长叶烯;采用Cu为催化剂、叔丁基过氧化氢(TBHP)为氧化剂、叔丁醇(TBA)为溶剂经烯丙位氧化得到异长叶烯酮。探讨了反应条件对异长叶烯氧化反应的影响,确定了适宜的氧化工艺条件为:Cu粉用量3%(以异长叶烯质量计),TBHP与异长叶烯物质的量比3.5∶1,溶剂TBA与异长叶烯的质量比1∶1,80℃温度下反应12 h,在此工艺条件下,异长叶烯酮得率达93%,纯度98.75%。

Isolongifolenone was synthesized by using heavy turpentine as the starting material. Firstly,the heavy turpentine was converted to isolongifolene by isomerization reaction with BF3（ C2H5）2O as catalyst. Isolongifolenone was finally obtained from isolongifolene by allylic oxidation with tert-butyl hydroperoxide（ TBHP） as oxidizer,Cu as catalyst and tert-butyl alcohol（ TBA）as solvent. By investigating the influence of different react conditions on the oxidation of isolongifolene,the optimum conditions were determined as follows： the mass fraction of Cu 3%（ based on the mass of isolongifolene）,the mole ratio of TBHP and isolongifolene 3. 5 ∶ 1,the mass ratio of TBA and isolongifolene 1 ∶ 1,reaction temperature 80 ℃ and reaction time 12 h. The yield of isofolenone was over 93%,and the purity was 98. 75% under these conditions.