催化学报

催化学报 ›› 2011, Vol. 32 ›› Issue (10): 1610-1616.DOI: 10.1016/S1872-2067(10)60271-9

• 研究论文 • 上一篇    下一篇

钠灯下α-蒎烯光敏氧化反应中区域选择性的催化调控

游奎一 1, 尹笃林 2,a, 毛丽秋 2, 刘平乐 1, 罗和安 1,b   

  1. 1湘潭大学化工学院, 湖南湘潭 411105; 2湖南师范大学化学化工学院, 湖南长沙 410081
  • 收稿日期:2011-06-13 修回日期:2011-08-20 出版日期:2011-09-30 发布日期:2015-02-12

Catalytic Modulation on the Regioselectivity of the Photosensitized Oxidation of α-Pinene with Molecular Oxygen under Sodium Lamp Irradiation

YOU Kuiyi1, YIN Dulin2,a, MAO Liqiu2, LIU Pingle1, LUO He’an1,b   

  1. 1College of Chemical Engineering, Xiangtan University, Xiangtan 411105, Hunan, China; 2College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, Hunan, China
  • Received:2011-06-13 Revised:2011-08-20 Online:2011-09-30 Published:2015-02-12

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摘要： 发展了一种简单有效的 α-蒎烯光敏催化氧化方法, 该方法以高压钠灯为绿色光源, 内循环氧气作为氧化剂和搅拌气, 自制水浴式光化学反应器. 考察了催化剂种类和反应条件对 α-蒎烯转化率和产物选择性的影响. 结果表明, α-蒎烯可通过催化一步生成单萜醇、醛和酮, 且通过催化剂的酸碱协同作用可调节产物的区域选择性. 当以 N,N-二甲基甲酰胺为溶剂时, α-蒎烯的转化率可达 98%, 主产物马鞭草烯酮和马鞭草烯醇的总选择性达到了 84%. 此外, 还探讨了 N,N-二甲基甲酰胺酸碱协同催化的作用机理, 并利用密度泛函计算结果对 α-蒎烯分子中化学反应活性和产物选择性之间的对应关系进行了合理的解释.

关键词: 光敏氧化, α-蒎烯, 催化调控, 分子氧, N,N-二甲基甲酰胺, 密度泛函理论

Abstract: A simple and efficient photosensitized catalytic oxidation approach for α-pinene with molecular oxygen in a temperature-controlled reactor with sparged dioxygen as oxidant and an immersed high-pressure sodium lamp as a green irradiation light source was developed. The effects of various catalysts and reaction parameters on reaction performance were studied. The results indicated that 98% conversion with 84% total selectivity for verbenone and verbenol was obtained when N,N′-dimethylformamide (DMF) was used as a solvent. The product distributions were remarkably affected by the reaction media and DMF was found to especially modulate the regioselectivity of the products. Moreover, a possible photosensitized catalytic oxidation reaction mechanism in DMF is proposed and a clear acid-base synergetic catalysis effect was evident. The relationship between chemical reactivity and selectivity was modeled using density functional theory at the B3LYP/6-311+G(d) level from optimized molecular configurations.

Key words: photosensitized oxidation, α-pinene, catalytic modulation, molecular oxygen, N,N′-dimethylformamide, density functional theory