钠灯下α-蒎烯光敏氧化反应中区域选择性的催化调控(英文)  

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

作　　者：游奎一[1] 尹笃林[2] 毛丽秋[2] 刘平乐[1] 罗和安[1] 

机构地区：[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

出　　处：《催化学报》2011年第10期1610-1616,共7页

基　　金：supported by the National Natural Science Foundation of China(21006081,20976043);Natural Science Foundation of Hu-nan Province(11JJ3024,09JJ8002);Scientific Research Fund of Hunan Provincial Education Department(11B122);Scientificand Technological Plan Projec tof Hunan Province(2010JT4051);Program for New Century Excellent Talents in University(NCET-10-0168)~~

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.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.

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 

分 类 号：O643.32[理学—物理化学]