CAJ | 학술논문

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.
발전료일충간단유효적α-파희광민최화양화방법,해방법이고압납등위록색광원,내순배양기작위양화제화교반기,자제수욕식광화학반응기.고찰료최화제충류화반응조건대α-파희전화솔화산물선택성적영향.결과표명,α-파희가통과최화일보생성단첩순、철화동,차통과최화제적산감협동작용가조절산물적구역선택성.당이N,N-이갑기갑선알위용제시,α-파희적전화솔가체98％,주산물마편초희동화마편초희순적총선택성체도료84％.차외,환탐토료N,N-이갑기갑선알산감협동최화적작용궤리,병이용밀도범함계산결과대α-파희분자중화학반응활성화산물선택성지간적대응관계진행료합리적해석.
A simple and efficient photosensitized catalytic oxidation approach for α-pinene with molecular oxygen in a temperature-eontrolled 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.