6-羟基-1,4-苯并二恶烷的合成及其在油脂中的抗氧化性研究

Synthesis of 2,3-dihydrobenzo[1,4]dioxin-6-ol and Its Antioxidant Activity in Oils

本文研究了芝麻酚类似物6-羟基-1,4-苯并二恶烷的合成及其在油脂中的抗氧化性。以邻苯二酚、二氯乙烷为起始原料,在碱性回流条件下经环化反应得到1,4-苯并二恶烷,然后通过Friedel-Crafts酰基化反应得到6-乙酰基-1,4-苯并二恶烷,之后经Bayer-Villiger氧化、水解酸化及柱层析分离得到目标化合物。对环化反应中Na OH溶液浓度、酰基化反应中溶剂种类以及氧化反应中氧化剂选择分别进行优化,得到实验较优条件:Na OH溶液浓度为50%,酰基化反应溶剂为硝基苯,Bayer-Villiger氧化反应氧化剂选择间氯过氧苯甲酸。采用红外光谱(IR)、质谱(MS)以及核磁共振(13C-NMR)对终产物进行结构鉴定和表征,确定目标产物为6-羟基-1,4-苯并二恶烷。测定了其在油脂中的抗氧化能力,结果表明该芝麻酚类似物在动植物油脂中都具有一定的抗氧化性。

In this paper, the synthesis and antioxidant activity of 2,3-dihydrobenzo[1,4]dioxin-6-ol, a sesamol analogue, are described. Using catechol and 1,2-dichloroethane as starting materials, 1,4-benzodioxane was prepared by cyclization under refluxing basic conditions, and then, Ffiedel-Crafts acylation was carried out to yield 6-acetyl-1,4-benzodioxane. The final product was obtained after Baeyer-Villiger oxidation, hydrolytic acidification, and column chromatography. The concentration of NaOH solution in the cyclization, the solvent used in the acylation, and the oxidizing agent in the oxidation were optimized. The optimum conditions for each step were as follows： concentration of NaOH, 50%; solvent for the acylation reaction, nitrobenzene; oxidizing agent in the Baeyer-Villiger oxidation, 3-chloroperbenzoic acid. Structural identification and characterization were conducted using infrared spectroscopy, mass spectrometry, and nuclear magnetic resonance spectroscopy （^13C-NMR）, and the final product was identified as 2,3-dihydro-benzo[1,4]dioxin-6-oL The antioxidant activity of the obtained product in oils was evaluated, and the results showed that this sesamol analogue displayed antioxidant activity in both animal and vegetable oils.