【作者】 晋平；

【导师】 张国亮；

【作者基本信息】 天津大学 ， 生物医学工程， 2006， 硕士

【摘要】 1,4-二氧杂螺[4.5]癸烷-8-酮是具有双官能团的重要有机合成原料,被广泛地应用于医药中间体、液晶材料和农药中间体的合成。本文通过对比分析现有的多种1,4-二氧杂螺[4.5]癸烷-8-酮合成路线的优缺点,选择了酸性溶液中选择性水解1,4,9,12-四氧杂二螺[4.2.4.2]十四烷的方法进行研究,对在醋酸催化下水解的选择性提出了可能的解释,并对该方法的工艺条件进行了改进。在此基础上,对醋酸水溶液中选择性水解1,4,9,12-四氧杂二螺[4.2.4.2]十四烷的动力学进行了测试。实验结果表明,以冰醋酸作催化剂,V(冰醋酸):V(H2O)=5:1的溶液作为反应介质,反应浓度为0.05g/mL,反应温度为65℃时,反应时间由15h缩短为约11min,产物的色谱收率由65%提高到80%。反应动力学研究表明,醋酸水解反应符合准一级反应动力学模型,其反应活化能为122.65kJ/mol。基于绿色化学的考虑,本文进一步考察了以阳离子交换树脂代替醋酸作为催化剂的可能性,结果表明以羧酸型阳离子交换树脂D152作为选择性去缩酮的催化剂,在75℃水溶液中反应160min,转化率为89%,选择性为77%。虽然一次收率略低,但是该反应无需有机溶剂,可直接在水溶液中进行,并且反应条件温和,无酸腐蚀和污染问题,后处理简单,催化剂无需处理可重复使用多次,生成的副产物1,4-环己二酮可用乙二醇缩酮化后重新进入反应循环,提高其总收率。通过熔点分析、红外光谱分析和核磁共振谱图分析等一系列分析方法验证了所合成的产物为目标产物1,4-二氧杂螺[4.5]癸烷-8-酮。更多还原

【Abstract】 1,4-Dioxaspiro[4.5]decan-8-one is an exceedingly useful bifunctional synthetic intermediate and has been widely used in synthetic organic chemistry such as pharmaceuticals, liquid crystals and insecticides. After compared the existing methods for synthesis1,4-Dioxaspiro[4.5]decan-8-one, taking 1,4,9,12-tetraoxadispiro [4.2.4.2] -tetradecano as raw material, 1,4-dioxaspiro[4.5]decan-8-one has been synthesized via selective deketalization in acidic aqueous solution. The possible mechanism of selectivity and influence factors has been discussed. Compared with the catalytic effects of different acids, acetic acid (HAc) has been selected as the catalyst, and the optimizing test of the operation conditions has also been determined. The results show that the chromatographic yield is raised to 80% from 65% and the reaction time is reduced to 11min from 15h under the optimum reaction conditions, in which reaction temperature is 65℃, the volume ratio of HAc to H2O 5:1 and the reaction concentration 0.05g ? mL-1. The dynamic research shows that the hydrolysis of 1,4,9,12-tetraoxadispiro [4.2.4.2] tetradecano fits the one order reaction model and the activation energy is 122.65 kJ/mol.Considering the demands of the green chemistry, the synthesis of 1,4-dioxaspiro- [4.5]decan-8-one by selective deketalization of 1,4,9,12-tetraoxadispiro[4.2.4.2]tetra- decano in aqueous solution over solid acid catalysts has been studied. For purpose of comparison, several different ion-exchange resins were investigated. The results show that the best-performing resin was weakly acidic cation exchange resin D152, with 89% conversion and 77% selectivity after 160min of reaction time at 75℃in aqueous solution. The strategy has demonstrated a green chemistry approach with features of aqueous media, mild condition, simple workup, and reusability of the catalyst.The product is characterized by IR and 1HNMR, 13CNMR.更多还原