1,4-二氧杂螺[4.5]癸烷-8-酮的合成  

Synthesis of 1,4-Dioxaspira[4.5]decan-8-one

作　　者：晋平[1] 刘亮[1] 张国亮[1] 张凤宝[1] 

机构地区：[1]天津大学化工学院,天津300072

出　　处：《高校化学工程学报》2006年第6期963-966,共4页Journal of Chemical Engineering of Chinese Universities

摘　　要：以1,4,9,12-四氧杂二螺[4.2.4.2]十四烷为原料,采用酸性条件下水解缩酮选择性地脱除单侧羰基保护的方法合成了1,4-二氧杂螺[4.5]癸烷-8-酮。通过对盐酸、硫酸、甲酸、醋酸等催化性能的比较,对选择性的机理和影响因素进行了探讨,确定醋酸作为催化剂。优化了反应工艺条件,并对产品进行了IR、1HNMR的确认。结果表明,以冰醋酸作催化剂,反应溶剂V(冰醋酸):V(H2O)=5:1,反应浓度为0.05g?mL?1,反应温度为65℃时,与原方法相比,反应时间由15h缩短为约11min,产物的色谱收率由65%提高到80%。1,4-Dioxaspiro[4,5]decan-8-one is an exceedingly useful bifunctional synthetic intermediate and has been widely used in synthesizing organic chemicals, such as pharmaceutical intermediates, liquid crystals and insecticides. Taken 1,4,9,12-tetraoxadispiro[4.2.4.2] tetradecane as raw material, 1,4-Dioxaspiro[4.5]decan-8-one was synthesized via selective deketalization in acidic solution, and the products were characterized by IR and ^1HNMR. After comparing the catalytic effects of different acids, the acetic acid （HAc） was selected as the catalyst. The possible mechanism of selectivity and its influence factors were discussed and the optimization of the operation conditions was also conducted. The results show that, comparing with the preparing method proposed by literature, under the optimum reaction conditions （i.e. reaction temperature=65℃, volume ratio HAc/H2O=5：1 and reactant concentration=0.05g·mL^-1）, the chromatographic yield of 1,4-Dioxaspiro[4.5]decan-8-one is raised to 80% from 65% and the reaction time is reduced to 11 min from 15 h.

关 键 词：1 4-二氧杂螺[4.5]癸烷-8-酮 1 4 9 12-四氧杂二螺[4.2.4.2]十四烷 选择性去保护 水解 

分 类 号：TQ234.2[化学工程—有机化工]