1,3-苯并二茂的微胶束催化氯甲基化新技术

Benzodioxole was monochloromethylated directly by aqueous formaldehyde and hydrogen chloride gas in CCl4 in the presence of quaternary ammonium salts: C16H33-（CH3）3NX（X=Br,Cl）, C12H25（CH3）3NCl,C12H25（CH3）2（C6H5CH2）NCl and （C4H9）4NBr. With hexadecyltrimethylammonium bromide at temperature 6065 ℃ and for 15 hours of reaction, 1,3-benzodioxole was converted to piperonyl chloride with conversion more than 98% and selectivity up to 97%. The method has advantages of high selectivity, high conversion, negligible by-products and easy workup of the main product.

3,4-亚甲二氧基正丙基苯的氯甲基化反应

在季铵盐四乙基溴化铵存在下，３，４－亚甲二氧基正丙基苯进行氯甲基化反应的转化率达９６．６％，定位选择性达１００％。对产物进行了气相色谱、红外光谱、核磁共振测定及元素分析。

对异辛基苯甲醚的氯甲基化

在季铵盐四丁基溴化铵作为相转移催化剂、氯化锌作为催化剂的双重催化条件下,物料配比为n(酚醚)∶n(甲醛)∶n(氯化锌)=1∶2∶1.25,反应温度30～40℃,对异辛基苯甲醚进行氯甲基化反应的转化率可达100%,收率达到95%。运用红外色谱、核磁共振测定等对产物结构进行确认。