A POTENTIALLY GENERAL REGIOSPECIFIC SYNTHESIS OF SUBSTITUTED QUINONES FROM DIMETHYL SQUARATE
A POTENTIALLY GENERAL REGIOSPECIFIC SYNTHESIS OF SUBSTITUTED QUINONES FROM DIMETHYL SQUARATE
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DOI：
10.1021/jo00051a040
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发表时间：
1992-12-04
影响因子：
3.6
通讯作者：
MOORE, HW
中科院分区：
文献类型：
--
作者：
GAYO, LM;WINTERS, MP;MOORE, HW
一个潜在的一般区域特异性合成的苯醌和萘醌。该方法从方酸二甲酯（1）开始，其在依次用有机锂试剂和然后用BF 3醚合物或TFAA在THF/甲醇中处理后转化为环丁烯酮缩酮3。用第二种锂试剂处理这些化合物，然后水解，得到环丁烯酮5。将炔基-、烯基-或芳基锂试剂加成到5上，然后水解缩酮键，得到相应的4-炔基-4-烯基-或4-芳基-4-羟基环丁烯酮7-9，这些化合物在乙苯中重排后容易重排成相应的醌或氢醌。以类似的方式，使用15作为试剂来制备单取代和二取代的氢醌和醌。
A potentially general regiospecific synthesis of benzo- and naphthoquinones is described. This method starts with dimethyl squarate (1), which is converted to the cyclobutenone ketal 3 upon sequential treatment with an organolithium reagent and then BF3 etherate or TFAA in THF/methanol. Treatment of these with a second lithium reagent followed by hydrolysis gives the cyclobutenones 5. Addition of an alkynyl-, alkenyl- or aryllithium agent to 5 followed by hydrolysis of the ketal linkage gives the corresponding 4-alkynyl- 4-alkenyl- or 4-aryl-4-hydroxycyclobutenones 7-9, and these readily rearrange to the respective quinones or hydroquinones upon thermolysis in refluxing benzene. In a similar fashion, 15 was employed as a reagent to prepare mono- and disubstituted hydroquinones and quinones.