对称桥头二取代金刚烷衍生物的合成

Synthesis of Symmetrical Disubstituted Bridgehead Adamantane Derivatives

以易得的1-金刚烷甲酸为原料,合成了一系列对称桥头二取代金刚烷衍生物.由1-金刚烷甲酸经Koch-Haaf羰基化反应得到1,3-金刚烷二甲酸(1);化合物1经还原得到1,3-金刚烷二甲醇(2);化合物2在HBr-ZnBr2体系中经溴代反应得1,3-二(溴甲基)金刚烷(3);同时经Apple-Lee反应将化合物2转化得到1,3-二(氯甲基)金刚烷(4).采用红外光谱和核磁共振氢谱等手段表征了产物的结构,提出了可能的反应机理,并对合成条件进行了优化.

The symmetric bridge disubstituted adamantane derivatives are the key raw materials or interme-diates for preparing multisubstituted adamantane derivatives with admantane as the core. With 1-adamantane carboxylic acid that is more efficient and economical as an initial reactant, a series of synthesis technologies of symmetrical disubstituted bridgehead adamantane derivatives which have significant applications, were studied in this work. Those synthesis technologies include the following：1,3-adamantane dicarboxylic acid（1） was synthesized by 1-adamantane carboxylic acid through Koch-Haaf carbonylation; compound 1 was reduced to get 1,3-adamantane dimethanol（2）;compound 2 reacted by bromination in HBr-ZnBr2 system to afford 1,3-dibromomethyl adamantane（3）. Meanwhile, compound 2 converted to 1,3-dichloromethyl adamantane（4） through Apple-Lee reaction. The structures of prepared products were confirmed by IR spectra and 1 H NMR spectroscopy. The possible reaction mechanism was proposed, and the synthesis conditions were discussed and optimized for each technology respectively.