高等学校化学学报
高等學校化學學報
고등학교화학학보
CHEMICAL JOURNAL OF CHINESE UNIVERSITIES
2014年
8期
1686-1690
,共5页
徐晓健%郭建维%朱东雨%钟星
徐曉健%郭建維%硃東雨%鐘星
서효건%곽건유%주동우%종성
金刚烷%1 ,3-金刚烷二甲酸%1 ,3-金刚烷二甲醇%1 ,3-二(溴甲基)金刚烷%1 ,3-二(氯甲基)金刚烷
金剛烷%1 ,3-金剛烷二甲痠%1 ,3-金剛烷二甲醇%1 ,3-二(溴甲基)金剛烷%1 ,3-二(氯甲基)金剛烷
금강완%1 ,3-금강완이갑산%1 ,3-금강완이갑순%1 ,3-이(추갑기)금강완%1 ,3-이(록갑기)금강완
Adamantane%1,3-Adamantane dicarboxylic acid%1,3-Adamantane dimethanol%1,3-Dibromo-methyl adamantane%1,3-Dichloromethyl adamantane
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。
以易得的1-金剛烷甲痠為原料,閤成瞭一繫列對稱橋頭二取代金剛烷衍生物。由1-金剛烷甲痠經Koch-Haaf羰基化反應得到1,3-金剛烷二甲痠(1);化閤物1經還原得到1,3-金剛烷二甲醇(2);化閤物2在HBr-ZnBr2體繫中經溴代反應得1,3-二(溴甲基)金剛烷(3);同時經Apple-Lee反應將化閤物2轉化得到1,3-二(氯甲基)金剛烷(4)。採用紅外光譜和覈磁共振氫譜等手段錶徵瞭產物的結構,提齣瞭可能的反應機理,併對閤成條件進行瞭優化。
이역득적1-금강완갑산위원료,합성료일계렬대칭교두이취대금강완연생물。유1-금강완갑산경Koch-Haaf탄기화반응득도1,3-금강완이갑산(1);화합물1경환원득도1,3-금강완이갑순(2);화합물2재HBr-ZnBr2체계중경추대반응득1,3-이(추갑기)금강완(3);동시경Apple-Lee반응장화합물2전화득도1,3-이(록갑기)금강완(4)。채용홍외광보화핵자공진경보등수단표정료산물적결구,제출료가능적반응궤리,병대합성조건진행료우화。
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.