氘代二茂铁炔酮的合成及其在机理研究中的应用  

The Synthesis of Deuterated Ferrocenyl Alkynone and Its Application in Mechanism Research

作　　者：叶红德[1] 童怀多 邹如意[1] 彭化南[1] 郑大贵[1] 肖依文[1] 宋焕权[1] 

机构地区：[1]上饶师范学院化学化工学院,江西省普通高校应用有机化学重点实验室,江西上饶334001 [2]江西省上饶中学,江西上饶334000

出　　处：《江西师范大学学报（自然科学版）》2012年第6期558-561,共4页Journal of Jiangxi Normal University(Natural Science Edition)

基　　金：江西省教育厅科技课题(GJJ09376);江西省普通高校重点实验室科技计划课题(GJJ11710);教育部第4批高等学校特色专业建设点课题(TS11524)资助项目

摘　　要：二茂铁炔醇FcCH（OH）C≡CH（Fc=二茂铁基）与乙基溴化镁反应,再与重水和氘代乙酸反应,得到氘代二茂铁炔醇FcCH（OH）C≡CD,氘代率为95%.氘代二茂铁炔醇用二氧化锰氧化,得到氘代二茂铁炔酮FcC（O）C≡CD,氘代率为92%.氘代二茂铁炔酮与半夹芯16e碳硼烷化合物CpCo（S2C2B10H10）反应,分离得到3个碳碳双键构型分别为Z/Z、Z/E和E/E的产物（FcCH=CHS）2（C2B10H10）.核磁共振氢谱结果表明：在CH=CHS结构单元中,与硫原子相连的CH单元上的氢原子氘代率约为60%~65%,远离硫原子的CH单元上的氢原子氘代率约为5%~10%.Ferrocenyl alkynol FcCH（OH）C≡CH（Fc=ferrocenyl） reacted with ethylmagnesium bromide and then with deuterated water and deuterated acetic acid to give deuterated ferrocenyl alkynol FcCH（OH）C≡CD.The deuterium content of the synthesized deuterated ferrocenyl alkynol was 95% as measured by 1H NMR.Deuterated ferrocenyl alkynol was oxidized by manganese dioxide to afford deuterated ferrocenyl alkynone FcC（O）C≡CD with the deuterium content of 92%.Deuterated ferrocenyl alkynone reacted with half-sandwich 16e carborane compound CpCo（S2C2B10H10） to afford three configurational isomers（FcCH=CHS）2（C2B10H10）,in which the configurations of two C=C double bonds were Z/Z,Z/E and E/E,respectively.The results of 1H NMR showed that in the CH=CHS units the deuterium content of the CH units linked with the sulfer atoms was about 60%~65% while that of the CH units far from the sulfer atoms was about 5%~10%.

关 键 词：氘代二茂铁炔醇 氘代二茂铁炔酮 合成 氘代率 机理 

分 类 号：O614.8[理学—无机化学]