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

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%.