氘代二茂铁炔酮的合成及其在机理研究中的应用

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；.

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

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 deu-terium 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 con-figurations 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；.