Cu配合物催化硼氢化钠还原CO2制备甲醇

利用廉价金属铜盐和N,N,N′,N′-四甲基乙二胺(TMED)、N,N′-二甲基乙二胺、乙二胺、联嘧啶等配体原位生成金属配合物,并用于催化硼氢化钠还原二氧化碳制备甲醇反应.分别考察了金属、配体、溶剂和阴离子对催化反应的影响,结果表明在常温常压条件下,催化剂CuI/TMED、CuI/N,N′-二甲基乙二胺、CuI/乙二胺、CuI/联嘧啶能高效催化硼氢化钠还原二氧化碳反应生成甲醇.在25℃和1 atm CO2条件下,CuI/TMED催化硼氢化钠还原二氧化碳反应生成甲醇的产率和TON最高分别达到47%和315.通过原位红外和核磁对催化反应进行研究,并提出可能的催化机理.

Synthesis of 5-vinyl-2-norbornene through Diels-Alder reaction of cyclopentadiene with 1,3-butadiene in supercritical carbon dioxide

An efficient method for the synthesis of 5-vinyl-2-norbornene from cyclopentadiene and 1,3-butadiene was developed.The Diels-Alder reaction of cyclopentadiene with 1,3-butadiene proceeded smoothly in supercritical carbon dioxide in the absence of any polymerization inhibitor to produce the corresponding5-vinyl-2-norbornene in satisfactory yield with high selectivity.