以3,4,5-三甲氧基甲苯(TMT)为原料,先由V ilsm e ier-Haack反应合成6-甲基-2,3,4-三甲氧基苯甲醛,然后在对甲基苯磺酸催化下经Dak in反应将其氧化为6-甲基-2,3,4-三甲氧基苯酚,最后用重铬酸钠催化氧化合成了辅酶Q0,过程总收率达到72.3%...以3,4,5-三甲氧基甲苯(TMT)为原料,先由V ilsm e ier-Haack反应合成6-甲基-2,3,4-三甲氧基苯甲醛,然后在对甲基苯磺酸催化下经Dak in反应将其氧化为6-甲基-2,3,4-三甲氧基苯酚,最后用重铬酸钠催化氧化合成了辅酶Q0,过程总收率达到72.3%。经正交实验得V ilsm e ier-Haack反应的最佳工艺为:n(TMT)∶n(POC l3)∶n(DMF)=1∶1.8∶2.2,反应温度70℃,反应时间7 h。在此工艺条件下,此步反应收率可达93.2%,w(6-甲基-2,3,4-三甲氧基苯甲醛)=98.5%;在Dakin反应中,以w(H2O2)=30%为氧化剂,30℃为最佳反应温度,反应时间1.5 h。展开更多
Aldehydes are valuable intermediates with widespread industrial applications,and their traditional synthesis relies on chemical oxidation that is often hazardous and environmentally unfriendly.Electrochemical oxidatio...Aldehydes are valuable intermediates with widespread industrial applications,and their traditional synthesis relies on chemical oxidation that is often hazardous and environmentally unfriendly.Electrochemical oxidation offers a more sustainable and milder alternative;however,it faces challenges such as aldehyde overoxidation and susceptibility to base-catalyzed Cannizzaro disproportionation.Electrochemical glycerol oxidation to glyceraldehyde is a representative example,which typically requires precious metal-based electrocatalysts but still suffers from low selectivity and activity.Here,we report a metal-free oxidation strategy mediated by 2,2,6,6-tetramethylpiperidine-1-oxyl.By systematically investigating the redox thermodynamics and kinetics of TEMPO across a broad pH range,we construct a Pourbaix diagram and elucidate the relative kinetics of each reaction step.These insights allow us to explain the anomalously high apparent Faradaic efficiency(~200%)observed under acidic conditions,and identify neutral media as the optimal environment for selective glyceraldehyde production.Under optimized conditions,our system achieves a glyceraldehyde Faradaic efficiency exceeding 93%and a partial current density of 23.3 mA cm^(-2)at 0.57 V—more than doubling the performance of the best reported precious metal-based systems.Furthermore,the versatility of this strategy extends to the selective oxidation of other primary alcohols to their corresponding aldehydes with near-unity selectivity.展开更多
文摘Aldehydes are valuable intermediates with widespread industrial applications,and their traditional synthesis relies on chemical oxidation that is often hazardous and environmentally unfriendly.Electrochemical oxidation offers a more sustainable and milder alternative;however,it faces challenges such as aldehyde overoxidation and susceptibility to base-catalyzed Cannizzaro disproportionation.Electrochemical glycerol oxidation to glyceraldehyde is a representative example,which typically requires precious metal-based electrocatalysts but still suffers from low selectivity and activity.Here,we report a metal-free oxidation strategy mediated by 2,2,6,6-tetramethylpiperidine-1-oxyl.By systematically investigating the redox thermodynamics and kinetics of TEMPO across a broad pH range,we construct a Pourbaix diagram and elucidate the relative kinetics of each reaction step.These insights allow us to explain the anomalously high apparent Faradaic efficiency(~200%)observed under acidic conditions,and identify neutral media as the optimal environment for selective glyceraldehyde production.Under optimized conditions,our system achieves a glyceraldehyde Faradaic efficiency exceeding 93%and a partial current density of 23.3 mA cm^(-2)at 0.57 V—more than doubling the performance of the best reported precious metal-based systems.Furthermore,the versatility of this strategy extends to the selective oxidation of other primary alcohols to their corresponding aldehydes with near-unity selectivity.
