室温条件下Salen配合物催化氧化安息香  

The Catalytic Oxidation of Benzoin by Salen Complexes at Room Temperature

作　　者：周步杰 毛国亮 陈中杭 方慧[1] 于文艳[1] 沈海民[1] 

机构地区：[1]浙江工业大学化学工程学院,浙江杭州310014

出　　处：《实验室研究与探索》2016年第8期21-26,共6页Research and Exploration In Laboratory

基　　金：国家自然科学基金项目(21306176);浙江省自然科学基金(LQ14B020002);浙江工业大学科研启动基金(G2817101103);浙江工业大学校自然科学基金(2014XY003)资助项目

摘　　要：以Salen配合物为催化剂,探究催化氧化安息香的清洁工艺条件。在室温条件下,由水杨醛、乙二胺反应制得席夫碱并与金属醋酸盐合成[M(Salen)](M=Mn,Co,Ni,Cu,Zn),同时使用红外光谱、核磁共振、XRD和XPS进行表征。以所得5种金属配合物为催化剂,探究对安息香氧化反应的催化性能。以空气为氧化剂,Co(Salen)为催化剂,优化了反应工艺。在优化条件下,探究了其他金属Salen配合物的催化性能,并用活性炭和分子筛固载Co(Salen),进行催化剂回收套用实验。实验表明,Mn(Salen)的催化性能最好,在催化剂含量为原料物质的量的6%,以DMF为溶剂,室温下反应60 min,苯偶酰的收率可达到80%以上。催化剂经分子筛吸附后可回收套用3次。该方法在室温下反应,节省能源,降低成本,符合绿色化学要求,为苯偶酰的清洁生产提供理论依据。To overcome the shortcomings in the catalytic oxidation of benzoin to benzils,such as environmental pollution,a cleaning process for catalytic oxidation of benzoin was explored using Salen complexes as catalysts. Five Schiff bases were synthesized from salicylaldehyde and ethylene diamine at room temperature,then [M（ Salen） ]（ M =Mn,Co,Ni,Cu,Zn） was synthesized at the presence of metal acetate. The structure of ligands and catalysts were characterized by infrared spectrum（ IR）,nuclear magnetic resonance（ NMR）,X-ray diffraction（ XRD） and X-ray photoelectron spectroscopy（ XPS）. The obtained five metal complexes were applied to the oxidation of benzoin to investigated their catalytic properties. The optimum process conditions for the reaction were explored with air as the oxidant and Co（ Salen） as a catalyst,and the catalytic performance of other metal Salen complexes and Co（ Salen）which was loaded on active carbon or molecular sieve were also explored. It was shown that Mn（ Salen） possessed the best catalytic properties. When the catalyst content was 6% of the substance,more than 80% benzil yielded can be reached at room temperature for 60 min with DMF as solvent. When Co（ Salen） was adsorbed onto molecular sieve,the catalyst can be recycled for three times. This synthetic strategy possesses advantages such as room temperature reaction,energy-saving,and low costs,which can properly realize the concept of green chemistry,and provide theoretical basis for the clean production of benzils.

关 键 词：席夫碱配合物 安息香 催化氧化 空气 室温 

分 类 号：O625.4[理学—有机化学]