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Synthesis of 2,5-Diformylfuran and Furan-2,5-Dicarboxylic Acid by Catalytic Air-Oxidation of 5-Hydroxymethylfurfural. Unexpectedly Selective Aerobic Oxidation of Benzyl Alcohol to Benzaldehyde with Metal=Bromide Catalysts
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 6 FEB 2001 , DOI: 10.1002/1615-4169(20010129)343:1<102::aid-adsc102>3.0.co;2-q
Walt Partenheimer , Vladimir V. Grushin

The alcohol group of hydroxymethylfurfural (compound 1, HMF) is preferentially oxidized by dioxygen and metal/bromide catalysts [Co/Mn/Br, Co/Mn/Zr/Br; Co/Mn=Br/(Co+Mn) = 1.0 mol/mol] to form the dialdehyde, 2,5-diformylfuran (compound 2, DFF) in 57% isolated yield. HMF can be also oxidized, via a network of identified intermediates, to the highly insoluble 2,5-furandicarboxylic acid (compound 5, FDA) in 60% yield. For comparison, benzyl alcohol gives benzaldehyde in 80% using the same catalyst system. Over-oxidation (to CO2) of HMF is much higher than that of the benzyl alcohol but can be greatly reduced by increasing catalyst concentration.

中文翻译:

5-羟基甲基糠醛的催化空气氧化合成2,5-二甲酰基呋喃和呋喃-2,5-二羧酸。金属溴化催化剂意外地将苄醇选择性好氧氧化为苯甲醛

羟甲基糠醛(化合物1,HMF)的醇基优先被双氧和金属/溴化物催化剂[Co / Mn / Br,Co / Mn / Zr / Br; Co / Mn = Br /(Co + Mn)= 1.0mol / mol]形成二醛2,5-二甲酰基呋喃(化合物2,DFF),分离产率为57%。HMF也可以通过已确定的中间体网络氧化为高度不溶的2,5-呋喃二甲酸(化合物5,FDA),产率为60%。为了进行比较,使用相同的催化剂体系,苯甲醇可生成80%的苯甲醛。HMF的过氧化(转化为CO 2)远高于苯甲醇,但可以通过提高催化剂浓度来大大降低。
更新日期:2017-01-31
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