One-Pot Synthesis of 2,5-Furandicarboxylic Acid from 2-Furoic Acid by a Pd-catalyzed Bromination-Hydroxycarbonylation Tandem Reaction in Acetate Buffer

在乙酸缓冲液中,通过钯催化的溴化-羟基羰基化串联反应,由2-呋喃甲酸一锅法合成2,5-呋喃二甲酸

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Abstract

The one-pot synthesis of 2,5-furandicarboxylic acid from 2-furoic acid with a yield of 57 % was achieved for the first time using a Pd-catalyzed bromination-hydroxycarbonylation tandem reaction in HOAc-NaOAc buffer. This synthetic protocol shows major improvements compared to previously reported methods, such as using biomass-based 2-furoic acid as low-cost raw material, one-pot synthesis without isolation of intermediate products, and no need for an acidification procedure. Experiments indicate that the involved Xantphos-modified Pd-catalyst and the buffer solution play significant promoting roles for each individual reaction whereas Br(2) (as the brominating reagent) had a negative effect on the second hydroxycarbonylation step, while CO was deleterious for the first bromination step. Hence, in this practical one-pot synthesis, Br(2) should be consumed in the first bromination step as fully as possible, and CO is introduced after the first bromination step has been completed.

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