One‐Pot Synthesis of Renewable Phthalic Anhydride from 5‐Hydroxymethfurfural by using MoO₃/Cu(NO₃)₂ as Catalyst

Abstract

Herein, a synthetic pathway to renewable phthalic anhydride (PA) from 5‐hydroxymethfurfural (HMF) in one pot is reported. The commonly available catalysts MoO3 and Cu(NO3)2 play a crucial role in integrating the multiple steps of the reaction, namely decarbonylation of HMF to active furyl intermediate (AFI), oxidation of HMF to maleic anhydride (MA), Diels–Alder cycloaddition of AFI and MA, and subsequent dehydration, in one pot. Under mild reaction conditions, a 63.2 % yield of PA is obtained from HMF. Compared with the currently reported route to renewable PA based on the Diels–Alder cycloaddition of biomass‐derived MA and furan, this convenient one‐pot synthesis represents a great improvement in efficiency.

Hydroxyapatite‐Supported Polyoxometalates for the Highly Selective Aerobic Oxidation of 5‐Hydroxymethylfurfural or Glucose to 2,5‐Diformylfuran under Atmospheric Pressure

“…The products of aerobic oxidation of 5‐HMF in water were 2.5 % of DFF, 10.3 % of FDCA, 26.1 % of maleic acid, and 31.5 % of maleic anhydride based on UHPLC‐Q‐Exactive/MS at 92.4 % conversion (Figure S6). The main product from aerobic oxidation of 5‐HMF in water was maleic anhydride, which provided an alternative pathway for producing maleic anhydride based on bio‐platform chemical such as 5‐HMF instead of petroleum‐based raw materials [63] . The mechanism and some parameters on 5‐HMF oxidation in water will be done in the future.…”

“…The main product from aerobic oxidation of 5-HMF in water was maleic anhydride, which provided an alternative pathway for producing maleic anhydride based on bio-platform chemical such as 5-HMF instead of petroleum-based raw materials. [63] The mechanism and some parameters on 5-HMF oxidation in water will be done in the future. The total organic carbon (TOC) on PMo 4 V 8 remained larger than 87.1 %, indicating that over-oxidation was occurred to generate CO 2 .…”

Bioderived furanic compounds as replacements for BTX in chemical intermediate applications

“…Jia and co-workers have developed a catalytic system based on MoO 3 and Cu(NO 3 ) 2 achieving about 63 % yield using K 2 S 2 O 8 as stoichiometric oxidant. 634,635 The production of biobased PA still needs much research as very few publications are reported for an efficient and competitive chemical route to produce this chemical at large scale. The path reported by Mahmoud and coworkers 633 has the potential to produce high yields of PA but the process is strictly limited by the cost of production of maleic anhydride and furan and the separation, which still needs to be validated.…”

“…Jia and co-workers have developed a catalytic system based on MoO 3 and Cu(NO 3 ) 2 achieving about 63% yield using K 2 S 2 O 8 as stoichiometric oxidant. 634,635…”

Phthalic anhydride (PA): a valuable substrate in organic transformations

“… 17 PA obtained renewably form 5-hydroxymethfurfural (HMF) using MoO 3 /Cu(NO 3 ) 2 as a catalyst. 18 Sha group in 2016 designed a conceptual process to prepare PA from corn stover, an agricultural residue. Their techno-economic assessment contends energy integration alternatives as well as water consumption and life cycle greenhouse emissions.…”