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Synlett 2011(2): 165-168  
DOI: 10.1055/s-0030-1259284
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Selective Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran by Polymer-Supported IBX Amide

Hyo-Jin Yoona, Jung-Woo Choia, Hyung-Seok Janga, Jin Ku Chob, Jang-Woong Byunc, Woo-Jae Chunga, Sang-Myung Leea, Yoon-Sik Lee*a
a School of Chemical and Biological Engineering, Seoul National University, Seoul 151-744, Korea
Fax: +82(2)8769625; e-Mail: yslee@snu.ac.kr;
b Green Process R&D Department, Korea Institute of Industrial Technology, Cheonan, 331-825, Korea
c BeadTech Inc, Institute for Chemical Processes, Seoul National University, Seoul 151-744, Korea
Further Information

Publication History

Received 12 October 2010
Publication Date:
23 December 2010 (online)

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Abstract

5-Hydroxymethyl-2-furfural (HMF) was selectively converted to 2,5-diformylfuran (DFF) under mild conditions by polymer-supported IBX amide reagent, thus providing a new platform for the production of highly valuable chemicals from biomass.

Key words

2,5-diformylfuran (DFF) - heterogeneous reagents -
oxidation - polymer-supported IBX

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Synthesis of Polymer-Supported IBX Amide Reagent Polymer-supported IBX amide reagent was prepared from aminomethyl polystyrene resin (AM PS, 2.1 mmol of NH2/g, Beadtech Inc.). After AM PS resin was pre-swollen with DMF at r.t. for 1 h, 2-iodobenzoic acid was coupled to the resin using DIPCDI/HOBt (3 equiv, each) at r.t. for 4 h to produce 2-iodobenzamide resin (1, Scheme  [³] ). The resin was then oxidized by tetrabutylammonium oxone (5 equiv) with methylsulfonic acid in CH2Cl2 for 12 h.¹³ The loading level of polymer-supported oxidants was determined to be 1.02 mmol/g by methoxybenzyl alcohol oxidation method.¹²

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Reusability Test of Polymer-Supported IBX Amide Reagent Upon completion of oxidation, DFF was extracted with CH2Cl2 and the remaining polymer-supported IBA (iodosobenzoic acid, reduced form of IBX) amide was separated by simple filtration. The filtered polymer-supported IBA was easily regenerated after treatment with tetrabutylammonium oxone (5 equiv) and methanesulfonic acid for 12 h as previously reported.¹²

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Direct Production of DFF from Fructose
In the one-pot reaction, Amberlist 15® resin (100 mg, purchased from Aldrich) as a solid-acid catalyst along
with polymer-supported IBX amide reagent (100 mg) as an oxidant reagent were reacted together with fructose
(1 mmol) under DMSO at 100 ˚C.

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Analysis of Products from Direct Conversion from Fructose
Direct conversion of fructose to DFF was analyzed using HPLC equipped with a refractive index detector. The column oven temperature was 30 ˚C, and mobile phase was a 25% MeCN aq solution applied at a flow rate of 1 mL/min. The amounts of HMF and DFF in the reaction mixture were also analyzed by HPLC with a UV detector, and the yields were calculated by GC-MS analysis. From this experiment, we identified two main byproducts as AMF (5-acetoxy-methyl-2-furaldehyde, MS: m/z = 168.15) and OBMF {5,5′-[oxybis(methylene)-bis-2-furaldehyde], MS: m/z = 234.05}.