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 -
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14
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 2 Cl2 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
15
Reusability Test
of Polymer-Supported IBX Amide Reagent
Upon completion
of oxidation, DFF was extracted with CH2 Cl2 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
16
Direct Production
of DFF from Fructose
® resin (100 mg, purchased from Aldrich) as
a solid-acid catalyst along
17
Analysis of Products
from Direct Conversion from Fructose
m/z = 168.15) and
OBMF {5,5′-[oxybis(methylene)-bis-2-furaldehyde],
MS: m/z = 234.05}.
