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

Hyo-Jin Yoon; Jung-Woo Choi; Hyung-Seok Jang; Jin Ku Cho; Jang-Woong Byun; Woo-Jae Chung; Sang-Myung Lee; Yoon-Sik Lee

doi:10.1055/s-0030-1259284

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synlett 2011(2): 165-168
DOI: 10.1055/s-0030-1259284

LETTER

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

Hyo-Jin Yoon^a, Jung-Woo Choi^a, Hyung-Seok Jang^a, Jin Ku Cho^b, Jang-Woong Byun^c, Woo-Jae Chung^a, Sang-Myung Lee^a, 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)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

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

References and Notes

1a Bridgwater AV. Chem. Eng. J. 2003, 91: 87

Google Scholar
1b Corma A. Iborra S. Velty A. Chem. Rev. 2007, 107: 2411

Google Scholar
2a Werpy T. Petersen G. Aden A. Bozell J. Holladay J. White J. Manheim A. Elliot D. Lasure L. Jones S. Gerber M. Ibsen K. Lumberg L. Kelley S. Top Value Added Chemicals from Biomass, In Results of Screening for Potential Candidates from Sugars and Synthesis Gas Vol. 1: U.S. Department of Energy (DOE); Oak Ridge, TN: 2004.

Google Scholar
2b Chheda JN. Huber GW. Dumesic JA. Angew. Chem. Int. Ed. 2007, 46: 7164

Google Scholar
3 Kunkes EL. Simonetti DA. West RM. Serrano-Ruiz JC. Gärtner C. Dumesic JA. Science 2008, 322: 417

Crossref Google Scholar
4a Lewkowski J. ARKIVOC 2001, (i): 17

Google Scholar
4b Lichtenthaler FW. Acc. Chem. Res. 2002, 35: 728

Google Scholar
4c Ribeiro ML. Schuchardt U. Catal. Commun. 2003, 4: 83

Google Scholar
5a Gandini A. Belgacem NM. Polym. Int. 1998, 47: 267

Google Scholar
5b Gandini A. Belgacem NM. Prog. Polym. Sci. 1997, 22: 1203

Google Scholar
6 Richter DT. Lash TD. Tetrahedron Lett. 1999, 40: 6735

Crossref Google Scholar
7a Takimiya K. Otsubo T. Ogura F. Ashitaka H. Morita K. Suehiro T. Chem. Lett. 1994, 23: 255

Google Scholar
7b Adams H. Bastida R. de Blas A. Carnota M. Fenton DE. Macías A. Rodriguez A. Rodriguez-Blas T. Polyhedron 1997, 16: 567

Google Scholar
8a Del Poeta M. Schell WA. Dykstra CC. Jones S. Tidwell RR. Czarny A. Bajic M. Kumar A. Boykin D. Perfect JR. Antimicrob. Agents Chemother. 1998, 42: 2495

Google Scholar
8b Hopkins KT. Wilson WD. Bendan BC. McCurdy DR. Hall JE. Tidwell RR. Kumar A. Bajic M. Boykin DW. J. Med. Chem. 1998, 41: 3872

Google Scholar
9a Sheibley DW. Manzo MA. Gonzalez-Sanabria OD. J. Electrochem. Soc. 1983, 130: 255

Google Scholar
9b Daub J. Salbeck J. Knöchel T. Fischer C. Kunkely H. Rapp KM. Angew. Chem., Int. Ed. Engl. 1989, 28: 1494

Google Scholar
10a Cottier L. Descotes G. Lewkowski J. Synth. Commun. 1994, 24: 939

Google Scholar
10b Partenheimer W. Grushin VV. Adv. Synth. Catal. 2001, 343: 102

Google Scholar
10c Grushin V, Partenheimer W, and Manzer LE. inventors; US 2003/0055271.
10d Halliday GA. Young RJ. Grushin VV. Org. Lett. 2003, 5: 2003

Google Scholar
10e Carlini C. Patrono P. Galletti AMR. Sbrana G. Zima V. Appl. Catal., A 2005, 289: 197

Google Scholar
10f Amarasekara AS. Green D. McMillan E. Catal. Commun. 2008, 9: 286

Google Scholar
10g Navarro OC. Canos AC. Chornet SI. Top. Catal. 2009, 52: 304

Google Scholar
11a Wirth T. Angew. Chem. Int. Ed. 2005, 44: 3656

Google Scholar
11b Ladziata U. Zhdankin VV. ARKIVOC 2006, (ix): 26

Google Scholar
11c Stang PJ. J. Org. Chem. 2003, 68: 2997

Google Scholar
11d Zhdankin VV. Stang PJ. Chem. Rev. 2002, 102: 2523

Google Scholar
11e Varvoglis A. Meth-Cohn O. Kirschning A. Rees C. Hypervalent Iodine in Organic Synthesis Academic Press; London: 1996.

Google Scholar
12a Chung W. Kim D. Lee Y. Tetrahedron Lett. 2003, 44: 9251

Google Scholar
12b Kim D. Chung W. Lee Y. Synlett 2005, 279

Google Scholar
12c Chung W. Kim D. Lee Y. Synlett 2005, 2175

Google Scholar
12d Jang H. Chung W. Lee Y. Tetrahedron Lett. 2007, 48: 3731

Google Scholar
12e Lei Z. Denecker C. Jegasothy S. Sherrington DC. Slater NKH. Sutherland AJ. Tetrahedron Lett. 2003, 44: 1635

Google Scholar
12f Mülbaier M. Giannis A. Angew. Chem. Int. Ed. 2001, 40: 4393

Google Scholar
12g Sorg G. Mengel A. Jung G. Rademann J. Angew. Chem. Int. Ed. 2001, 40: 4395

Google Scholar
13 Trost BM. Braslau R. J. Org. Chem. 1988, 53: 532

Crossref Google Scholar

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] ). 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

15

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

16

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.

17

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}.