PDF《molecular oxygen》

1 Supporting Information for Oxidation of 5-hydroxymethylfurfural to maleic anhydride with molecular oxygen Zhongtian Du,a Jiping Ma,a,b Feng Wang,a Junxia Liu,a,b and Jie Xu a, * a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China b Graduate University of the Chinese Academy of Sciences, Beijing 100039, China Fax: (+86)-411-8437-9245 E-mail: xujie@dicp.

ac.cn Contents: 1. General Equipments and Materials (pp. 2-4) 2. Typical Procedure and Products Analysis (pp. 5-7) 3. Additional Results (pp.8 and 9) 4. Original GC,GC-MS, NMR and Photo Traces (pp.10-14)

2 1. General Equipments and Materials The typical experiments were carried out in a closed glass-lined stainless steel autoclave equipped with a magnetic stirring, a pressure gauge and automatic temperature control apparatus.

1 H NMR and

13 C NMR spectra were recorded on a Bruker

400 MHz spectrometer at room temperature in DMSO-d6. GC-MS was performed on Agilent 6890N GC/5973MS. 5-Hydroxymethylfurfural (HMF) was purchased from Wutong Aroma Chemicals Co., Ltd. 5-(Hydroxymethyl)furfuryl alcohol was obtained from Toronto Research Chemical Inc and used without further purification. 2,5-Diformylfuran (DFF) was synthesized by oxidation of HMF using our previous method (Fig. S2 and S3).

1 2,5-Furandicarboxylic acid was prepared by oxidation of DFF with KMnO4 (Fig. S4, S5 and S12).

2 Furfuryl alcohol was distilled under reduced pressure before use. 5-Methylfurfuryl alcohol was obtained from Acros Organics and used without any pretreatment. Acetonitrile contained about 1% (v/v) acetic acid. All other reagents were commercial available and used as received. VO(acac)2 was purchased from Alfa Aesar and used without further purification. VOSO4?xH2O (USP28) was dried at

120 o C overnight. VO(pic)2 [bis(pyridine-2-carboxylato)oxovanadium(IV)] and VO(mal)2 [bis(maltolato)oxovanadium (IV)] was synthesized according to the literatures. 3,4 Fig. S1: Molecular structures and abbreviation of some HMF derivatives References:

1 J. P. Ma, Z. T. Du, J. Xu, Q. H. Chu and Y. Pang, Chemsuschem, 2010, DOI: 10.1002/cssc.201000273.

2 D. W. Yoon, D. E. Gross, V. M. Lynch, J. L. Sessler, B. P. Hay and C. H. Lee, Angew. Chem. Int. Ed., 2008, 47, 5038-5042. (See its ESI-5)

3 M. Melchior, K. H. Thompson, J. M. Jong, S. J. Rettig, E. Shuter, V. G. Yuen, Y. Zhou, J. H. McNeill and C. Orvig, Inorg. Chem., 1999, 38, 2288-2293.

4 P. Caravan, L. Gelmini, N. Glover, F. G. Herring, H. L. Li, J. H. McNeill, S. J. Rettig, I. A. Setyawati, E. Shuter, Y. Sun, A. S. Tracey, V. G. Yuen and C. Orvig, J. Am. Chem. Soc., 1995, 117, 12759-12770.

3 Fig. S2:

1 H NMR (DMSO-d6) of 2,5-diformylfuran (The signal at 2.5 is attributed to DMSO solvent residue, and that of at 3.3 is attributed to water existed in DMSO-d6) Fig. S3:

13 C NMR (DMSO-d6) of 2,5-diformylfuran (DFF) O O O O O O b a a b

4 Fig. S4:

1 H NMR (DMSO-d6) of 2,5-furandicarboxylic acid (The signal at 2.5 is attributed to DMSO solvent residue) Fig. S5:

13 C NMR (DMSO-d6) of 2,5-furandicarboxylic acid O O O HO OH O O O HO OH a b a b

5 2. Typical Procedure and Products Analysis 2.1 Typical Procedure for Catalytic Oxidation A typical procedure for catalytic oxidation of HMF was as follows: VO(acac)2 (33.1 mg, 0.125 mmol) and HMF (315 mg, 2.5 mmol) was placed into the autoclave followed by

5 ml acetonitrile. After the autoclave was closed, oxygen was charged to 1.0 MPa. It was heated to

90 o C within

20 min. The oxygen was recharged if consumed during the oxidation. After