Methodologies for chemical utilization of CO₂ to valuable compounds through molecular activation by efficient catalysts

Abstract

The reactions of CO₂ with oxirane to produce cyclic carbonate, and with aziridine to afford oxazolidine have been of interest as a useful method for its fixation by a chemical process. Highly efficient processesemploying recyclable CO₂-phlilic homogeneous catalyst were devised for environmentally benign synthesis of cyclic carbonates and oxazolidinones under supercritical CO₂ without any organic solvent. These processes represent pathways for greener chemical fixations of CO₂ to afford industrial useful materials such as organic carbonates and oxazolidinones with great potential applications.

Key words： carbon dioxide; chemical utilization; molecular catalyst; carbonate; oxazolidinone

Acknowledgements

The authors gratefully acknowledge the National Natural Science Foundation of China (Grant Nos. 20421202, 20672054), the Tianjin Natural Science Foundation, the 111 project (B06005) and State Key Laboratory of Fine Chemicals, Dalian University of Technology (No. KF0506) for their financial support.

References

1 Dou X Y, Wang J Q, Du Y, Wang E, He L N. Guanidinium salt functionalized PEG: an effective and recyclable homogeneous catalyst for the synthesis of cyclic carbonates from CO₂ and epoxides under solvent-free conditions. Synlett, 2007, 19: 3058–3062

2 Du Y, Wu Y, Liu A H, He L N. Quaternary ammonium bromide functionalized polyethylene glycol: A highly efficient and recyclable catalyst for selective synthesis of 5-aryl-2-oxazolidinones from carbon dioxide and aziridines under solvent-free conditions. J Org Chem, 2008, 73: 4709–4712

3 Miao C X, Wang J Q, Wu Y, Du Y, He L N., Bifunctional metal-salen complexes as efficient catalysts for the fixation of CO₂ with epoxides under solvent-free conditions. Chem Sus Chem, 2008, 1: 236–241

4 Du Y, Cai F, Kong D L, He L N. Organic solvent-free process for the synthesis of propylene carbonate from supercritical carbon dioxide and propylene oxide catalyzed by insoluble ion exchange resins. Green Chem, 2005, 7(7): 518–523

5 Du Y, Wang J Q, Chen J Y, Cai F, Tian J S, Kong D L, He L N. A poly(ethylene glycol)-supported quaternary ammonium salt for highly efficient and environmentally friendly chemical fixation of CO₂ with epoxides under supercritical conditions. Tetrahedron Lett, 2006, 47(8): 1271–1275

6 Miao C X, Wang J Q, He L N. Catalytic processes for chemical conversion of carbon dioxide into cyclic carbonates and polycarbonates. The Open Org Chem J, 2008, 2: 68–82; http://www.bentham.org/open/toocj/openaccess2.htm

7 Du Y, He L N, Kong D L. Magnesium-catalyzed synthesis of organic carbonate from 1,2-diol/alcohol and carbon dioxide. Catal Commun, 2008, 9: 1754–1758

8 Darensbourg D J, Holtcamp M W. Catalysts for the reactions of epoxides and carbon dioxide. Coord Chem Rev, 1996, 153: 155–174

9 Tian J S, Miao C X, Wang J Q, Cai F, Du Y, Zhao Y, and He L N. Efficient synthesis of dimethyl carbonate from methanol, propylene oxide and CO₂ catalyzed by recyclable inorganic base/phosphonium halide-functionalized polyethylene glycol. Green Chem, 2007, 9: 566–571

10 Wang J Q, Cai F, Wang E, He L N. Supercritical carbon dioxide and poly(ethylene glycol): an environmentally benign biphasic solvent system for aerobic oxidation of styrene, one-pot synthesis of dimethyl carbonate catalyzed by n-Bu₄NBr/n-Bu₃N from methanol, epoxides, and supercritical CO₂. Green Chem, 2007, 9: 882–887

11 Tian J S, Wang J Q, Chen J Y, Fan J G, Cai F, He L N. One-pot synthesis of dimethyl carbonate catalyzed by n-Bu₄NBr/n-Bu₃N from methanol, epoxides, and supercritical CO₂. Appl Catal A: Gen, 2006, 301(2): 215–221

12 Du Y, Kong D L, Wang H Y, Cai F, Tian J S, Wang J Q, He L N. Sn-catalyzed synthesis of propylene carbonate from propylene glycol and CO₂ under supercritical conditions. J Mol Catal A: Chem, 2005, 241: 233–237

13 Yasuda H, He L N, Sakakura T. Efficient synthesis of cyclic carbonate from carbon dioxide catalyzed by polyoxometalate: remarkable effects of metal substitution. J Catal, 2005, 233: 119–122

14 Yasuda H, He L N, Sakakura T. Cyclic carbonate synthesis from supercritical carbon dioxide and epoxide over lanthanide oxychloride. J Catal, 2002, 209: 547–550

15 Zhao Y, He L N, Zhaung Y Y, Wang J Q. Dimethyl carbonate synthesis via transterification catalyzed by quaternary ammonium salts functionalized chitosan. Chin Chem Lett, 2008, 19: 286–290

16 Tomishige K, Yasuda H, Yoshida Y, Nurunnabi M, Li B, Kunimori K. Catalytic performance and properties of ceria based catalysts for cyclic carbonate synthesis from glycol and carbon dioxide. Green Chem, 2004, 6: 206–214

17 Parkin G. Synthetic analogues relevant to the structure and function of Zinc enzymes. Chem Rev, 2004, 104: 699–768

18 Pacheco M A, Marshall C L. Review of dimethyl carbonate (DMC) manufacture and its characteristics as a fuel additive. Energy Fuels, 1991, 11: 2–29

19 AurelioL, Brownlee R T C, Hughus A B. Synthetic preparation of N-methyl-a-amino acids. Chem Rev, 2004, 104: 5823–5846