The first synthesis of a cyclic carbonate from a ketal in SC-CO2

Abstract In this paper the synthesis of a cyclic organic carbonate by a halogen-free route is described. The ketal formed from cyclohexanone and 1,2-ethanediol was reacted with carbon dioxide, either in SC-CO2 or in organic solvents under CO2 pressure. Transition-metal complexes with functionalized fluorinated di-ketone ligands were used as catalyst. The synthetic methodology based on SC-CO2 is effective for the synthesis of ethylene carbonate. The use of methanol as co-solvent in SC-CO2 prevents the formation of the ethylene carbonate and only the alcoholysis of the ketal is observed. In organic solvents, no reaction takes place.

[1]  M. Aresta,et al.  Selective carbomethoxylation of aromatic diamines. with mixed carbonic acid diesters in the presence of phosphorous acids , 1999 .

[2]  M. Aresta,et al.  Iron(0) oxidation by hydrogen chloride in tetrahydrofuran: a simple way to anhydrous iron(II) chloride , 1977 .

[3]  N. Isaacs,et al.  High pressure routes to dimethyl carbonate from supercritical carbon dioxide , 1999 .

[4]  E. Reverchon.  SUPERCRITICAL ANTISOLVENT PRECIPITATION OF MICRO- AND NANO-PARTICLES , 1999 .

[5]  Walter Leitner,et al.  Chemical synthesis using supercritical fluids , 1999 .

[6]  D. D. Perrin,et al.  Purification of laboratory chemicals , 1966 .

[7]  M. Aresta,et al.  Reaction of aromatic diamines with diphenylcarbonate catalyzed by phosphorous acids: a new clean synthetic route to mono- and dicarbamates , 1998 .

[8]  M. Aresta,et al.  Direct synthesis of organic carbonates by oxidative carboxylation of olefins catalyzed by metal oxides: developing green chemistry based on carbon dioxide , 2000 .

[9]  Michele Aresta,et al.  Carbon dioxide as building block for the synthesis of organic carbonates: Behavior of homogeneous and heterogeneous catalysts in the oxidative carboxylation of olefins , 2002 .

[10]  Takeshi Sako,et al.  Synthesis of dimethyl carbonate from carbon dioxide: catalysis and mechanism , 2000 .

[11]  †. Danielle Ballivet-Tkatchenko,et al.  Reactivity of Carbon Dioxide with n-Butyl(phenoxy)-, (alkoxy)-, and (oxo)stannanes: Insight into Dimethyl Carbonate Synthesis , 2000 .