Synthesis of N,N-dimethylformamide by heterogeneous catalytic hydrogenation of supercritical carbon dioxide

Abstract

Publisher Summary This chapter discusses the synthesis of N,N -dimethylformamide (dmf) by the heterogeneous catalytic hydrogenation of supercritical carbon dioxide (scCO 2 ). The chapter focuses on a heterogeneous catalytic route for the synthesis of dmf from CO 2 , H 2 , and dimethylamine (dma) under supercritical conditions, employing sol–gel derived hybrid materials as catalysts. Highly active and stable catalysts can be produced by the incorporation of specially tailored silylether complexes within a porous silica network, thus providing access to the catalytically active centers. The highest turnover numbers achieved with these catalysts are more than three orders of magnitude higher than that reported so far for heterogeneous catalyzed dmf synthesis. The fixed complexes are usually more stable against oxygen and water than their free analogs. The chapter also illustrates the gelation process for silica modified with RuCl 2 {PPh 2 (CH 2 ) 2 Si(OEt) 3 } 3.