Supercritical carbon dioxide dimethyl carbonate reaction

A potential green route to dimethyltin carbonate can be based on the reaction of methanol and carbon dioxide, catalyzed by dimethyltin dimethoxide. In supercritical CO2 as solvent, the dimethoxide reacts to give the monocarbonate, which at 180 °C and 300 atm pressure gives dimethyl carbonate, probably by an intramolecular rearrangement, with regeneration of the dimethoxide (Equation (139)).385,386... 

A fourth type of product, a carbamate RNHCOOR , can be obtained from primary or secondary amines, if these are treated with CO, O2, and an alcohol R OH in the presence of a catalyst. " Primary amines react with dimethyl carbonate in supercritical CO2 (see p. 414) to give a carbamate. " Carbamates can also be obtained from nitroso compounds, by treatment with CO, R OH, Pd(OAc)2, and Cu(OAc)2, " and from nitro compounds. " When allylic amines (R2C=CHRCHRNR 2) are treated with CO and a palladium-phosphine catalyst, the CO inserts to produce the p,y-unsa-turated amides (R2C=CHRCHRCONR 2) in good yields. " Ring-expanded lactams are obtained from cyclic amines via a similar reaction (see also, 16-22). Silyloxy carbamates (RNHC02SiR 3) can be prepared by the reaction of a primary amine with carbon dioxide and triethylamine, followed by reaction with triisopropylsilyl triflate and tetrabutylammonium fluoride. ... 

Elucidation of solvation characteristics of supercritical fluids is indispensable to their utilization as media for separation or reaction. One powerful method for elucidating chemical equilibrium and solvation in SCFs is voltammetry. However, voltammetric measurement in pure supercritical CO2 is extremely difficult because CO2 is nonpolar. Electrochemical processes in several polar SCFs including acetonitrile, ammonia, and sulfur dioxide, were investigated by Bard and coworkers in the late 1980s (61-65). Dombro et al. reported the electrochemical synthesis of dimethyl carbonate from carbon monoxide and methanol in super-... 

---