Direct Conversion of Low-Concentration CO2 into N-Aryl and N-Alkyl Carbamic Acid Esters Using Tetramethyl Orthosilicate with Amidines as a CO2 Capture Agent and a Catalyst.

Herein, we report the direct conversion of low-concentration CO2 (15 vol %), equivalent to the CO2 concentration in the exhaust gas from a thermal power station, into carbamic acid esters (CAEs), which are precursors for pharmaceuticals, agrochemicals, and isocyanates. The reaction was performed using Si(OMe)4 as a nonmetallic regenerable reagent and 1,8-diazabicyclo[5.4.0]undec-7-ene as a CO2 capture agent and catalyst. This reaction system does not require the addition of metal complex catalysts or metal salt additives and is therefore simpler than our previously reported reaction system involving Ti(OR)4 and a Zn(II) catalyst. A variety of N-aryl, N-alkyl, and bis CAEs (precursors of polyurethane raw materials) were obtained in moderate to high yields (45-77% for 6 examples, 84-89% for 7 examples). In addition, bis CAEs were successfully synthesized from simulated exhaust gas containing impurities such as SO2, NO2, and CO or on a gram scale. We believe that this method can eliminate the use of toxic phosgene as the raw material for isocyanate production and mitigate CO2 emissions.