Selenium-Catalyzed Oxidative Carbonylation of Aniline and Alcohols to N-Phenylcarbamates

Abstract

A facile one-pot, phosgene-free synthesis of N-phenylcarbamates is demonstrated. Catalyzed by selenium, oxidative carbonylation of aniline with alcohols in the presence of carbon monoxide and oxygen affords the corresponding N-phenylcarbamates, mostly in fair to good yields. Selenium can be easily recovered because of its phase-transfer catalysis function.

Keywords:

• Aniline
• N-phenylcarbamates
• oxidative carbonylation
• selenium

ACKNOWLEDGMENTS

We sincerely acknowledge the financial supports from the Program for Innovative Research Team in University of Henan Province, China (2008IRTSTHN002) and the Education Department of Henan Province, China (2009B150013).

Notes

^a Reaction conditions: aniline, 5 mmol; ethanol, 50 mmol; selenium, 0.25 mmol; triethylamine, 10 mmol; CO, 1.6 MPa; O₂, 0.4 MPa; time, 6 h.

^b Based on aniline.

^c Isolated yield.

^a Reaction conditions: aniline, 5 mmol; ethanol, 50 mmol; selenium, 0.25 mmol; triethylamine, 10 mmol; CO, 1.6 MPa; O₂, 0.4 MPa; temperature, 180 °C.

^b Based on aniline.

^c Isolated yield.

^a Reaction conditions: aniline, 5 mmol; ethanol, 50 mmol; selenium, 0.25 mmol; triethylamine, 10 mmol; temperature, 180 °C; time, 6 h.

^b Based on aniline.

^c Isolated yield.

^a Reaction conditions: aniline, 5 mmol; selenium, 0.25 mmol; triethylamine, 10 mmol; CO, 1.6 MPa; O₂, 0.4 MPa; temperature, 180 °C; time, 6 h.

^b Based on aniline.

^c Isolated yield.

^a Reaction conditions: aniline, 5 mmol; ethanol, 50 mmol; selenium, 0.25 mmol; CO, 1.6 MPa; O₂, 0.4 MPa; temperature, 180 °C; time, 6 h.

^b Based on aniline.

^c Isolated yield.

^a Reaction conditions: aniline, 5 mmol; ethanol, 50 mmol; triethylamine, 10 mmol; CO, 1.6 MPa; O₂, 0.4 MPa; temperature, 180 °C; time, 6 h.

^b Based on aniline.

^c Isolated yield.

^a Reaction conditions: aniline, 5 mmol; alcohol, 50 mmol; selenium, 0.25 mmol; triethylamine, 10 mmol; CO, 1.6 MPa; O₂, 0.4 MPa; temperature, 180 °C; time, 6 h.

^b Isolated yield.