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Pure Appl. Chem., 2012, Vol. 84, No. 3, pp. 461-471

Published online 2011-10-04

Environmentally benign and effective syntheses of N-substituted carbamates via alcoholysis of disubstituted ureas over TiO2/SiO2 catalyst*

Liguo Wang1,2, Jianpeng Shang1,2, Shimin Liu1,2, Lequan Liu1, Shiguo Zhang1 and Youquan Deng1*

1 Centre for Green Chemistry and Catalysis, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
2 Graduate University of Chinese Academy of Sciences, Beijing 100039, China

Abstract: Catalytic syntheses of cyclohexyl carbamates via alcoholysis of dicyclohexyl urea (DCU), which can be synthesized from CO2 and amines, were first investigated with low-molecular-weight alcohols, i.e., methanol, ethanol, butan-1-ol. TiO2/SiO2 catalyst was prepared by wet impregnation method using tetrabutyl titanate as titanium source. The catalyst was characterized by inductively coupled plasma/atomic emission spectroscopy (ICP/AES), N2 adsorption, X-ray diffraction (XRD), field emission/scanning electron microscopy (FE/SEM), transmission electron microscopy TEM), and NH3/temperature-programmed desorption (TPD) in detail. TiO2/SiO2 with 5 wt % loadings and calcination at 600 °C exhibited better catalytic activity, and excellent yields of >95 % with 98 % selectivities for desired carbamates were achieved. Accordingly, the strong acidity was considered to be responsible for its superior activity. Moreover, the catalytic activity can essentially be preserved during the recycling tests. The scope was also expanded to synthesize other alkyl or aryl carbamates via alcoholysis of the corresponding disubstituted ureas, and 94 % yields with 96 % selectivities can be achieved. It provided a good candidate for the organic carbamates syntheses via a phosgene/halogen-free and effective route.
*Pure Appl. Chem. 84, 411–860 (2012). A collection of invited papers for the IUPAC project 2008-016-1-300 “Chlorine-free Synthesis for Green Chemistry”.