A simple and highly efficient method was developed for the transformation of furfural (a biomass derived aldehyde) to furfurylamine by reductive amination using an aqueous solution of ammonia and molecular hydrogen as an amine source and a reducing agent, respectively. By choosing a suitable catalyst, such as Rh/Al 2 O 3 , and reaction conditions, a very high selectivity of furfurylamine (∼92%) can be achieved within the reaction time of 2 h at 80°C. A detailed analysis of the reaction system sheds some light on the reaction pathway and provides an understanding about each elementary step. The reaction was believed to proceed via an imine pathway although no such intermediate was detected because of the highly reactive nature. Optimization of different reaction parameters such as hydrogen pressure, temperature and substrate/ammonia mole ratio is shown to be critical to achieve high selectivity of furfurylamine. Timedependent reaction profiles suggested that a Schiff base type intermediate was in the detectable range, which offers indirect evidence of the formation of imine. Competitive hydrogenation and amination of an aldehyde group were strongly dictated by the nature of the metal used. The studied protocol represents an environmentally benign process for amine synthesis, which can be effectively extended to the other aldehydes also. The studied catalyst could be recycled successfully without any significant loss of catalytic activity. † Electronic supplementary information (ESI) available. See Reaction conditions: catalyst = 0.002 g, substrate = 0.2 g, substrate/ammonia (mole ratio) = 0.03, temperature = 80°C, reaction time = 2 h, P H 2 = 2 MPa. a Reaction time = 4 h. b Reaction time = 5 h.
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The synthesis of propylene carbonate from propylene oxide and carbon dioxide under supercritical conditions in the presence of 1-octyl-3-methylimidazolium tetrafluoroborate was achieved in nearly 100% yield and 100% selectivity within 5 minutes, whose TOF value is 77 times larger than those so far reported.
The hydrogenation of HMF has been conducted in a neutral aqueous medium. Without any additive, HMF was hydrogenated to 2,5-bis-(hydroxymethyl)furan (BHMF) with complete conversion and selectivity (98.9%) using Pt/MCM-41 as catalyst. A very low temperature of 35°C and 0.8 MPa of hydrogen pressure was used to accomplish the highest selectivity of BHMF within a reaction time of 2 h. Different reaction parameters such as reaction time, hydrogen pressure and the amount of water was optimized to achieve the highest catalytic activity. In particular, the presence or absence of water and the amount of water played an important role to determine the conversion and product distribution of the reaction. For instance, in the absence of water or a large excess of water, the selectivity of BHMF was decreased. In addition, instead of water the influence of three different groups of organic solvent were also explored to obtain BHMF under the studied reaction conditions. It has been observed that the studied organic solvents strongly influenced the catalytic performance, such as solvents with a negative δ value, which followed a clear trend with the substrate conversion, whereas no impact was observed for solvents with a positive δ value. Catalyst recycling experiments revealed that the catalyst could be recycled several times without any significant loss of catalytic activity.
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