“…Acyclic ureas and organic carbonates, both of which are typically synthesized with phosgene or CO as the carbonyl source, are also used as alternative carbonyl agents. The direct synthesis of 2-imidazolidinone from CO 2 and EDA is one of the promising and environmentally benign methods because the byproduct is only water, and various methods have been reported such as non-catalytic systems − and catalytic systems including homogeneous catalyst systems, − modified ionic liquids, − and heterogeneous catalyst systems. − However, in these reaction systems, pure and high-pressure CO 2 is required for obtaining the high yield of the target product based on EDA, which means that additional processes, equipment, and energy costs such as CO 2 desorption, purification, and compression are necessary. , Therefore, the direct transformation of captured CO 2 is a simple and desirable process.…”
CeO 2 acted as an effective and reusable heterogeneous catalyst for the direct synthesis of 2-imidazolidinone from ethylenediamine carbamate (EDA-CA) without further addition of CO 2 in the reaction system. 2-Propanol was the best solvent among the solvents tested from the viewpoint of selectivity to 2-imidazolidinone, and the use of an adequate amount of 2-propanol provided high conversion and selectivity for the reaction. This positive effect of 2-propanol on the catalytic reaction can be explained by the solubility of EDA-CA in 2-propanol under the reaction conditions and no formation of solvent-derived byproducts. This catalytic system using the combination of the CeO 2 catalyst and the 2-propanol solvent provided 2-imidazolidinone in up to 83% yield on the EDA-CA basis at 413 K under Ar. The reaction conducted under Ar showed a higher reaction rate than that with pressured CO 2 , which clearly demonstrated the advantage of the catalytic system operated at low CO 2 pressure or even without CO 2 .
“…Acyclic ureas and organic carbonates, both of which are typically synthesized with phosgene or CO as the carbonyl source, are also used as alternative carbonyl agents. The direct synthesis of 2-imidazolidinone from CO 2 and EDA is one of the promising and environmentally benign methods because the byproduct is only water, and various methods have been reported such as non-catalytic systems − and catalytic systems including homogeneous catalyst systems, − modified ionic liquids, − and heterogeneous catalyst systems. − However, in these reaction systems, pure and high-pressure CO 2 is required for obtaining the high yield of the target product based on EDA, which means that additional processes, equipment, and energy costs such as CO 2 desorption, purification, and compression are necessary. , Therefore, the direct transformation of captured CO 2 is a simple and desirable process.…”
CeO 2 acted as an effective and reusable heterogeneous catalyst for the direct synthesis of 2-imidazolidinone from ethylenediamine carbamate (EDA-CA) without further addition of CO 2 in the reaction system. 2-Propanol was the best solvent among the solvents tested from the viewpoint of selectivity to 2-imidazolidinone, and the use of an adequate amount of 2-propanol provided high conversion and selectivity for the reaction. This positive effect of 2-propanol on the catalytic reaction can be explained by the solubility of EDA-CA in 2-propanol under the reaction conditions and no formation of solvent-derived byproducts. This catalytic system using the combination of the CeO 2 catalyst and the 2-propanol solvent provided 2-imidazolidinone in up to 83% yield on the EDA-CA basis at 413 K under Ar. The reaction conducted under Ar showed a higher reaction rate than that with pressured CO 2 , which clearly demonstrated the advantage of the catalytic system operated at low CO 2 pressure or even without CO 2 .
“…This therefore inspired us to try and understand why. Based on literatures, 22,23 the reduction temperature for monometallic Ni is around 380°C, whereas the reduction temperature of Sn oxides to Sn 0 occurs at temperatures around 600°C or higher. As shown in the TPR profiles in Figure 3A, Ni‐Sn/Al 2 O 3 ‐C sample gives results which are broadly consistent with monometallic systems.…”
Modification of Ni/Al2O3 catalysts with Sn is appealing for tuning catalyst activity and selectivity for hydrogenation reactions. However, a strong interaction between the Al2O3 and Sn ions can lead to problems when a traditional impregnation strategy is employed. For example, tin aluminate complexes can form and uneven distribution of the metals can occur. In this work, a support coordination induction strategy is developed, in which the use of a rod‐shaped Al2O3 with a high number penta‐coordinated Al3+ surface species prepared from a rotating liquid film reactor was used. The unsaturated Al3+ coordination sites on this support induce the formation of a stable and uniform Ni‐Sn intermetallic phase without the appearance of either monometallic Ni or SnO2 particles. This uniform Ni‐Sn intermetallic phase was then shown to be responsible for enhanced activity, selectivity, and stability for alkyne hydrogenation relative to samples which lacked the same level of Ni‐Sn uniformity.
“…diamine (NNDMEDA), and 1,3-diaminopropane (1,3-PDA), respectively, with pressurized CO 2 in good yields (entries 1, 2, and 4-8 in Table 12). [92,93,96,99] However, as stated above, these reports lack the detailed data in kinetic region, making the comparison of activity of these catalysts with that of other reported catalysts inappropriate. Two different supported catalysts were employed for synthesizing cyclic urea compound(s) in both kinetic and equilibrium regions.…”
Carbon dioxide (CO2) utilization as a carbonyl source is an attractive and promising approach to yielding value‐added organic urea derivatives, which are currently produced with toxic reagents such as phosgene and carbon monoxide, along with the contribution to mitigating global warming. However, the direct intermolecular reaction between CO2 and amines into organic urea derivatives has thermodynamic limitations, and such obstacles need to be considered well in order to establish efficient reaction systems. Herein, this review describes the thermodynamic aspects for producing several organic urea compounds, viz., N,N’‐dibutylurea, N,N’‐di(tert‐butyl)urea, 2‐imidazolidinone (ethylene urea), N,N’‐dimethyl‐2‐imidazolidinone, tetrahydro‐2‐pyrimidinone (propylene urea), and N,N’‐diphenylurea, based on the results of computational calculations. Besides, a variety of the state‐of‐the‐art reaction systems with/without catalyst for synthesizing such organic urea compounds operated under pressurized CO2 have been summarized and discussed to make not only advantages but also disadvantages clear. We have also overviewed the very recently reported approaches that employ alkylcarbamic acids as substrates and instead does not require external CO2. The thermodynamic and catalytic insights garnered here could be a fruitful guideline for fairly assessing each reaction system and further improving the efficiency of CO2 utilization as a carbonyl source.
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