5602-96-0Relevant articles and documents
Reductive Carbonylation of Nitroarenes Using a Heterogenized Phen-Pd Catalyst
Padmanaban, Sudakar,Ganesan, Vinothkumar,Yoon, Sungho,Lee, Yunho
, p. 1552 - 1561 (2022/01/27)
The reductive carbonylation of nitroarenes in the presence of MeOH and CO(g) is one of the interesting alternative routes without utilizing toxic phosgene and corrosive HCl generation for the synthesis of industrially useful carbamate compounds that serve as important intermediates for polyurethane production. Since homogeneous palladium catalysts supported by phen (phen = 1,10-phenanthroline) are known to be effective for this catalysis, the heterogenized Pd catalyst was developed using the phen-containing solid support. In this study, we report the synthesis of a phen-based heterogeneous Pd catalyst, Pd@phen-POP, which involves the solvent knitting of a phen scaffold via the Lewis-acid-catalyzed Friedel-Crafts reaction using dichloromethane as a source for linker in the presence of AlCl3 as a catalyst. The resulting solid material has been thoroughly characterized by various physical methods revealing high porosity and surface area. Similar to the homogeneous pallidum catalyst, this heterogeneous catalyst shows efficient reductive carbonylation of various nitroarenes. The catalytic reaction using nitrobenzene as a model compound presents a high turnover number (TON = 530) and a reasonable turnover frequency (TOF = 45 h-1), with a high selectivity (92%) for the carbamate formation. According to the recycling study, the heterogeneous catalyst is recyclable and retains ～90% of the original reactivity in each cycle.
Atomically Dispersed Copper on N-Doped Carbon Nanosheets for Electrocatalytic Synthesis of Carbamates from CO2 as a C1 Source
Li, Shi-Ming,Shi, Yi,Zhang, Jing-Jie,Wang, Ying,Wang, Huan,Lu, Jia-Xing
, p. 2050 - 2055 (2021/03/24)
The synthesis of carbamates by electrocatalytic reduction of CO2 is an effective method to realize the utilization of CO2 resources. The development of high-performance electrocatalysts to complete this process more efficiently is of great significance to sustainable development. Owing to their unique structural characteristics, single-atom catalysts are expected to promote the reaction process more efficiently. In this study, an atomically dispersed Cu species on N-doped carbon nanosheet composite material (Cu?N?C) was prepared by metal-organic framework derivatization. Compared with traditional Cu bulk electrodes, the Cu?N?C material has better catalytic performance for the synthesis of methyl N-phenylcarbamate; and the optimized yield reached 71 % at room temperature and normal pressure. The Cu?N?C material has good stability that the catalytic performance does not decrease after repeated use for 10 times. In addition, the Cu?N?C material has good applicability to this catalytic system, and a variety of amines can be smoothly converted into corresponding carbamates.
METHOD FOR PRODUCING CARBAMATE
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Paragraph 0014-0024, (2021/08/13)
PROBLEM TO BE SOLVED: To provide a method that can produce carbamate with high yield and high selectivity, and excellent economical efficiency, using more different kinds of amines. SOLUTION: A method for producing carbamate has a reaction step where, in the presence of calcium carbide and potassium carbonate, a reaction is induced among amine, methanol, and carbon dioxide. The reaction step is preferably performed at a temperature of 165-180°C. The reaction step is preferably performed at a carbon dioxide pressure of 3-5 MPa. The reaction step is preferably performed using an acetonitrile solvent. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2021,JPOandINPIT
