CeO2-catalyzed transformation of various amine carbamates into organic urea derivatives in corresponding amine solvent

Peng, Jie; Yabushita, Mizuho; Li, Yingai; Fujii, Ryotaro; Tamura, Masazumi; Nakagawa, Yoshinao; Tomishige, Keiichi

doi:10.1016/j.apcata.2022.118747

Cited by 16 publications

(48 citation statements)

References 65 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We note that the diffusion of reactant molecules did not matter in the current study since the granule size of CeO 2 (i.e., 1.0−1.7 and 1.7−2.4 mm) did not affect the reaction results at all at both the relatively low and high conversion levels (see Figure S9 and Table S7); therefore, in all the following tests, we employed the CeO 2 catalysts with their granule size of 1.0−1.7 mm. Besides, consistent with the case using a batch-type reactor, 29 the blank reactions operated at 363 and 383 K without catalyst did not convert EDA-CA (Table S8). A lack of such reaction in the liquid phase offers the ease of the assessment and understanding of the following reaction results.…”

Section: Ceo 2 -Catalyzed Conversion Of Eda-ca Into Eu In a Fixed-bed...supporting

confidence: 86%

“…Catalytic synthesis of EU from EDA-CA in the EDA solvent with a batch reactor was performed by following the same procedure as mentioned in our previous study. 29 Typically, 0.34 g of CeO 2 , 0.29 g of EDA-CA, and 1.64 g of EDA were sealed into a 190 mL autoclave with a stirring bar. The reactor was purged with 1 MPa Ar twice and pressurized to 1 MPa with Ar at room temperature.…”

Section: Methodsmentioning

confidence: 99%

“…S11. As a control, we also investigated the same reaction over the anatase TiO 2 (101) surface (Figure S14), which was previously found to be almost inactive for the EU production from EDA-CA in an EDA solvent, 29 by the DFT calculations. Similar to the case of CeO 2 described above, the bridged carbamate species is formed over the TiO 2 surface by transferring a proton to the surface.…”

Section: Kinetic Study and Dft Calculations For Investigation Of A Pl...mentioning

confidence: 99%

“…As demonstrated in Section 3.1, the flow reaction system enabled the selective production of EU from EDA-CA in the EDA solvent, while our previous batch reaction inevitably formed both EU and LU. 29 In this section, therefore, we aimed to scrutinize the origin of this difference in the product selectivity by kinetic study. Figure S16 and Table S14 show the time courses for the formation of LU from EU with or without the CeO 2 catalyst at the initial stage, recorded with a batch-type reactor.…”

Section: Kinetic Study For the Formation Of Lu: Insights Of Differenc...mentioning

confidence: 99%

“…We also reported the effective catalytic transformation of EDA-CA over CeO 2 in an EDA solvent under an Ar atmosphere in a batch reactor. 29 The EDA solvent retards the thermal decomposition of EDA-CA apparently completely. In this system, two urea derivatives, EU and N,N′bis(2-aminoethyl)urea (LU), were produced; for example, at 413 K for 16 h under Ar, the yields of EU and LU were 62 and 38%, respectively.…”

Section: Introductionmentioning

confidence: 98%

See 4 more Smart Citations

Continuous Flow Synthesis of 2-Imidazolidinone from Ethylenediamine Carbamate in Ethylenediamine Solvent over the CeO₂ Catalyst: Insights into Catalysis and Deactivation

et al. 2023

Self Cite

View full text Add to dashboard Cite

Synthesis of 2-imidazolidinone (EU) from ethylenediamine carbamate (EDA-CA), which was produced via chemical absorption of CO2 in ethylenediamine (EDA), with a fixed-bed flow reactor was performed using CeO2 and EDA as a heterogeneous catalyst and reaction solvent, respectively. In the previously reported batch system for the same reaction, the yield of EU was low (62%) due to its sequential reaction with EDA into N,N′-bis(2-aminoethyl)urea (LU) with 38% yield in the liquid phase under the optimized reaction conditions at 413 K. In stark contrast, the flow reaction enabled the highly selective and high-yielding production of EU (94% yield) under the optimized reaction conditions at 363 K. This difference in the selectivity of EU originated from the lower ratio of the amount of EDA to that of the CeO2 catalyst in the current flow reaction system compared to the previous batch system. The highly crystallized CeO2 surface bearing both acid and base sites was found to be responsible for its high catalytic performance. The combination of the kinetics, density functional theory calculations, and adsorption experiments demonstrated that EDA-CA is preferentially adsorbed onto the surface of CeO2 even in the presence of an excess amount of EDA, which is used as a solvent, to be activated and transformed into EU. The solid-state 13C magic angle spinning/cross polarization nuclear magnetic resonance spectroscopy revealed that the CeO2 catalyst was deactivated gradually in a long-term reaction operation due to the formation and deposition of polyurea-like organic compounds on the catalyst surface.

show abstract

Section: Ceo 2 -Catalyzed Conversion Of Eda-ca Into Eu In a Fixed-bed...supporting

confidence: 86%

Section: Methodsmentioning

confidence: 99%

Section: Kinetic Study and Dft Calculations For Investigation Of A Pl...mentioning

confidence: 99%

Section: Kinetic Study For the Formation Of Lu: Insights Of Differenc...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

See 3 more Smart Citations

Continuous Flow Synthesis of 2-Imidazolidinone from Ethylenediamine Carbamate in Ethylenediamine Solvent over the CeO₂ Catalyst: Insights into Catalysis and Deactivation

et al. 2023

Self Cite

View full text Add to dashboard Cite

show abstract

Thermodynamic and Catalytic Insights into Non‐Reductive Transformation of CO₂ with Amines into Organic Urea Derivatives

Yabushita,

Fujii,

Nakagawa

et al. 2024

ChemCatChem

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Comparative Study between 2‐Furonitrile and 2‐Cyanopyridine as Dehydrants in Direct Synthesis of Dialkyl Carbonates from CO₂ and Alcohols over Cerium Oxide Catalyst

Sun,

Li,

Yabushita

et al. 2023

ChemSusChem

Self Cite

View full text Add to dashboard Cite

The shift of equilibrium by removing water with nitrile dehydrants is crucial for CeO2‐catalyzed synthesis of dialkyl carbonates from CO2 and alcohols. Two nitriles – 2‐cyanopyridine and 2‐furonitrile – were previously found as effective dehydrants, yet their detailed comparison as well as exploration of potential of 2‐furonitrile remain insufficient. Herein, the performance of 2‐cyanopyridine and 2‐furonitrile was compared in the synthesis of various dialkyl carbonates. 2‐furonitrile was found to be superior to 2‐cyanopyridine in the synthesis of dialkyl carbonates from CO2 and bulky or long‐chain (≥C3) alcohols. Namely, the yield of diisopropyl carbonate (up to 50 %) achieved using CeO2 and 2‐furonitrile is comparable to or even higher than previously reported ones. Meanwhile, 2‐cyanopyridine acted as a better dehydrant than 2‐furonitrile in the synthesis of dimethyl carbonate and diethyl carbonate. The adsorption experiments and density functional theory calculations have indicated that the better performance of 2‐furonitrile compared to 2‐cyanopyridine in the synthesis of dialkyl carbonates from bulky or long‐chain alcohols is due to the weaker interaction of 2‐furonitrile with the CeO2 surface. Such weak interaction of 2‐furonitrile offers a larger reaction field on the catalyst surface for both CO2 and alcohols.

show abstract

CeO2-catalyzed transformation of various amine carbamates into organic urea derivatives in corresponding amine solvent

Cited by 16 publications

References 65 publications

Continuous Flow Synthesis of 2-Imidazolidinone from Ethylenediamine Carbamate in Ethylenediamine Solvent over the CeO₂ Catalyst: Insights into Catalysis and Deactivation

Continuous Flow Synthesis of 2-Imidazolidinone from Ethylenediamine Carbamate in Ethylenediamine Solvent over the CeO₂ Catalyst: Insights into Catalysis and Deactivation

Thermodynamic and Catalytic Insights into Non‐Reductive Transformation of CO₂ with Amines into Organic Urea Derivatives

Comparative Study between 2‐Furonitrile and 2‐Cyanopyridine as Dehydrants in Direct Synthesis of Dialkyl Carbonates from CO₂ and Alcohols over Cerium Oxide Catalyst

Contact Info

Product

Resources

About

CeO2-catalyzed transformation of various amine carbamates into organic urea derivatives in corresponding amine solvent

Cited by 16 publications

References 65 publications

Continuous Flow Synthesis of 2-Imidazolidinone from Ethylenediamine Carbamate in Ethylenediamine Solvent over the CeO2 Catalyst: Insights into Catalysis and Deactivation

Continuous Flow Synthesis of 2-Imidazolidinone from Ethylenediamine Carbamate in Ethylenediamine Solvent over the CeO2 Catalyst: Insights into Catalysis and Deactivation

Thermodynamic and Catalytic Insights into Non‐Reductive Transformation of CO2 with Amines into Organic Urea Derivatives

Comparative Study between 2‐Furonitrile and 2‐Cyanopyridine as Dehydrants in Direct Synthesis of Dialkyl Carbonates from CO2 and Alcohols over Cerium Oxide Catalyst

Contact Info

Product

Resources

About

Continuous Flow Synthesis of 2-Imidazolidinone from Ethylenediamine Carbamate in Ethylenediamine Solvent over the CeO₂ Catalyst: Insights into Catalysis and Deactivation

Continuous Flow Synthesis of 2-Imidazolidinone from Ethylenediamine Carbamate in Ethylenediamine Solvent over the CeO₂ Catalyst: Insights into Catalysis and Deactivation

Thermodynamic and Catalytic Insights into Non‐Reductive Transformation of CO₂ with Amines into Organic Urea Derivatives

Comparative Study between 2‐Furonitrile and 2‐Cyanopyridine as Dehydrants in Direct Synthesis of Dialkyl Carbonates from CO₂ and Alcohols over Cerium Oxide Catalyst