CuSe2/CeO2 as a novel heterogeneous catalyst for reductive carbonylation of nitroarenes for generating urethanes

Tran, Anh Vy; Nguyen, Thanh Tung; Lee, Hye Jin; Bae, Se Won; Baek, Jayeon; Kim, Hoon Sik; Kim, Yong Jin

doi:10.1016/j.apcata.2019.117245

Cited by 10 publications

(6 citation statements)

References 46 publications

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“…Throughout our study on the reductive carbonylation of NB over different catalyst combinations consisting of Se-based and other metal halides to prepare MPC, we found that not only Cu II Se 2 , which has been already found by our research group as an active and novel heterogeneous catalyst [46], but also Fe II Se 2 is found to be far more active than Cu II Se 2 species. Like the case of Cu II Se 2 , the ferrous diselenide (FeSe 2 ) is also generated during the carbonylation reaction using the catalyst system consisting of FeCl 3 and SeO 2 , but its activity was enhanced with the co-presence of pyridine.…”

Section: Introductionmentioning

confidence: 54%

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An Escape from Noble Metals for Generating Urethanes via Reductive Carbonylation of Nitroarenes over FeSe2/γ-Al2O3 †

Tran

Nguyen

et al. 2020

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The reaction of FeCl3, SeO2, and Pyridine (Py) in the presence of methanol (MeOH) under CO pressure generates a black precipitate, which has been confirmed as ferric di-selenide, FeSe2 through different structure characterization methods. Furthermore, impregnation of 5 wt% of FeSe2 onto γ-Al2O3 exhibits better catalytic performance than FeSe2 due to the highly dispersed and smaller particle sizes ca. 200–300 nm. The reductive carbonylation of nitrobenzene (NB) was investigated over FeSe2/γ-Al2O3 as a heterogeneous catalyst, delivering an excellent yield and high selectivity of methyl-N-phenyl carbamate (MPC). Moreover, a set of reactions was performed with variation in the reaction time, temperature, and pressure to investigate the effects of these factors. In particular, FeSe2/γ-Al2O3 is highly stable and can be recycled for up to five cycles without significant loss in catalytic performance. A mechanistic study was also conducted on this low-cost catalyst system, especially proposing a crucial role of FeSe2 (μ-CO) active species.

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Section: Introductionmentioning

confidence: 54%

“…However, it shows poorer activity in terms of both conversion and yield (Entry 3). A reported catalyst, CuSe 2 /CeO 2 was also tested at the same conditions; however, it gives lower yield (63.5% yield of MPC at 68% conversion of NB) than that of FeSe 2 (Entry 9) [46]. S2 and S6).…”

Section: Characterization Of Active Species and Its Supported Systemmentioning

confidence: 99%

An Escape from Noble Metals for Generating Urethanes via Reductive Carbonylation of Nitroarenes over FeSe2/γ-Al2O3 †

Tran

Nguyen

et al. 2020

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“…Recently, Tran et al reported a CuSe 2 /CeO 2 as a novel heterogeneous catalyst for the reductive carbonylation of NB. 47 This catalytic system showed >99% conversion with 96.4% MPC yield using an NB/CuSe 2 molar ratio of 44 under 8.3 MPa of CO at 160 °C in 4 h. In 2020, the same group reported a FeSe 2 system supported by γ-Al 2 O 3 as a heterogeneous catalyst revealing an improved TON of 85. 48 Although the recyclability was studied, a limited MPC was generated.…”

Section: ■ Introductionmentioning

confidence: 92%

“…Despite the high catalytic activity of homogeneous catalysts, their recovery and recycling are a major concern for industrial applications. For effective separation of the homogeneous catalysts, various heterogeneous catalysts for the reductive carbonylation of nitroarenes have been developed by employing selenium, metal selenides of Fe and Cu supported on ceria and γ-Al 2 O 3 , and supported Rh, Ru, and Pd complexes. − Unfortunately, the reactivity of these heterogeneous catalytic systems is lower relative to that of homogeneous Pd-based catalysts. For instance, Cenini et al attempted the use of Pd/Al 2 O 3 and Rh/Al 2 O 3 as heterogeneous catalytic systems for the reductive carbonylation of nitrobenzene (NB) .…”

Section: Introductionmentioning

confidence: 99%

“…However, the high reactivity of these catalytic systems is associated with the in situ formation of homogeneous catalysts via metal leaching from the support under catalytic conditions, rendering the catalytic systems nonrecyclable. Recently, Tran et al reported a CuSe 2 /CeO 2 as a novel heterogeneous catalyst for the reductive carbonylation of NB . This catalytic system showed >99% conversion with 96.4% MPC yield using an NB/CuSe 2 molar ratio of 44 under 8.3 MPa of CO at 160 °C in 4 h. In 2020, the same group reported a FeSe 2 system supported by γ-Al 2 O 3 as a heterogeneous catalyst revealing an improved TON of 85 .…”

Section: Introductionmentioning

confidence: 99%

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Reductive Carbonylation of Nitroarenes Using a Heterogenized Phen-Pd Catalyst

et al. 2022

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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 phencontaining 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 AlCl 3 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.

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Montmorillonite K30 Supported Tungstophosphoric Acid as an Efficient Catalyst for Condensation Reaction of Methyl N-phenylcarbamate for Generating Diurethane

et al. 2021

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CuSe2/CeO2 as a novel heterogeneous catalyst for reductive carbonylation of nitroarenes for generating urethanes

Cited by 10 publications

References 46 publications

An Escape from Noble Metals for Generating Urethanes via Reductive Carbonylation of Nitroarenes over FeSe2/γ-Al2O3 †

An Escape from Noble Metals for Generating Urethanes via Reductive Carbonylation of Nitroarenes over FeSe2/γ-Al2O3 †

Reductive Carbonylation of Nitroarenes Using a Heterogenized Phen-Pd Catalyst

Montmorillonite K30 Supported Tungstophosphoric Acid as an Efficient Catalyst for Condensation Reaction of Methyl N-phenylcarbamate for Generating Diurethane

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