A modified mixed‐acid catalytic system for Beckmann rearrangement of cyclohexanone oxime

Du, Chencan; Zhang, Jisong; Li, Liantang; Wang, Kai; Luo, Guangsheng

doi:10.1002/aic.16603

Cited by 15 publications

(7 citation statements)

References 30 publications

(69 reference statements)

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“…In contrast, liquid-phase catalytic Beckmann rearrangement has become a topic of current interest because of its advantages such as mild reaction conditions, easy workup, and industrial practicability. As a consequence, different catalysts such as organic catalysts, , metal chlorides, − and ionic liquids, − have been investigated in this reaction. However, most of them suffer one or more shortcomings, such as expensive starting materials, harsh experimental conditions, complicated synthesis, and purification operations.…”

Section: Introductionmentioning

confidence: 99%

Reusable Deep Eutectic Solvents for Clean ε-Caprolactam Synthesis under Mild Conditions

Sun

Liu

Fang

et al. 2022

ACS Sustainable Chem. Eng.

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A deep eutectic solvent (DES) with adjustable Brønsted acidity was prepared easily by choline chloride (ChCl) and trifluoromethanesulfonic acid (TfOH). The obtained DES [ChCl][TfOH] 3 exhibited great stability and excellent catalytic performance in the Beckmann rearrangement reaction as solvent and catalyst. High cyclohexanone oxime (CHO) conversion (100%) and ε-caprolactam selectivity (98.8%) were obtained under mild conditions, such as DESs 0.03 mol, CHO 0.01 mol, 100 °C for 2 h. DES [ChCl][TfOH] 3 was easily prepared, recovered, and reused simply for seven runs without noticeable loss of catalytic performance. The free energy (ΔG) and activation energy (E a ) of the reaction were −32.8 and 39.82 kJ mol −1 , respectively. And, DFT results showed that the intermolecular hydrogen bond between ChCl and TfOH improved the thermal stability of DES (the six-membered ring structure formed containing Cl and N atoms) and provided a good sponge effect for the active hydrogen catalytic center required for the reaction (the hydrogen bond formed by Cl and hydroxyl). This process offered several advantages including good yields, short reaction times, and easy catalyst recoveries and makes the DES catalytic system a potentially practical procedure for Beckmann rearrangement.

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Section: Introductionmentioning

confidence: 99%

Reusable Deep Eutectic Solvents for Clean ε-Caprolactam Synthesis under Mild Conditions

Sun

Liu

Fang

et al. 2022

ACS Sustainable Chem. Eng.

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“…In this work, since a small amount of CB was dissolved in sulfuric acid, the reaction involved a homogeneous liquid system. Because the nitration reaction is rapid, it is necessary to ensure sufficient mixing performance, which is related to the flow rates of the two streams 25,26 . The concentration distribution of CB in the mixed solution was simulated by computational fluid dynamics (CFD).…”

Section: Resultsmentioning

confidence: 99%

Determination of the kinetics of chlorobenzene nitration using a homogeneously continuous microflow

Cui

Song

et al. 2022

AIChE Journal

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The nitration of chlorobenzene with concentrated mixed acids is a fast and highly exothermic process, which suffers from considerable mass transfer resistance and poor heat transfer rates. The reaction kinetics has not been thoroughly reported before. In this work, a continuous‐flow microreactor system and a homogeneous reaction condition were proposed to obtain accurate chlorobenzene nitration kinetics parameters at high mixed acid concentrations. A general model for predicting the observed reaction rate constants was established. With a new method for estimating the equilibria associated with HNO3 in aqueous sulfuric acid, the rate constants based on nitronium ion and activation energies were obtained. Compared with batch reactors, the continuous‐flow microreactor system allows for a sufficient heat transfer efficiency and accurate residence time control, making it possible to study the reaction performance more quickly and sensitively. This work may provide a reliable reference for the kinetic study of similar processes.

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“…Because the nitration reaction is rapid, it is necessary to ensure sufficient mixing performance, which is related to the flow rates of the two streams. 24,25 The concentration distribution of CB in the mixed solution was simulated by computational fluid dynamics (CFD). The flow rates of the solution 1 and solution 2 were 0.4 mL/min and 0.9 mL/min, respectively, as shown in Figure S3 .…”

Section: Mixing Performance In the Microreactor Systemmentioning

confidence: 99%

Determination of the kinetics of chlorobenzene nitration using a homogeneously continuous microflow

Deng

et al. 2021

Preprint

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The nitration of chlorobenzene with concentrated mixed acids is a fast and highly exothermic process, which suffers from considerable mass transfer resistance and poor heat transfer rates. The reaction kinetics has not been thoroughly reported before. In this work, a continuous-flow microreactor system and a homogeneous reaction condition were proposed to obtain accurate chlorobenzene nitration kinetics data at high mixed acid concentrations. A general model for predicting the observed reaction rate constants was established. With a new method for estimating the equilibria associated with HNO3 in aqueous sulfuric acid, the rate constants based on nitronium ion and activation energies were obtained. Compared with batch reactors, the continuous-flow microreactor system allows for a sufficient heat transfer efficiency and accurate residence time control, making it possible to study the reaction performance more quickly and sensitively. This work may provide a reliable reference for the kinetic study of similar processes.

show abstract

A modified mixed‐acid catalytic system for Beckmann rearrangement of cyclohexanone oxime

Cited by 15 publications

References 30 publications

Reusable Deep Eutectic Solvents for Clean ε-Caprolactam Synthesis under Mild Conditions

Reusable Deep Eutectic Solvents for Clean ε-Caprolactam Synthesis under Mild Conditions

Determination of the kinetics of chlorobenzene nitration using a homogeneously continuous microflow

Determination of the kinetics of chlorobenzene nitration using a homogeneously continuous microflow

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