<i>N</i>‐Hydroxyphthalimide (NHPI) Promoted Aerobic Baeyer‐Villiger Oxidation in the Presence of Aldehydes

Wang, Lingyao; Wang, Yongtao; Du, Renfeng; Dao, Rina; Yuan, Haoran; Cheng, Liang; Yao, Jia; Li, Haoran

doi:10.1002/cctc.201801165

Cited by 19 publications

(23 citation statements)

References 56 publications

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“…In this figure, we learned that both CHOL and CHONE selectivities in the reaction system decreased while ϵ‐CL selectivity increased with the conversion of cyclohexane. These results indicated that ϵ‐CL was easily produced from the in‐situ formed CHONE by Baeyer‐Villiger oxidation in the reaction system …”

Section: Methodsmentioning

confidence: 80%

Selective One‐Step Aerobic Oxidation of Cyclohexane to ϵ‐Caprolactone Mediated by N‐Hydroxyphthalimide (NHPI)

Wang

Zhang

et al. 2019

ChemCatChem

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dichloroethane (20 mL) were placed into a three-necked round bottom flask (50 mL) equipped with an oxygen balloon and a magnetic stir bar. The mixture was stirred at 40°C for 24 hours. The reaction was monitored by GC instrument. The conversion was calculated on the basis of the peak area ratio of cyclohexane against the internal standard, biphenyl. The product yields were calculated on the basis of the peak area ratio of cyclohexanol, cyclohexanone, and ɛ-caprolactone against the internal standard. Control experiment was conducted in the absence of NHPI.General EPR experiments in different solvents. To a 25 mL Schlenk tube with a magnetic stirrer was added 0.2122 g (2 mmol) of benzaldehyde, 0.0163 g (0.1 mmol) of NHPI and 10 mL of 1,2dichloroethane (DCE). The mixture was stirred at 40°C for 30 min at atmospheric pressure. Thereafter, EPR was measured immediately. The EPR spectra of the reaction solution were obtained by using a computer controlled X-band (9.5 GHz) EPR spectrometer (Bruker A300). The solvent DCE was replaced by CH 3 CN and Toluene. Control experiments were conducted in the absence of benzaldehyde in different solvents. General EPR experiments with NHPI.To a 50 mL three-necked glass flask fitted with a water cooled reflux condenser, a magnetic stir bar and an oxygen balloon was added 0.4245 g (4 mmol) of benzaldehyde and 20 mL of 1,2-dichloroethane (DCE). The mixture was stirred at 40°C for 30 min at atmospheric pressure. Then 0.0326 g (0.2 mmol) of NHPI was added into the mixture and the mixture was stirred for another 30 min. The EPR spectra of the reaction solution (Figure 1(c), green) were obtained by using a computer controlled X-band (9.5GHz) EPR spectrometer (Bruker A300). Thereafter, EPR was measured immediately upon addition of 0.168 g (2 mmol) of cyclohexane into the reaction system (blue). The reaction was continued for 2 h before measuring EPR (red).

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Section: Methodsmentioning

confidence: 80%

Selective One‐Step Aerobic Oxidation of Cyclohexane to ϵ‐Caprolactone Mediated by N‐Hydroxyphthalimide (NHPI)

Wang

Zhang

et al. 2019

ChemCatChem

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“…The autoxidation reactions of alkene 4a (Scheme A,B) appear to proceed through a radical mechanism characteristic of triplet oxygen, as evidenced by the complete inhibition of the reaction in the presence of butylated hydroxytoluene (BHT, Scheme C) . Although the addition of molecular oxygen to alkenes generally involves the excited singlet state of oxygen, autoxidation reactions of alkenes and alkynes involving triplet oxygen have also been observed. − Many of these reactions involve geometrically strained compounds, − including the autoxidations of aryl-substituted alkylidenecyclopropanes. , …”

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Strain-Promoted Oxidation of Methylenecyclopropane Derivatives using N-Hydroxyphthalimide and Molecular Oxygen in the Dark

Anderson

Woerpel

2020

Org. Lett.

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“…Figure 6 In-situ IR spectra of the cyclohexanone oxidation catalyzed by NHPI (inset is the effect of NHPI on the benzaldehyde conversion) [42] (color online).…”

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“…a) 条件: 环己酮, 2.0 mmol; 1,2-二氯乙烷, 20 mL; 温度, 313 K; NHPI, 0.02 mol; 醛, 4.0 mmol. b) 转化率与选择性是基于气相内标法(a)[42] …”

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Research progress on the aerobic synthesis of ε-caprolactam

Yuan¹,

Wang²,

Du³

et al. 2020

Sci. Sin.-Chim

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Lactones are widely applied in the fields of pharmacy and polymer. Among them, ε-caprolactam is the monomer of biodegradable poly-caprolactone and also usually used as the modifier of polyester, which almost owns the capacity of 100,000 ton/year. Its demand would grow rapidly with the increasingly strict requirement in environmental protection. In this review, the progress on the aerobic synthesis of caprolactone and the further study on the oxidant modification and new path were mainly discussed. Our group focused on the one-pot transformation of cyclohexanone K/A oil and cyclohexane to ε-caprolactam, respectively, which would be more efficient and environmentally friendly methods and own potential prospect of the industrial application.

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N‐Hydroxyphthalimide (NHPI) Promoted Aerobic Baeyer‐Villiger Oxidation in the Presence of Aldehydes

Cited by 19 publications

References 56 publications

Selective One‐Step Aerobic Oxidation of Cyclohexane to ϵ‐Caprolactone Mediated by N‐Hydroxyphthalimide (NHPI)

Selective One‐Step Aerobic Oxidation of Cyclohexane to ϵ‐Caprolactone Mediated by N‐Hydroxyphthalimide (NHPI)

Strain-Promoted Oxidation of Methylenecyclopropane Derivatives using N-Hydroxyphthalimide and Molecular Oxygen in the Dark

Research progress on the aerobic synthesis of ε-caprolactam

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N‐Hydroxyphthalimide (NHPI) Promoted Aerobic Baeyer‐Villiger Oxidation in the Presence of Aldehydes

Cited by 19 publications

References 56 publications

Selective One‐Step Aerobic Oxidation of Cyclohexane to ϵ‐Caprolactone Mediated by N‐Hydroxyphthalimide (NHPI)

Selective One‐Step Aerobic Oxidation of Cyclohexane to ϵ‐Caprolactone Mediated by N‐Hydroxyphthalimide (NHPI)

Strain-Promoted Oxidation of Methylenecyclopropane Derivatives using N-Hydroxyphthalimide and Molecular Oxygen in the Dark

Research progress on the aerobic synthesis of &epsilon;-caprolactam

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Research progress on the aerobic synthesis of ε-caprolactam