Epoxidation of allyl chloride with H2O2 catalyzed by three structurally related quaternary ammonium modified polyoxophosphotungstates

Zhao, Xiuxian; Sun, Junhua; Sun, Guoxin; You, Qidong; Jiang, Xuchuan; Cui, Yu

doi:10.1016/j.apcata.2020.117846

Cited by 10 publications

(4 citation statements)

References 53 publications

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“…Additionally, an alkyl quaternary ammonium salt was an excellent phase transfer catalyst which could significantly reduce the interfacial tension between the organic and the inorganic phases at the same time. , If the structure of the quaternary ammonium salt combined with heteropoly compounds can satisfy the insolubility in both the organic and the inorganic phases, it will be one of the excellent choices for α-olefin epoxidation catalysts.…”

Section: Introductionmentioning

confidence: 99%

Design of Organic–Inorganic Phase Transfer Hybrid Catalyst and Its Application in the Epoxidation of α-Olefins

Ju,

Zhang,

Guo

et al. 2024

Ind. Eng. Chem. Res.

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The catalytic epoxidation of α-olefin with long carbon chains has always been a challenge. Traditional homogeneous or heterogeneous catalysts showed poor performance toward the reaction. In this paper, layered organic−inorganic catalysts were prepared by the reaction of phosphotungstic acid and a Gemini quaternary ammonium salt, which could convert long α-olefin to epoxide with a selectivity of 85% in the absence of organic solvents. Combined with characterization results, it was confirmed that the catalyst was layered structure materials, which was supported by a quaternary ammonium salt chain, and the active molecules were distributed between the layered structures. The possible mechanism was also discussed preliminarily.

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Section: Introductionmentioning

confidence: 99%

Design of Organic–Inorganic Phase Transfer Hybrid Catalyst and Its Application in the Epoxidation of α-Olefins

Ju,

Zhang,

Guo

et al. 2024

Ind. Eng. Chem. Res.

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“…Keggin heteropolyanions (HPAs) of general formula [XM 12 O 40 ] n − (mainly M = Mo or W and X = P, Si, or Ge) are one of the most explored subsets of POMs in catalytic applications, particularly in the oxidation of organic substrates. − Much of the interest in these anions has emerged from their catalytic efficiency in oxidation reactions when combined with H 2 O 2 as an oxidant. Relevant examples involve homogeneous ,,− ,− and heterogeneous oxidations − catalyzed by Keggin HPAs. One of the most successful routes to prepare active Keggin-based oxidation catalysts lies in the preparation of organic–inorganic hybrid materials.…”

Section: Introductionmentioning

confidence: 99%

Formation, Reactivity, and Catalytic Behavior of a Keggin Polyoxometalate/Bipyridine Hybrid in the Epoxidation of Cyclooctene with H₂O₂

et al. 2023

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The present study further explores the behavior of polyoxometalate-based hybrid compounds as catalysts for liquidphase cyclooctene epoxidation with H 2 O 2 . Precisely, it unveils the nature of the relevant active species derived from the hybrid based on Keggin polyoxometalate (POM) and bipyridines (bpy) of formula (2,2′-Hbpy) 3 [PW 12 O 40 ] (1). Whereas (i) it is generally accepted that the catalytic oxidation of organic substrates by H 2 O 2 involving Keggin HPAs proceeds via an oxygen transfer route from a peroxo intermediate and (ii) the catalytically active peroxo species is commonly postulated to be the polyperoxotungstate {PO 4 [W(O)(O 2 ) 2 ] 4 } 3− complex (PW 4 ), we show that the studied epoxidation reaction seems to be more sophisticated than commonly reported. During the catalytic epoxidation, 1 underwent a partial transformation into two oxidized species, 2 and 3. Compound 3 corresponding to 2,2′-bipyridinium oxodiperoxotungstate of formula [WO(O 2 ) 2 (2,2′-bpy)] was shown to be the main species responsible for the selective epoxidation of cyclooctene since 2 (in which the POM is associated with a protonated mono-Noxide derivative of 2,2′-bpy of formula (2,2′-HbpyO) 3 [PW 12 O 40 ]) exhibited no activity. The structures of 1, 2, and 3 were solved by single-crystal X-ray diffraction and were independently synthesized. The speciation of 1 was monitored under catalytic conditions by 1 H and 1 H DOSY NMR spectroscopies, where the formation in situ of 2 and 3 was revealed. A reaction mechanism is proposed that highlights the pivotal, yet often underestimated, role of H 2 O 2 in the reached catalytic performances. The active species responsible for the oxygen transfer to cyclooctene is a hydroperoxide intermediate species that is formed by the interaction between the anionic structure of the catalyst and H 2 O 2 . The latter operates as a "conservative agent" whose presence in the catalytic system is required to prevent the catalysts from deactivating irreversibly.

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“…Various catalysts such as metal complexes, − silicates, − molecular sieve, − and poly(oxometalates) − have been reported for the H 2 O 2 -based catalytic epoxidation. Homogeneous catalysts exhibit high catalytic activity but have difficulties in recycling and reuse . Poly(oxometalates), as heterogeneous catalysts, are easy to separate from the reaction system, which have drawn great attention as catalysts for the epoxidation reaction with the dual characteristics of oxidizing ability and strong acidity.…”

Section: Introductionmentioning

confidence: 99%

“…Homogeneous catalysts exhibit high catalytic activity but have difficulties in recycling and reuse. 29 Poly(oxometalates), as heterogeneous catalysts, are easy to separate from the reaction system, which have drawn great attention as catalysts for the epoxidation reaction with the dual characteristics of oxidizing ability and strong acidity. Among the reported poly-(oxometalates), the phosphotungstate catalyst showed high H 2 O 2 utilization efficiency and high conversion of olefins.…”

Section: Introductionmentioning

confidence: 99%

Kinetic Studies and Reaction Network in the Epoxidation of Styrene Catalyzed by the Temperature-Controlled Phase-Transfer Catalyst [(C₁₈H₃₇)₂(CH₃)₂N]₇[PW₁₁O₃₉]

Chen

Wang

et al. 2022

Ind. Eng. Chem. Res.

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The olefin epoxidation reaction is of great interest in recent years since epoxide is considered an important intermediate for a wide application range. H2O2-based catalytic epoxidation possesses the advantages of being cheap, green, and safe, which are quite advantageous in chemical technology. A phase-transfer catalyst, especially the phosphotungstate catalyst, has been applied in the epoxidation reaction with a high reaction rate and moderate reaction conditions. In this work, a phase-transfer catalyst, [(C18H37)2(CH3)2N]7[PW11O39], has been synthesized, and it showed high catalytic efficiency in styrene epoxidation. The influence of reaction time, temperature, oxidant concentration and amount, catalyst amount, and substrate concentration on the reaction performance was studied. A styrene conversion of 90.1% and selectivity of 90.6% could be achieved at 85 °C for 1 h with 3 equiv of H2O2 and 1.5 mol % catalyst. More importantly, kinetic models for the reaction network have been studied to optimize the reaction conditions and limit the side reactions.

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Epoxidation of allyl chloride with H2O2 catalyzed by three structurally related quaternary ammonium modified polyoxophosphotungstates

Cited by 10 publications

References 53 publications

Design of Organic–Inorganic Phase Transfer Hybrid Catalyst and Its Application in the Epoxidation of α-Olefins

Design of Organic–Inorganic Phase Transfer Hybrid Catalyst and Its Application in the Epoxidation of α-Olefins

Formation, Reactivity, and Catalytic Behavior of a Keggin Polyoxometalate/Bipyridine Hybrid in the Epoxidation of Cyclooctene with H₂O₂

Kinetic Studies and Reaction Network in the Epoxidation of Styrene Catalyzed by the Temperature-Controlled Phase-Transfer Catalyst [(C₁₈H₃₇)₂(CH₃)₂N]₇[PW₁₁O₃₉]

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Epoxidation of allyl chloride with H2O2 catalyzed by three structurally related quaternary ammonium modified polyoxophosphotungstates

Cited by 10 publications

References 53 publications

Design of Organic–Inorganic Phase Transfer Hybrid Catalyst and Its Application in the Epoxidation of α-Olefins

Design of Organic–Inorganic Phase Transfer Hybrid Catalyst and Its Application in the Epoxidation of α-Olefins

Formation, Reactivity, and Catalytic Behavior of a Keggin Polyoxometalate/Bipyridine Hybrid in the Epoxidation of Cyclooctene with H2O2

Kinetic Studies and Reaction Network in the Epoxidation of Styrene Catalyzed by the Temperature-Controlled Phase-Transfer Catalyst [(C18H37)2(CH3)2N]7[PW11O39]

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Formation, Reactivity, and Catalytic Behavior of a Keggin Polyoxometalate/Bipyridine Hybrid in the Epoxidation of Cyclooctene with H₂O₂

Kinetic Studies and Reaction Network in the Epoxidation of Styrene Catalyzed by the Temperature-Controlled Phase-Transfer Catalyst [(C₁₈H₃₇)₂(CH₃)₂N]₇[PW₁₁O₃₉]