Understanding the Origin of Maleic Anhydride Selectivity during the Oxidative Scission of Levulinic Acid

Zhu, Ran; Chatzidimitriou, Anargyros; Liu, Bowei; Kerwood, Deborah J.; Bond, Jesse Q.

doi:10.1021/acscatal.9b04289

Cited by 16 publications

(21 citation statements)

References 67 publications

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“…General analysis of the oxidation process of 5-(hydroxymethyl) furfural (1). Compounds: 5-(hydroxymethyl)furfural (1), 5-methylenefuran-2(5H)-one (protoanemonin) (2), maleic acid (4), acetic acid (5), maleic anhydride (11), malonic acid (6), succinic acid (8), malic acid (9), and glycolic acid (10). acid could be transferred from the aqueous phase of hydrogen peroxide to the organic phase of chlorinated solvent, improving the interaction with the substrates in the same phase.…”

Section: Self-catalysed Oxidation Process: Generation Of Formic Acid mentioning

confidence: 99%

“…Monitoring of the oxidation reaction of 5-(hydroxymethyl)furfural (1) by 1 H NMR analysis. [a] Time (h) [b] 70 30 6 5 5 --4 ----4 [b] 100 60 -7 9 --11 ----8 [b] 100 22 -14 6 4 12 16 ----24 [c] 100 --1 -22 -1 30 21 7 13 [a] Reaction conditions: 5-(hydroxymethyl)furfural 1 2, 5-(hydroxymethyl)furan-2-ol (7), formic acid (FA), (Z)-5-hydroxy-4-oxopent-2-enoic acid (3), maleic acid (4), maleic anhydride (11), acetic acid (5), malonic acid (6), succinic acid (8), malic acid (9), and glycolic acid (10).…”

Section: Self-catalysed Oxidation Process: Generation Of Formic Acid mentioning

confidence: 99%

“…[19] In consequence, the resulting crude was purified by flash column chromatography to afford the monomer protoanemonin (2) and its dimer anemonin in 48% and 14% yield, respectively, with an overall yield of 62%. In addition, maleic anhydride (11) was obtained in 32% yield (Figures 4 and S8).…”

Section: Self-catalysed Oxidation Process: Generation Of Formic Acid mentioning

confidence: 99%

“…1) by 1 H NMR analysis. [a] Time 7), formic acid (FA), (Z)-5-hydroxy-4-oxopent-2-enoic acid (3), maleic acid (4), maleic anhydride (11), acetic acid (5), malonic acid (6), succinic acid (8), malic acid ( 9), and glycolic acid (10).…”

Section: Self-catalysed Oxidation Process: Generation Of Formic Acid ...mentioning

confidence: 99%

“…It is notable to emphasize that there are few reports on the transformation of biomass into γ-alkylidenebutenolides. Very recently, Zhu et al [11] reported the VO x /γÀ Al 2 O 3 -catalyzed transformation of the levulinic acid into maleic anhydride at high temperature using an atmosphere of oxygen and helium through the intermediate γ-alkylidenebutenolide (protoanemonin), whose formation explaining the high selectivity of the methyl scission during levulinic acid oxidation. Neverthelesses, to the best of our knowledge, there is only one report of 5-(hydroxymethyl)furfural (1) transformation into protoanemonin (2).…”

Section: Introductionmentioning

confidence: 99%

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Obtaining Protoanemonin through Selective Oxidation of D‐Fructose and 5‐(Hydroxymethyl)furfural in a Self‐catalysed Reaction

et al. 2020

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Although different ways of converting 5-(hydroxymethyl)furfural (1) to various substrates with high value have been sought, few transformations have obtained building blocks that can be very useful in the area of fine chemistry. Herein, we report the synthesis of protoanemonin (5-methylenefuran-2(5H)-one) from D-fructose via compound (1), a versatile γ-alkylidenebutenolide, using an efficient selfcatalysed process with formic acid, with high reaction performance and selectivity (up to 94% yield and 98% conversion from (1), while 28% yield from D-fructose). This efficient and simple operational process involved a two-phase aqueous-organic system between chlorinated solvents (CH x Cl y) and hydrogen peroxide as the initial oxidizing agent. The reaction presents a key cleavage in the 5-hydroxymethyl moiety of (1), due to the Baeyer-Villiger oxidation (BVO) process that generates formic acid in situ. Ultimately, DFF and HMF were successfully obtained in 80% and 98% yield, respectively, starting from D-fructose and using Preyssler heteropolyacids as Brønsted acid catalysts under an atmosphere of oxygen in the absence of hydrogen peroxide.

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Section: Self-catalysed Oxidation Process: Generation Of Formic Acid mentioning

confidence: 99%

Section: Self-catalysed Oxidation Process: Generation Of Formic Acid mentioning

confidence: 99%

Section: Self-catalysed Oxidation Process: Generation Of Formic Acid mentioning

confidence: 99%

Section: Self-catalysed Oxidation Process: Generation Of Formic Acid ...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Obtaining Protoanemonin through Selective Oxidation of D‐Fructose and 5‐(Hydroxymethyl)furfural in a Self‐catalysed Reaction

et al. 2020

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Oxidative Cleavage of C−C Bonds in Non‐aromatic Oxygenates with Molecular Oxygen for Synthesis of Carboxylic Acids

Nakagawa,

Yabushita,

Tomishige

2023

Asian J Org Chem

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Oxidative carbon‐carbon cleavage reactions of non‐aromatic oxygenates such as vicinal diols are reviewed. In comparison with aromatic oxygenates where the benzyl positions are easily oxidized, non‐aromatic alcohols are difficult to be oxidized. The use of excess base in combination with metal catalysts is a typical approach, and the oxidations of 1,2‐cyclohexanediol and dihydroxylated derivatives of oleic acid have been reported with good yields of (di)carboxylate. Oxidation under acidic conditions typically uses vanadium as a key component of catalyst. Vanadium alone is active in oxidation of hydroxyketones and not effective in oxidation of saturated alcohols and polyols. Oxidation of sugars to formic acid is catalyzed by vanadium. For the oxidation of vicinal diols, the combination of platinum and vanadium is effective. There are some recently‐discovered systems for carbon‐carbon dissociation reactions of 1,2‐difunctionalized compounds, such as 2‐methoxycyclohexanone oxidation to adipic acid with polyoxometalate catalysts. On the other hand, the progress of research in the oxidation of cyclohexanone to adipic acid, which is an important industrial process, is less rapid, and we commented on the situation.

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Potassium Acetate/18‐Crown‐6 Pair: Robust and Versatile Catalyst for Synthesis of Polyols from Ring‐Opening Copolymerization of Epoxides and Cyclic Anhydrides^†

et al. 2022

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Comprehensive Summary Efficient synthesis of polyester polyols with tunable molecular weight and microstructures from cyclic anhydride/epoxide mixtures by taking advantage of chain transfer reaction remains a great challenge, because most of the catalysts exhibit poor tolerance to chain transfer agent (CTA). In this contribution, we demonstrated that potassium acetate (KOAc) and 18‐crown‐6 (18‐C‐6) combination has great potential in the synthesis of diverse polyester polyols with controllable molecular weight and high‐end group fidelity. Compared with KOAc, KOAc/18‐C‐6 pair could induce a much faster chain transfer between the active and dormant chains, and thus produce polyester polyols with narrow and monomodal distribution. In addition, polyester polyols could be efficiently prepared in laboratory by using commercially available cyclic anhydride without further purification (containing about 2% diacid residual as CTA) with an extremely low catalyst loading ([catalyst pair] : [anhydride] : [epoxide] = 1 : 50000 : 250000, [catalyst pair] = 0.0004 mol%). KOAc/18‐C‐6 could also promote the self‐switchable copolymerization of cyclic anhydride/epoxide/cyclic ester mixtures. Ring‐ opening copolymerization of cyclic ester was initiated automatically after the full conversion of cyclic anhydride, finally producing polyester polyols with ABA‐type block structure.

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Understanding the Origin of Maleic Anhydride Selectivity during the Oxidative Scission of Levulinic Acid

Cited by 16 publications

References 67 publications

Obtaining Protoanemonin through Selective Oxidation of D‐Fructose and 5‐(Hydroxymethyl)furfural in a Self‐catalysed Reaction

Obtaining Protoanemonin through Selective Oxidation of D‐Fructose and 5‐(Hydroxymethyl)furfural in a Self‐catalysed Reaction

Oxidative Cleavage of C−C Bonds in Non‐aromatic Oxygenates with Molecular Oxygen for Synthesis of Carboxylic Acids

Potassium Acetate/18‐Crown‐6 Pair: Robust and Versatile Catalyst for Synthesis of Polyols from Ring‐Opening Copolymerization of Epoxides and Cyclic Anhydrides^†

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Understanding the Origin of Maleic Anhydride Selectivity during the Oxidative Scission of Levulinic Acid

Cited by 16 publications

References 67 publications

Obtaining Protoanemonin through Selective Oxidation of D‐Fructose and 5‐(Hydroxymethyl)furfural in a Self‐catalysed Reaction

Obtaining Protoanemonin through Selective Oxidation of D‐Fructose and 5‐(Hydroxymethyl)furfural in a Self‐catalysed Reaction

Oxidative Cleavage of C−C Bonds in Non‐aromatic Oxygenates with Molecular Oxygen for Synthesis of Carboxylic Acids

Potassium Acetate/18‐Crown‐6 Pair: Robust and Versatile Catalyst for Synthesis of Polyols from Ring‐Opening Copolymerization of Epoxides and Cyclic Anhydrides†

Contact Info

Product

Resources

About

Potassium Acetate/18‐Crown‐6 Pair: Robust and Versatile Catalyst for Synthesis of Polyols from Ring‐Opening Copolymerization of Epoxides and Cyclic Anhydrides^†