Synthesis of Benzaldehyde and Benzoic Acid by Selective Oxidation of Benzyl Alcohol with Iron(III) Tosylate and Hydrogen Peroxide: A Solvent-Controlled Reaction

Zhao, Yang; Yu, Chao; Wu, Shutian; Zhang, Wenli; Xue, Weilan; Zeng, Zuoxiang

doi:10.1007/s10562-018-2515-0

Cited by 28 publications

(11 citation statements)

References 32 publications

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“…Consequently, there is growing interest in the application of benign oxidants, such as molecular oxygen and air, through which high yields of benzaldehyde can be achieved, although typically the use of elevated reaction temperatures, in the range of 100 °C, is required. − By comparison, the use of commercial hydrogen peroxide (H 2 O 2 ) as an oxidant has been shown to allow significantly lower reaction temperatures to be utilized. With a range of precious- − and nonprecious-metal − catalysts having been studied, the catalytic generation of oxygen-based radical species is widely reported to be a key step in the oxidation mechanism, with the proton abstraction of the alcohol moiety (PhCH 2 O H ) being crucial in the formation of the aldehyde. , Nevertheless, a number of drawbacks associated with the use of commercial H 2 O 2 exist, namely those associated with the anthraquinone (AO) process, the means by which the vast majority (∼95%) of H 2 O 2 is produced on an industrial scale. Although highly efficient, the AO process is only economically viable when it is operated at a large scale, necessitating the centralization of production.…”

Section: Introductionmentioning

confidence: 99%

“…With a range of precious- 11−13 and nonpreciousmetal 14−18 catalysts having been studied, the catalytic generation of oxygen-based radical species is widely reported to be a key step in the oxidation mechanism, with the proton abstraction of the alcohol moiety (PhCH 2 OH) being crucial in the formation of the aldehyde. 18,19 Nevertheless, a number of drawbacks associated with the use of commercial H 2 O 2 exist, namely those associated with the anthraquinone (AO) process, the means by which the vast majority (∼95%) of H 2 O 2 is produced on an industrial scale. Although highly efficient, the AO process is only economically viable when it is operated at a large scale, necessitating the centralization of production.…”

Section: ■ Introductionmentioning

confidence: 99%

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Enhanced Selective Oxidation of Benzyl Alcohol via In Situ H₂O₂ Production over Supported Pd-Based Catalysts

et al. 2021

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Bimetallic Pd-Fe catalysts supported on TiO 2 are shown to be highly effective toward the selective oxidation of benzyl alcohol to benzaldehyde via the in situ production of H 2 O 2 from molecular H 2 and O 2 , under conditions where no reaction is observed with molecular O 2 alone. The rate of benzyl alcohol oxidation observed over supported Pd-Fe nanoparticles is significantly higher than those of either Pd-Au or Pd-only analogues. This enhanced activity can be attributed to the bifunctionality of the Pd-Fe catalyst to both synthesize H 2 O 2 and catalyze the production of oxygen-based radical specie,s as indicated by an electron paramagnetic resonance analysis. Further studies also reveal the noninnocent nature of the solvent, resulting in the propagation of radical generation pathways.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Enhanced Selective Oxidation of Benzyl Alcohol via In Situ H₂O₂ Production over Supported Pd-Based Catalysts

et al. 2021

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“…Therefore, the construction of green and highly active heterogeneous catalysts for the solvent‐free aerobic oxidation of benzyl alcohol is highly demanded. Recently, tremendous efforts have been made to study noble‐metal heterogeneous catalysts, such as Pt‐ and Pd‐based catalysts, owing to their satisfactory catalytic activity . Nevertheless, taking into account the exorbitant price and finite reserves of noble metals, non‐noble‐metal heterogeneous catalysts have broader application prospects in the catalytic field.…”

Section: Introductionmentioning

confidence: 99%

Holey Lamellar High‐Entropy Oxide as an Ultra‐High‐Activity Heterogeneous Catalyst for Solvent‐free Aerobic Oxidation of Benzyl Alcohol

et al. 2020

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The development of noble-metal-free heterogeneous catalysts is promising for selective oxidation of aromatic alcohols;h owever,t he relatively lowc onversion of non-noble metal catalysts under solvent-free atmospheric conditions hinders their industrial application. Now,aholey lamellar high entropyoxide (HEO) Co 0.2 Ni 0.2 Cu 0.2 Mg 0.2 Zn 0.2 Omaterial with mesoporous structure is prepared by an anchoring and merging process.The HEO has ultra-high catalytic activity for the solvent-free aerobic oxidation of benzyl alcohol. Up to 98 %conversion can be achieved in only 2h,toour knowledge, the highest conversion of benzyl alcohol by oxidation to date. By regulating the catalytic reaction parameters,benzoicacid or benzaldehyde can be selectively optimizedasthe main product. Analytical characterizations and calculations provide adeeper insight into the catalysis mechanism, revealing abundant oxygen vacancies and holey lamellar framework contribute to the ultra-high catalytic activity.

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“…The catalytic performance of 1 was also compared with some recent literature reports (Table 4) [50][51][52][53]. It is clear from Table 4 that complex 1 exhibits a good catalytic efficiency (a maximum yield of 91.3% was achieved in 1 h) in comparison to the reported ones.…”

Section: Methodsmentioning

confidence: 88%

Cu(II) and Fe(III) Complexes Derived from N-Acetylpyrazine-2-Carbohydrazide as Efficient Catalysts Towards Neat Microwave Assisted Oxidation of Alcohols

et al. 2019

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The mononuclear Cu(II) complex [Cu((kNN O-HL)(H 2 O) 2 ] (1) was synthesized using N-acetylpyrazine-2-carbohydrazide (H 2 L) and characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray crystallography. Two Fe(III) complexes derived from the same ligand viz, mononuclear [Fe((kNN O-HL)Cl 2 ] (2) and the binuclear [Fe(kNN O-HL)Cl(µ-OMe)] 2 (3) (synthesized as reported earlier), were also used in this study. The catalytic activity of these three complexes (1-3) was examined towards the oxidation of alcohols using tert-butyl hydroperoxide (TBHP) as oxidising agent under solvent-free microwave irradiation conditions. Primary and secondary benzyl alcohols (benzyl alcohol and 1-phenylethanol), and secondary aliphatic alcohols (cyclohexanol) were used as model substrates for this study. A comparison of their catalytic efficiency was performed. Complex 1 exhibited the highest activity in the presence of TEMPO as promoter for the oxidation of 1-phenylethanol with a maximum yield of 91.3% of acetophenone. Catalysts 2019, 9, 1053 2 of 15 catalytic reactions [3-9,29-40]. Although many catalysts have been developed to overcome ecological drawbacks, namely those using cheap and abundant metals, like copper and iron, metal catalytic systems operating under sustainable conditions are still challenging. Considering all the above mentioned points herein we present the synthesis of a new mononuclear Cu(II) complex, [Cu((kNN O-HL)(H 2 O) 2 ] (1), derived from the N-acetylpyrazine-2-carbohydrazide (H 2 L) ligand. Two Fe(III) complexes, the mononuclear [Fe((kNN O-HL)Cl 2 ] (2) and the binuclear [Fe(kNN O-HL)Cl(µ-OMe)] 2 (3), have also been synthesized using the same ligand as reported earlier [41]. The three complexes (1-3) were screened as catalytic precursors to assess their catalytic performances in the oxidation of alcohols. In the present investigation, we chose primary or secondary benzyl alcohols (benzyl alcohol, 1-phenyl alcohol) and secondary aliphatic alcohols (cyclohexanol) as model substrates and tert-butyl hydroperoxide (TBHP) as oxidising agent under microwave irradiation. MW irradiation acts as an alternative technique due to its simplicity and energy saving characteristics [6], usually leading to higher product yields and selectivities. In this investigation, the best catalytic conditions were optimized by comparing several cofactors like temperature, reaction time, influence of the presence of additives, etc. Results and Discussion Synthesis and CharacterizationsThe pro-ligand N-acetylpyrazine-2-carbohydrazide (H 2 L) was used to synthesize the mononuclear Cu(II) complex [Cu(kNN O-HL)(H 2 O) 2 ] (1) (Scheme 1). The Fe(III) complexes [Fe(kNN O-HL)Cl 2 ] (2) and [Fe(kNN O-HL)Cl(µ-OMe)] 2 (3) derived from the same pro-ligand were obtained by a method from the literature [41]. As previously observed, in this case, the N-acetylpyrazine-2-carbohydrazide also acts as a mononegative tridentate N,N,O donor (HL − ) towards the metal centre [41] and shows different coordination behaviour from a relate...

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Synthesis of Benzaldehyde and Benzoic Acid by Selective Oxidation of Benzyl Alcohol with Iron(III) Tosylate and Hydrogen Peroxide: A Solvent-Controlled Reaction

Cited by 28 publications

References 32 publications

Enhanced Selective Oxidation of Benzyl Alcohol via In Situ H₂O₂ Production over Supported Pd-Based Catalysts

Enhanced Selective Oxidation of Benzyl Alcohol via In Situ H₂O₂ Production over Supported Pd-Based Catalysts

Holey Lamellar High‐Entropy Oxide as an Ultra‐High‐Activity Heterogeneous Catalyst for Solvent‐free Aerobic Oxidation of Benzyl Alcohol

Cu(II) and Fe(III) Complexes Derived from N-Acetylpyrazine-2-Carbohydrazide as Efficient Catalysts Towards Neat Microwave Assisted Oxidation of Alcohols

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Synthesis of Benzaldehyde and Benzoic Acid by Selective Oxidation of Benzyl Alcohol with Iron(III) Tosylate and Hydrogen Peroxide: A Solvent-Controlled Reaction

Cited by 28 publications

References 32 publications

Enhanced Selective Oxidation of Benzyl Alcohol via In Situ H2O2 Production over Supported Pd-Based Catalysts

Enhanced Selective Oxidation of Benzyl Alcohol via In Situ H2O2 Production over Supported Pd-Based Catalysts

Holey Lamellar High‐Entropy Oxide as an Ultra‐High‐Activity Heterogeneous Catalyst for Solvent‐free Aerobic Oxidation of Benzyl Alcohol

Cu(II) and Fe(III) Complexes Derived from N-Acetylpyrazine-2-Carbohydrazide as Efficient Catalysts Towards Neat Microwave Assisted Oxidation of Alcohols

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Enhanced Selective Oxidation of Benzyl Alcohol via In Situ H₂O₂ Production over Supported Pd-Based Catalysts

Enhanced Selective Oxidation of Benzyl Alcohol via In Situ H₂O₂ Production over Supported Pd-Based Catalysts