Copper(I) Chloride/Kieselguhr: a Versatile Catalyst for Oxidation of Alkyl Halides and Alkyl Tosylates to the Carbonyl Compounds

Hashemi, Mohammed M.; Beni, Yousef A.

doi:10.1039/a807641c

Cited by 41 publications

(9 citation statements)

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“…The oxidation of benzylic chlorides to the corresponding aldehydes has been reported using different systems, namely CuCl/Kieselguhr/O 2 [ 47 ], 2-dimethylamino- N , N -dimethylaniline N -oxide [ 48 ], 3,6-bis(triphenylphosphonium)cyclohexene peroxodisulfate [ 49 ], NaIO 4 -DMF [ 50 ], H 5 IO 6 in [C 12 mim][FeCl 4 ] ionic liquid [ 51 ], TEMPO (cat)/KNO 2 (cat)/O 2 [ 52 ], NMO/KI (cat) in [emim]Cl ionic liquid, MW [ 53 ] and molybdate-based catalyst/H 2 O 2 [ 54 ]. Based on that, we started this study by screening several oxidants (1.5 equiv.)…”

Section: Resultsmentioning

confidence: 99%

Oxidation of 5-Chloromethylfurfural (CMF) to 2,5-Diformylfuran (DFF)

et al. 2017

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2,5-Diformylfuran (DFF) is an important biorenewable building block, namely for the manufacture of new polymers that may replace existing materials derived from limited fossil fuel resources. The current reported methods for the preparation of DFF are mainly derived from the oxidation of 5-hydroxymethylfurfural (HMF) and, to a lesser extent, directly from fructose. 5-Chloromethylfurfural (CMF) has been considered an alternative to HMF as an intermediate building block due to its advantages regarding stability, polarity, and availability from glucose and cellulose. The only reported method for the transformation of CMF to DFF is restricted to the use of DMSO as the solvent and oxidant. We envisioned that the transformation could be performed using more attractive conditions. To that end, we explored the oxidation of CMF to DFF by screening several oxidants such as H2O2, oxone, and pyridine N-oxide (PNO); different heating methods, namely thermal and microwave irradiation (MWI); and also flow conditions. The combination of PNO (4 equiv.) and Cu(OTf)2 (0.5 equiv.) in acetonitrile was identified as the best system, which lead to the formation of DFF in 54% yield under MWI for 5 min at 160 °C. Consequently, a range of different heterogeneous copper catalysts were tested, which allowed for catalyst reuse. Similar results were also observed under flow conditions using copper immobilized on silica under thermal heating at 160 °C for a residence time of 2.7 min. Finally, HMF and 5,5′-oxybis(5-methylene-2-furaldehyde) (OBMF) were the only byproducts identified under the reaction conditions studied.

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Section: Resultsmentioning

confidence: 99%

Oxidation of 5-Chloromethylfurfural (CMF) to 2,5-Diformylfuran (DFF)

et al. 2017

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“…30 Moreover, kieselguhr is of special interest owing to its effectiveness in the retention of enzyme activity, 31 and its nice catalytic ability. 32,33 In this work, we incorporated HRP in the kieselguhr membrane. It was observed that HRP exhibits good direct electrochemical transfer reactions.…”

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confidence: 99%

Incorporation of Horseradish Peroxidase in a Kieselguhr Membrane and the Application to a Mediator-free Hydrogen Peroxide Sensor

et al. 2001

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Hydrogen peroxide (H2O2) is a product of many enzymecatalyzed redox reactions. 1 Therefore, the determination of H2O2 is of great importance in both biological and industrial fields. [2][3][4][5] Electrochemical techniques have long been considered for the determination of H2O2, in view of its simplicity, low-cost and real-time detection properties. 6,7 Nevertheless, H2O2 is not an ideal species to detect with an electrochemical biosensor, because the electrode kinetics is very slow at most electrode surfaces. 8,9 It therefore requires high overpotentials to drive the reaction at an electrode, which often leads to low sensitivity and unacceptable interferences. 10 Therefore, peroxidase is often employed, to lower the activation energy for the reduction of H2O2 and to catalyze its electrochemical reduction at electrode surfaces. [11][12][13][14][15][16] Horseradish peroxidase (HRP) is a widely used peroxidase, due to its reasonable stability, commercial availability and effectiveness towards the reduction of H2O2. 17,18 Many good HRP-based H2O2 sensors have been constructed. [19][20][21][22][23] However, the redox center of HRP is electrically insulated by its thick protein shell, thus hindering its direct electrical communication with electrodes. Therefore, redox mediators usually have to be employed to shuttle electrons between the heme site of HRP and the electrodes.Meanwhile, although the direct electroreduction of H2O2 in the presence of HRP was observed at purposely pretreated carbon electrode surfaces, direct (i.e., mediator-free) electron transfer between the electrode and HRP is rather slow. Thus, no direct electrochemistry of HRP is observable in such cases. [24][25][26] Consequently, it is less efficient in the bioelectrocatalytic reduction of H2O2 and the biosensors exhibit lower sensitivity than those sensors that employ redox mediators.Recent studies have shown that the electron-transfer reactivity of proteins could be effectively enhanced after the proteins were incorporated in some membranes. 27 For example, Ferri et al. entrapped HRP within a tributylmethyl phosphonium chloride (TBMPC) polymer bound anionic exchange resin.The heterogeneous electron-transfer rate of HRP was greatly promoted and a pair of redox peaks of HRP was observed, corresponding to Fe(III)/Fe(II) conversion. 28 Hence, it combines the specificity of an enzymatic reaction with facile interfacial electron transfer, which shows great promise in biosensing applications. 29 Kieselguhr is a kind of inorganic material with a porous structure, which is promising as an immobilization matrix because of its good mechanical, thermal and chemical stability. 30 Moreover, kieselguhr is of special interest owing to its effectiveness in the retention of enzyme activity, 31 and its nice catalytic ability. 32,33 In this work, we incorporated HRP in the kieselguhr membrane. It was observed that HRP exhibits good direct electrochemical transfer reactions. Furthermore, a mediator-free H2O2 sensor is accordingly constructed. ExperimentalHRP (EC 1.11...

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“…In course of our systematic study of the development of supported reagents and catalysts for the oxidation of organic compounds, [16][17][18][19][20][21][22][23][24] we have nearly presented preparation and use of 4-aminoperoxybenzoic acid supported on silica gel as a convenient procedure for the oxidation of benzylic methylene compounds to corresponding ketones, [21] and for selective oxidation of aryl ketones to a-diketones. [23] Now we report that 4-aminoperoxybenzoic acid supported on silica gel is an efficient and convenient oxidant for the oxidation of ketones to esters in high yields (Scheme 1).…”

Section: Resultsmentioning

confidence: 99%

Efficient Method for Oxidation of Ketones to Esters with 4-Aminoperoxybenzoic Acid Supported On Silica Gel

Ghazanfari

Hashemi

Shahidi

2008

Synthetic Communications

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Copper(I) Chloride/Kieselguhr: a Versatile Catalyst for Oxidation of Alkyl Halides and Alkyl Tosylates to the Carbonyl Compounds

Abstract: Copper(I) Chloride adsorbed on Kieselguhr in the presence of oxygen catalyses oxidation of alkyl halides and alkyl tosylates to the aldehydes and ketones in high yields.

Cited by 41 publications

References 10 publications

Oxidation of 5-Chloromethylfurfural (CMF) to 2,5-Diformylfuran (DFF)

Oxidation of 5-Chloromethylfurfural (CMF) to 2,5-Diformylfuran (DFF)

Incorporation of Horseradish Peroxidase in a Kieselguhr Membrane and the Application to a Mediator-free Hydrogen Peroxide Sensor

Efficient Method for Oxidation of Ketones to Esters with 4-Aminoperoxybenzoic Acid Supported On Silica Gel

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