Electrochemical and spectroscopic study of 2-iodobenzoic acid and 2-iodosobenzoic acid anodic oxidation in aqueous environment

Devadas, Balamurugan; Svoboda, Jan; Krupička, Martin; Bystroň, Tomáš

doi:10.1016/j.electacta.2020.136080

Cited by 13 publications

(10 citation statements)

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“…The values of diffusion coefficients of the investigated compounds in the CH 3 COOH−H 2 SO 4 media are of the order of 10 −10 m 2 s −1 , i. e. roughly one order of magnitude smaller compared to those observed for some of these compounds in aqueous environment [8] . The largest diffusion coefficient value of about 3×10 −10 m 2 s −1 was found for IB , which is the smallest molecule with lowest molecular mass among the selected group of compounds.…”

Section: Resultsmentioning

confidence: 78%

“…The practical applicability of this process is, however, limited by very low solubility of 2‐IBA in acidic aqueous environment (<1 mM). In the consecutive work, we have investigated this process in more detail and discovered that current efficiency of 2‐iodosylbenzoic acid synthesis (as well as 2‐IBA conversion) decreases dramatically when operating in alkaline system where 2‐IBA is present in the form of carboxylate [8] . In order to pursue anodic oxidation of of 2‐IBA to the corresponding iodosyl derivative, we turned our attention to nonaqueous solutions.…”

Section: Introductionmentioning

confidence: 99%

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Anodic Oxidation of Iodobenzene and Iodobenzoic Acids in Acetic Acid Environment – Electrochemical Investigation and Density Functional Theory Study

et al. 2021

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Kinetic and mechanistic aspects of an anodic oxidation of iodobenzene and its selected derivatives leading to the corresponding iodosyl compounds, were investigated in anhydrous acidic acetic acid environment using boron‐doped diamond electrode. The first electron removal leading to the formation of radical cation was identified as the rate determining step of the process. Oxidation potential values of the investigated compounds were rationalised by their solution phase ionisation energies (in conformation of the radical cations as products of the first electron removal), calculated by advanced DFT methods. Unexpectedly low oxidation potential of 2‐iodobenzoic acid and its functional derivatives compared to iodobenzene, 3‐iodo and 4‐iodobenzoic acids was explained by decreased electron density at iodine atom leading to planar 2‐iodobenzoic acid radical cation. This is connected with reordering of its frontier molecular orbitals compared to non‐planar neutral molecule.

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Section: Resultsmentioning

confidence: 78%

Section: Introductionmentioning

confidence: 99%

Anodic Oxidation of Iodobenzene and Iodobenzoic Acids in Acetic Acid Environment – Electrochemical Investigation and Density Functional Theory Study

et al. 2021

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“…In 2018 Bystron’s group reported the first electrochemical synthesis of organic iodine (V) compound, 2-iodoxybenzoic acid (IBX, 20 ), through anodic oxidation of 2-iodobenzoic acid (IBA) in a divided cell using a boron-doped diamond (BDD) electrode in 0.2 M H 2 SO 4 aqueous solution ( Bystron et al, 2018 ; Devadas et al, 2020 ) ( Scheme 1H ). This anodic oxidation process exhibited excellent selectivity and high current efficiency (>50%).…”

Section: Electrochemical Synthesis Of Hypervalent Iodine Reagentsmentioning

confidence: 99%

“…No undesired organic products were generated with O 2 as the only by-product. The aqueous environment was recognized as a crucial aspect of this anodic oxidation process because iodine (V) compounds could be electrochemically generated only in aqueous electrolyte solutions ( Devadas et al, 2020 ).…”

Section: Electrochemical Synthesis Of Hypervalent Iodine Reagentsmentioning

confidence: 99%

Recent Updates on Electrogenerated Hypervalent Iodine Derivatives and Their Applications as Mediators in Organic Electrosynthesis

2022

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With the renaissance of chemical electrosynthesis in the last decade, the electrochemistry of hypervalent iodine compounds has picked up the pace and achieved significant improvements. By employing traceless electrons instead of stoichiometric oxidants as the alternative clean “reagents”, many hypervalent iodine compounds were efficiently electro-synthesized via anodic oxidation methods and utilized as powerful redox mediators triggering valuable oxidative coupling reactions in a more sustainable way. This minireview gives an up-to-date overview of the recent advances during the past 3 years, encompassing enhanced electrosynthesis technologies, novel synthetic applications, and ideas for improving reaction sustainability.

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“…A primary hypothesis examined in the present work is that chemically versatile O-atom and group-transfer reagents based on Ar–I such as iodosobenzoic acid (IBA) or iodoxybenzoic acid (IBX) and their derivatives can be synthesized electrochemically using water as the O-atom source for potential use in O-atom transfer catalysis. There is little reported in terms of electrocatalysis or electrosynthesis of O-atom transfer reagents, except for a report of the electrochemical formation of iodoxybenzoic acid (IBX) from iodobenzoic acid precursor (PhICO 2 H) in aqueous solutions. , This stands in contrast to the extensive progress with the electrochemistry of hypervalent iodine as mediators in electrocatalytic reactions such as fluorination and other group-transfer reactions. − …”

Section: Introductionmentioning

confidence: 99%

Carbon-Electrode-Mediated Electrochemical Synthesis of Hypervalent Iodine Reagents Using Water as the O-Atom Source

Folkman

Finke

Galán‐Mascarós

et al. 2021

ACS Sustainable Chem. Eng.

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Photoelectrocatalytic water splitting is an important goal of modern chemistry that is hindered by the slow kinetics of anodic water oxidation. Additionally, the O2 byproduct of water oxidation catalysis is of little economic value. One way to increase the energy efficiency as well as economic feasibility of photoelectrocatalytic water splitting as an industrial process is to couple the oxidation of water to the formation of value-added, oxygenated products such as olefin epoxidation or other selective oxygenation or oxidation reactionsrather than the coupling of two O-atom equivalents to O2. However, attempts at direct olefin epoxidation at the same anode where water oxidation catalysis is happening suffer from competing one-electron oxidation or overoxidation of the olefin substrate. Hence, an O-atom-transfer mediator is needed. Hypervalent iodine reagents are known to perform olefin epoxidations via O-atom transfer, oxidation reactions, as well as a myriad of other group-transfer reactions. A drawback addressed in the following work is that the synthesis of hypervalent iodine reagents typically requires the use of a powerful oxidant such as IO4 – or KHSO5 with multiple steps and potentially explosive intermediates or side products. Herein, we report proof-of-principle electrochemical syntheses of a series of hypervalent iodine reagents, including: λ3-o-iodosobenzoic acid (IBA) in up to 58% isolated yield with a Faradaic efficiency 89%; the previously inaccessible λ3-ethyl 2-iodosobenzoate (IBA-ester) with ∼78% Faradaic efficiency; the well-known λ5-2-iodoxyphenyl tert-butyl sulfone (IBX-sulfone) with ∼51% Faradaic efficiency; and a mixture of λ3-2-iodosobenzene sulfonic acid (IBA-sulfonic acid) with λ5-2-iodoxybenzene sulfonic acid (IBX-sulfonic acid) with an overall Faradaic efficiency of >78%. Mechanistic studies using H2 18O in the electrochemical synthesis demonstrate that the O-atom in the product is initially transferred from the oxidized, O-atom-containing surface of the glassy carbon electrode, with 18O from H2 18O then replacing the O-atom vacancy on the carbon electrode surface. Overall, the present contribution demonstrates the electrochemical, green synthesis of novel and well-known hypervalent iodine reagents using the O-atom from H2O. The reported studies also provide insights into the electrochemical mechanism needed to optimize the synthesis yields as well as to exploit those syntheses using O-atom equivalents generated via (photo)electrochemical water splitting.

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Electrochemical and spectroscopic study of 2-iodobenzoic acid and 2-iodosobenzoic acid anodic oxidation in aqueous environment

Cited by 13 publications

References 43 publications

Anodic Oxidation of Iodobenzene and Iodobenzoic Acids in Acetic Acid Environment – Electrochemical Investigation and Density Functional Theory Study

Anodic Oxidation of Iodobenzene and Iodobenzoic Acids in Acetic Acid Environment – Electrochemical Investigation and Density Functional Theory Study

Recent Updates on Electrogenerated Hypervalent Iodine Derivatives and Their Applications as Mediators in Organic Electrosynthesis

Carbon-Electrode-Mediated Electrochemical Synthesis of Hypervalent Iodine Reagents Using Water as the O-Atom Source

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