Selective Chloride-Mediated Neat Ethanol Oxidation to 1,1-Diethoxyethane via an Electrochemically Generated Ethyl Hypochlorite Intermediate

Li, Siqi; Bartlett, Bart M.

doi:10.1021/jacs.1c05976

Selective Chloride-Mediated Neat Ethanol Oxidation to 1,1-Diethoxyethane via an Electrochemically Generated Ethyl Hypochlorite Intermediate

Journal Article · Thu Sep 23 00:00:00 EDT 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.1c05976· OSTI ID:1829039

Li, Siqi ^[1]; ^[2]

Univ. of Michigan, Ann Arbor, MI (United States); University of Michigan
Univ. of Michigan, Ann Arbor, MI (United States)

Selective primary alcohol oxidation to form aldehydes products without overoxidation to carboxylic acids remains a key chemistry challenge. Using simple alkylammonium chloride as the electrolyte with a glassy carbon working electrode in neat ethanol solvent, 1,1-diethoxyethane (DEE) was prepared with >95% faradaic efficiency (FE). DEE serves as a storage platform protecting acetaldehyde from overoxidation and volatilization. UV–vis spectroscopy shows that the reaction proceeds through an ethyl hypochlorite intermediate as the sole chloride oxidation product, and that this intermediate decomposes unimolecularly (rate constant k = (6.896 ± 0.516) × 10^–4 s^–1) to form HCl catalyst and acetaldehyde, which undergoes rapid nucleophilic attack by ethanol solvent to form the DEE product. As a result, this indirect oxidation mechanism enables ethanol oxidation at much less positive potentials due to the fast kinetics for chloride anion oxidation.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Michigan, Ann Arbor, MI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0006587

OSTI ID:: 1829039

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 39 Vol. 143; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Selective Chloride-Mediated Neat Ethanol Oxidation to 1,1-Diethoxyethane via an Electrochemically Generated Ethyl Hypochlorite Intermediate

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