Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2022 May;11(5):e202200059.
doi: 10.1002/open.202200059.

Beyond Kolbe and Hofer-Moest: Electrochemical Synthesis of Carboxylic Anhydrides from Carboxylic Acids

Andreas P Häring  1 , Dennis Pollok  1 , Benjamin R Strücker  1 , Vincent Kilian  1 , Johannes Schneider  1 , Siegfried R Waldvogel  1
Affiliations

Beyond Kolbe and Hofer-Moest: Electrochemical Synthesis of Carboxylic Anhydrides from Carboxylic Acids

Andreas P Häring et al. ChemistryOpen. 2022 May.

Abstract

Herein we report a conceptually new non-decarboxylative electrolysis of carboxylic acids to obtain their corresponding anhydrides as highly valuable reagents in organic synthesis. All carbon atoms of the starting material are preserved in the product in an overall redox-neutral reaction. In a broad substrate scope of carboxylic acids the anhydrides are generated with high selectivity, which demonstrates the versatility of the developed method. Beneficially, no dehydrating reagents are required in comparison to conventional methods and the synthesis is based on uncritical starting materials using graphite and stainless steel as very inexpensive and eco-friendly electrode materials.

Keywords: carboxylic acids; carboxylic anhydrides; electrochemistry; electrosynthesis; sustainable chemistry.

PubMed Disclaimer

Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Conventional synthesis approaches of carboxylic acid anhydrides and electrolysis of carboxylic acids in organic media towards Kolbe, non‐Kolbe, and Hofer–Moest products in comparison to this work.
Figure 1
Figure 1
Electrochemically generated carboxylic anhydrides; [a] reaction conditions: undivided cell, under air, 298 K, 0.7 m carboxylic acid 1 in 5.0 mL MeCN, 0.10 m KSCN, 1.1 F, 50 mA cm−2, graphite anode, stainless steel cathode; quantification by 1H NMR spectroscopy with 1,3,5‐trimethoxybenzene as internal standard; selectivity=yield/conversion; for individual deviations from standard conditions see Supporting Information; [b] quantification by GC‐FID with dibutyl fumarate or dibromomethane as internal standard; [c] quantification by inverse‐gated 13C NMR spectroscopy with 1,3,5‐trimethoxybenzene as internal standard; [d] isolated yield.
Scheme 2
Scheme 2
Control experiments with deviations from standard conditions; Yields determined by 1H NMR spectroscopy with 1,3,5‐trimethoxybenzene as internal standard; standard conditions: undivided cell, under air, 298 K, 0.70 m carboxylic acid in 5.0 mL MeCN, 0.10 m KSCN, 1.1 F, 50 mA cm−2, graphite anode, stainless steel cathode.
See this image and copyright information in PMC

References

    1. Held H., Rengstl A., Mayer D., in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany, 2000, p. 3.
    1. El-Faham A., Albericio F., Chem. Rev. 2011, 111, 6557–6602. - PubMed
    1. Alizadeh A., Khodaei M. M., Nazari E., Bull. Korean Chem. Soc. 2007, 28, 1854–1856.
    1. Chen Q., Fan X.-H., Zhang L.-P., Yang L.-M., RSC Adv. 2014, 4, 53885–53890.
    1. Kocz R., Roestamadji J., Mobashery S., J. Org. Chem. 1994, 59, 2913–2914.

Publication types

LinkOut - more resources