Selective and Scalable Dehydrogenative Electrochemical Synthesis of 3,3′,5,5′-Tetramethyl-2,2′-biphenol

Maximilian Selt; Stamo Mentizi; Dieter Schollmeyer; Robert Franke; Siegfried R. Waldvogel

doi:10.1055/s-0039-1690706

Synlett, Table of Contents

Synlett 2019; 30(18): 2062-2067
DOI: 10.1055/s-0039-1690706

letter

Selective and Scalable Dehydrogenative Electrochemical Synthesis of 3,3′,5,5′-Tetramethyl-2,2′-biphenol

Maximilian Selt

^aInstitut of Organic Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128 Mainz, Germany Email: waldvogel@uni-mainz.de

^bMAterial Science IN MainZ (MAINZ), Graduate School of Excellence, Staudingerweg 9, 55128 Mainz, Germany

,

Stamo Mentizi

^aInstitut of Organic Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128 Mainz, Germany Email: waldvogel@uni-mainz.de

,

Dieter Schollmeyer

^aInstitut of Organic Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128 Mainz, Germany Email: waldvogel@uni-mainz.de

,

Robert Franke

^cEvonik Performance Materials GmbH, Paul-Baumann- Straße 1, 45772 Marl, Germany

^dLehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780 Bochum, Germany

,

Siegfried R. Waldvogel ∗

^aInstitut of Organic Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128 Mainz, Germany Email: waldvogel@uni-mainz.de

^bMAterial Science IN MainZ (MAINZ), Graduate School of Excellence, Staudingerweg 9, 55128 Mainz, Germany

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Abstract

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Abstract

3,3′,5,5′-Tetramethyl-2,2′-biphenol is a compound of high technical significance, as it exhibits superior properties as building block for ligands in the transition-metal catalysis. However, side reactions and overoxidation are challenging issues in the conventional synthesis of this particular biphenol. Here, an electrochemical method is presented as powerful and sustainable alternative to conventional chemical strategies, which gives good yields up to 51%. Despite using inexpensive and well-available bromide-containing supporting electrolytes, the issue of bromination and general byproduct formation is effectively suppressed by adding water to the electrolyte. Additionally, the scalability of this method was demonstrated by conducting the electrolysis on a 122 g scale.

Key words

electrosynthesis - oxidation - phenol - anode - biphenol - sustainable synthesis

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References and Notes

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21 General Protocol for Screening Reactions A solution of 2,4-dimethylphenol (1, 2–10 mmol) and the respective supporting electrolyte (0.2–1.0 mmol) in 5 mL HFIP or HFIP with 18 vol% methanol or HFIP with 5–40 vol% water was transferred into a screening electrolysis cell equipped with a glassy carbon anode and a glassy carbon cathode. A constant current electrolysis with a current density of 3.9–25.6 mA·cm^–2 was performed at 20–60 °C. After application of 1.0–1.7 F per mol of 1, the electrolysis was stopped, and the solvent mixture was recovered in vacuo (50 °C, 200–70 mbar). Subsequently, the sample was prepared according to the respective internal calibration (IK1–IK4, see section 2 in the Supporting Information).
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30 Chemical catalogue: TCI (25.02.2019), CAS-No: 71-91-0, >98.0%.
31 Chemical catalogue: TCI (25.02.2019), CAS-No: 1941-30-6, >98.0%.
32 Chemical catalogue: TCI (25.02.2019), CAS-No: 1643-19-2, >99.0%.
33 Chemical catalogue: TCI (25.02.2019), CAS-No: 5197-95-5, >98.0%.

Supplementary Material

Supporting Information