Amine Oxidation by Electrochemically Generated Peroxodicarbonate

Abstract

The N-oxidation of tertiary amines was achieved by using electrochemically generated peroxodicarbonate solutions as sustainable oxidizers. The presence of EDTA and 2,2,2-trifluoroacetophenone as a mediator was found to be crucial for converting water-insoluble substrates. Various tertiary amines were converted into their corresponding N-oxides in yields of up to 98%. The scope includes economically important surfactants and potential platform oxidizers.

Key words

oxidation - peroxodicarbonate - boron-doped diamond - electrochemistry - amine oxides - organocatalysis

Publication History

Received: 30 March 2022

Accepted after revision: 24 May 2022

Accepted Manuscript online:
24 May 2022

Article published online:
15 June 2022

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• 24 N,N-Dimethyldodecylamine N-Oxide (2b); Typical Procedure for Lipophilic Amines The titrated peroxodicarbonate solution (3.4 equiv) was added to N,N-dimethyldodecylamine (1.00 mmol), EDTA (73.1 mg, 0.25 mmol, 0.25 equiv), and TFAP (35.5 μL, 0.25 mmol, 0.25 equiv) in a 50 mL vial containing a Teflon-coated stirring bar. The mixture was stirred at RT for 5 h and then extracted with EtOAc (5 × 20 mL). The organic solvent was removed under reduced pressure to give a white solid; yield: 226 mg (0.97 mmol, 97%); mp: 130–133 °C (Et₂O). ¹H NMR (300 MHz, CDCl3): δ = 3.28–3.20 (m, 2 H), 3.18 (s, 6 H), 1.95–1.81 (m, 2 H), 1.41–1.19 (m, 18 H), 0.87 (m, 3 H). ¹³C NMR (100 MHz, CDCl3): δ = 72.1, 58.9, 32.0, 29.7 (2 C), 29.6, 29.5, 29.4 (2 C), 26.8, 24.1, 22.8, 14.2. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₄H₃₂NO: 230.2484; found: 230.2487. The analytical data (NMR) matched those reported in the literature.^25b
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