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Synlett 2022; 33(10): 993-997
DOI: 10.1055/s-0040-1719920
DOI: 10.1055/s-0040-1719920
letter
A Facile Oxidation of Tertiary Amines to Lactams by Using Sodium Chlorite: Process Improvement by Precise pH Adjustment with CO2
We are thankful for the support of the National Natural Science Foundation of China (21372081, 21172072).
Abstract
By using cheap and innocuous sodium chlorite, a series of tertiary amines have been oxidized to the corresponding lactams with good selectivity and high yield. In this method, neither transition-metal catalyst nor oxidant was used. In the oxidation step, the pH of the sodium chlorite was precisely adjusted to pH around 6 using CO2, such pH is a compromise between oxidative properties, chemical stability, and unwanted precipitation. In addition, buffer salts are not necessary, which allows this oxidation reaction to be performed under safe and environmentally benign conditions.
Key words
amine oxidation - sodium chlorite - transition-metal-free - carbon dioxide - pH adjustmentSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1719920.
- Supporting Information
Publication History
Received: 21 February 2022
Accepted after revision: 01 April 2022
Article published online:
05 May 2022
© 2022. Thieme. All rights reserved
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- 18 General Procedure for the Oxidation of Tertiary Amines to Corresponding Amides A solution of (4-nitrophenyl) morpholine (1.04 g, 5 mmol) in CH3CN (10 mL) was added into a 100 mL three-port, round-bottom flask, and it was stirred under CO2 atmosphere at 50 °C. Then a solution of sodium chlorite (more than 80%, 1.69 g, 15 mmol) in water (5 mL) was added in 20 min. TLC and HPLC showed that the reaction was completed in 2.5 h. The reaction was quenched with aqueous saturated sodium sulfite. The mixture was extracted with DCM (3 × 30 mL). The combined organic solution was dried over anhydrous sodium sulphate. Removal of all volatiles left a residue, which was purified by flash chromatography on silica gel (hexane/EtOAc, from 5:1 to 3:1) to give 2a (1.05 g, 95% yield). Analytical Data for (4-Nitrophenyl) morpholin-3-one (2a, Table [1], Entry 2) Light-yellow solid; 1H NMR (400 MHz, CDCl3): δ = 8.28 (d, J = 8.0 Hz, 2 H), 7.61 (d, J = 8.0 Hz, 2 H), 4.38 (s, 2 H), 4.10 (t, J = 4.0 Hz, 2 H), 3.86 (t, J = 4.0 Hz, 2 H). 13C NMR (101 MHz, CDCl3): δ = 166.8, 146.74, 145.74, 124.71, 124.56, 68.67, 63.96, 48.89.