Bleach (NaOCl) Oxidation

Mechanism + Description

In acidic media, the loss of water with the addition of the OCl- anion, followed by the loss of HCl to generate the aldehyde that is oxidized to the acid by a similar mechanism.

General comments

NaOCl is usually used as a terminal/stoichiometric co-oxidant with catalysts that provide a stronger oxidant than HOCl alone. In some cases, NaOCl alone can give the acids of esters from primary alcohols.

Key references

Leduc, A. B.; Jamison, T. F. Continuous Flow Oxidation of Alcohols and Aldehydes Utilizing Bleach and Catalytic TetrabutylammoniumBromide. Org. Process Res. Dev. 2012, 16(5), 1082–1089.

Stevens, R. V.; Chapman, K. T.; Stubbs, C. A.; Tam, W. W.; Albizati, K. F. Further Studies on the Utility of Sodium Hypochlorite in Organic Synthesis. Selective Oxidation of Diolsand Direct Conversion of Aldehydes to Esters. Tetrahedron Lett. 1982, 23 (45), 4647–4650.

Zhang, Y.; Born, S. C.; Jensen, K. F. Scale-Up Investigation of the Continuous Phase-Transfer-Catalyzed Hypochlorite Oxidation of Alcohols and Aldehydes. Org. Process Res. Dev. 2014, 18 (11), 1476−1481.

Relevant Scale-Up Examples with Scheme

No scale-up examples identified.