The name "sodium percarbonate" (SPC) does not reflect the structure of this oxidizing agent, which is in fact a carbonate perhydrate: 2 Na2CO3 • 3 H2O2. Although SPC is very storage-stable if dry, the solid material has a slight vapour pressure of hydrogen peroxide leading to exchange with water or to violent reactions with oxidizable substrates, even in the solid state.
Sodium percarbonate is a source of highly concentrated hydrogen peroxide in non-aqueous systems, even if the material is not fully soluble. The addition of small amounts of water or sonication can increase the rate of oxidation. For example, sodium percarbonate allows the convenient preparation of peroxyacids from acid chlorides, and even from the acids themselves. Thus, SPC can be used in epoxidations and Baeyer-Villiger oxidations in the presence of an acylating agent:
The slight change in reactivity in aqueous solution might be attributed to the formation of true percarbonates, but the dominant chemistry is that of hydrogen peroxide:
Percarbonate behaves as an electrophile, because the driving force is the formation of carbonate:
For a more detailed explanation, please refer to A. McKillop, W. R. Sanderson, Tetrahedron, 1995, 51, 6145-6166. DOI
Sodium percarbonate in trifluoroacetic acid is an effective reagent for the Baeyer-Villiger oxidation of ketones to esters. The scope and limitations of the reaction were explored.
G. A. Olah, Q. Wang, N. J. Trivedi, G. K. S. Prakash, Synthesis, 1991, 739-740.
The oxidation of primary and secondary alcohols by sodium percarbonate in the presence of catalytic amounts of both molybdenyl acetylacetonate and Adogen 464 gave fair to high yields of the corresponding carbonyl compounds.
S. Maignien, S. Aït-Mohand, J. Muzart, Synlett, 1996, 439-440.
In MTO-catalyzed epoxidation, aqueous hydrogen peroxide is typically added dropwise to a dichloromethane solution of the olefin, pyrazole as accelerant, and MTO. The use of sodium percarbonate (SPC) offers a slow release of hydrogen peroxide, that can be accelerated using trifluoroacetic acid.
A. R. Vaino, J. Org. Chem., 2000, 65, 4210-4212.
The use of ammonium iodide as the catalyst and sodium percarbonate as the co-oxidant enables a transition-metal-free direct α-C-H amination of ketones. A wide range of ketone ((hetero)aromatic or nonaromatic ketones) and amine (primary/secondary amines, anilines, or amides) substrates undergo cross-coupling to generate synthetically useful α-amino ketones.
Q. Jiang, B. Xu, A. Zhao, J. Jia, T. Liu, C. Guo, J. Org. Chem., 2014, 79, 8750-8756.
Sodium percarbonate is an ideal and efficient oxygen source for the oxidation of tertiary nitrogen compounds to N-oxides in excellent yields in the presence of various rhenium-based catalysts under mild reaction conditions.
S. L. Jain, J. K. Joseph, B. Sain, Synlett, 2006, 2661-2663.