Oxidation of hydrocarbons. 18. Mechanism of the reaction between permanganate and carbon-carbon double bonds

The nature of the products obtained when permanganate reacts with olefins is determined by rapid reactions that occur after the rate-limiting step (which is known to involve the formation of an intermediate cyclic manganate(V) diester). A study of the reactions of manganate(V) oxide has shown that i...

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Bibliographic Details
Published inJournal of the American Chemical Society Vol. 111; no. 19; pp. 7534 - 7538
Main Authors Lee, Donald G, Chen, Tao
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 01.09.1989
Subjects
400201 - Chemical & Physicochemical Properties
CALCULATION METHODS
CHEMICAL REACTIONS
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
MANGANESE COMPOUNDS
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDATION
OXYGEN COMPOUNDS
PERMANGANATES
TRANSITION ELEMENT COMPOUNDS
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Summary:The nature of the products obtained when permanganate reacts with olefins is determined by rapid reactions that occur after the rate-limiting step (which is known to involve the formation of an intermediate cyclic manganate(V) diester). A study of the reactions of manganate(V) oxide has shown that its primary reactions are disproportionation and oxidation to manganate(VI) by permanganate. Disproportionation is slow under highly basic conditions and very rapid under moderately basic or neutral conditions. The converse is true for the reaction between manganate(V) and permanganate. Consequently, although the principle reaction of the intermediate cyclic manganate(V) diester is likely disproportionation under neutral conditions, oxidation is the primary reaction in very basic solutions. It is shown how these kinetic measurements account for the observed products-diols in basic solutions and ketols under neutral conditions.
Bibliography:ark:/67375/TPS-KGW3RT1N-P
istex:46B0C4BD159E8B86D8E83C71D7A24358B4699D56
ISSN:0002-7863
1520-5126
DOI:10.1021/ja00201a039