Factors governing product distribution in the oxidation of alkenes by manganese(III) acetate in acetic acid and acetic anhydride

Abstract

A systematic investigation has been carried out into the effect of different reaction parameters on the oxidation of oct-1-ene by manganese(iii) acetate in acetic acid and acetic anhydride. The most important factor in dictating the ratio of products is the composition of the solvent. In the absence of anhydride y-decanolactone is virtually the sole product. Even small quantitites of anhydridy lead to the lactone being replaced b y other products derived from cationic intermediates C, H, ,CHCH,COX (X = OH or OAc). Further increases in the amount of anhydride encourage the formation of decanoic acid until, in 90% anhydride, this becomes the predominant product. The results cannot be interpreted simply in terms of competition for the alkene by the radicals *CH,CO,H and *CH,COOCOCH,. Decanoic acid formation is also favoured by low temperatures, low concentration of oxidants, and by the addition of acetate ions. A comparision is made of the efficiency of addition when the initiating species is manganese( 111) or a peroxide.

Mn(III) oxidation of peptides: A mechanistic investigation of kinetic variations in hydrophobic‐induced oxidation of tetrapeptides of elastin sequences

“…The visible spectrum of freshly prepared Mn(OAc) 3 solution showed λ max at 440 nm is probably due to undissociated Mn(OAc) 3 . But Midgley and Thomas [23] noted that when alkaline metal acetates were added to Mn(OAc) 3 it appears at 400 nm. This is due to the formation of an acetato com-…”

Esterification of Carboxylic Acids and Etherification of Phenols with Amide Acetals

“…The detailed procedure for the preparation of 82 is described in an English translation. 91 In addition to the examples discussed above, a number of aliphatic, 68,[92][93][94][95][96][97][98][99][100][101][102] aromatic, and heterocyclic [103][104][105][106] carboxylic acids 1, as well as some phenols 16, 107 have been converted by amide acetals, such as 7a-c, into the corresponding esters 4 and phenyl ethers 18. Iminium cations 6b and 6c derived from DMF diethyl acetal 7b and DMF dibenzyl acetal 7c, respectively, will react, for steric reasons, much slower with their amide acetals 7b and 7c to give the corresponding diethyldimethylammonium or dibenzyldimethylammonium carboxylates.…”

“…Although DMF dimethyl acetal 7a and DMF diethyl acetal 7b have been used in a number of esterifications of aliphatic and aromatic or heteroaromatic carboxylic acids68,[92][93][94][95][96][97][98][99][100][101][102][103][104][105][106] and etherifications of phenols,107 they have, nevertheless, not yet become standard reagents for the conversion of carboxylic acids 1 into their methyl or ethyl esters 4, respectively, or for the conversion of phenols 16 into their corresponding methyl or ethyl ethers 18, to replace diazomethane or other reagents. This is apparently because of the product yields achieved from their reactions.…”

Manganese(iii) acetate mediated radical reactions in the presence of an ionic liquid

“…After filtration, the manganese acetate was reacted with potassium permanganate to re-oxidise the manganese(II) back to manganese(III). 9 The manganese(III) acetate can therefore easily be recycled although this does depend on the nature of ionic liquid. For example, when the related ionic liquid [bmim][PF 6 ] was used, complete removal of the manganese byproducts was problematic.…”