Alcohols, primary with Oxone

Primary, secondary and tertiary thioamides and thionreas are readily converted to their corresponding 0x0 analogs with Oxone in refinxing CH3CN . Thiono esters were converted to esters, while thioketones remained intact nnder these reaction conditions. Hydrazines can be selectively converted to esters and acids in high yields by nsing Oxone in an alcohol and a water, respectively . However, Mane and coworkers showed that hydrazides can be smoothly converted into the corresponding Af,Af -diacylhydrazines in excellent yields with Oxone in water (equation 67) . ... 

Protecting Group RemovaL Several types of alcohol and carbonyl protecting groups can be removed with solutions of Oxone. Deprotection with Oxone offers a mild alternative to traditional methods which often require harshly acidic or basic conditions. Primary alkyl and phenolic TBS ethers are cleaved with aqueous methanolic Oxone (eq 85). Primary alkyl TBS ethers are much more labile and thus can be cleaved in the presence of phenolic TBS ethers by limiting the reaction time. Secondary and tertiary TBS ethers and TBDPS ethers are unaffected. When the reactions were carried out in the absence of Oxone with solutions of HCl and HF adjusted to the same pH as the Oxone solution, no cleavage was observed for any type of TBS ether after 2.5-3 h, suggesting that Oxone s deprotective ability is not due solely to its acidic nature. 

Aliphatic alcohols are converted to a symme-RCOOCH2R) by oxidation with PCC on aluminum without solvent. Oxone in aqueous methanol also converts aryl aldehydes to the corresponding ester. Ally lie alcohols are converted to conjugated esters with Mn02, NaCN in methanol-acetic acid. Primary alcohols are oxidized to the methyl ester with tri-chloroisocyanuric acid in methanol. This reagent also converts diols to lactones. 

In acidic oxidations of primary alcohols, esterification of the alcohol by the acid produced by its oxidation sometimes takes place. Thus the oxidation of ethanol with potassium peroxymonosulfate (Oxone) in the presence of concentrated sulfuric acid at 70 °C gives a quantitative yield of ethyl acetate [205]. 

Oxone oxidizes metal complexes including tris[(2-oxazolinyl)-phenolato] manganese(III) which, in conjunction with -Bu4NBr, is an effective oxidant for aromatic and primary and secondary aliphatic alcohols. ... 

---