Halides methanesulfonic acid ester

The interest in functionalized ionic liquids is growing because ionic liquids bearing ether, amino or alcohol functionalities have been shown to display special properties, including the ability to dissolve a larger amoimt of metal halide salts and to extract heavy metal ions from aqueous solutions. Imidazolium-based ionic liquids with ether and hydroxyl (see Section 2.2.1), thiourea, thioether and urea (see Section 2.2.8) " have been prepared following the standard quatemization procedure. A straightforward approach has been described for the preparation of imidazolium (as well as pyridinium) cations with ester, ketone or cyanide functionalities 1-methylimidazole reacts with methanesulfonic acid to provide the imidazolium salt 11, which undergoes a Michael-type reaction with methyl vinyl ketone as a ,j8-unsaturated compound to produce the ionic liquid 12 (Scheme 5). ... 

Methanesulfonates. The most common use of methanesulfonyl chloride is for the synthesis of sulfonate esters from alcohols. This can be readily accomplished by treatment of an alcohol with mesyl chloride in the presence of a base (usually Triethy-lamine or Pyridine). The methanesulfonates formed are functional equivalents of halides. As such they are frequently employed as intermediates for reactions such as displacements, eliminations, reductions, and rearrangements. Selective mesylation of a vicinal diol is a common method of preparation of epoxides." Alkynyl mesylates can be used for the synthesis of trimethylsilyl allenes. Oxime mesylates undergo a Beckmann rearrangement upon treatment with a Lewis acid. Aromatic mesylates have been used as substrates for nucleophilic aromatic substitution. Mesylates are more reactive than tosylates toward nucleophilic substitution, but less reactive toward solvolysis. 

Protection of Alcohols. In addition to being used as a halide equivalent, methanesulfonates have also been used as protecting groups for alcohols and phenols. The use of methanesulfonate as a protecting group for alcohols is mainly limited to carbohydrate synthesis due to the lability of the methanesulfonate group toward nucleophilic attack. The sulfonate ester is stable to acidic conditions and can be cleaved by Sodium Amalgam. ... 

---