Acylation of cellulose in a novel solvent system: Solution of dibenzyldimethylammonium fluoride in DMSO

Abstract

A novel electrolyte, dibenzyldimethylammonium fluoride has been obtained essentially anhydrous (BMAF-0.1H2O) by a simple route. Its thermal stability, relative to tetra(1-butyl)ammonium fluoride trihydrate (TBAF3H2O) has been demonstrated by thermogravimetric analysis. DMSO solution of (BMAF-0.1H2O) dissolves microcrystalline- and fibrous celluloses; the dissolved biopolymers have been acylated by ethanoic-, butanoic-, and hexanoic anhydride. The degrees of substitution of the esters are higher than with TBAF3H2O/DMSO. The reasons are discussed in terms of differences in electrolyte structure and contents of water of hydration, whose presence leads to side reactions and decreases of the basicity of (F−). This conclusion is corroborated by molecular dynamics simulations of the interactions of glucose dodecamer/R4NF-hydrate/DMSO. These show that the interactions oligomer-F−-water is operative only for TBAF3H2O/DMSO. The efficiency of BMAF-0.1H2O/DMSO is explained based on better accessibility of the biopolymer due to efficient hydrogen-bonding between its hydroxyl groups and the essentially desolvated (F−).