Sucrose was tritylated and acetylated to give a crystalline tri-O-trityl-penta-O-acetyl sucrose derivative, and detritylation of this product by graded hydrolysis with acetic acid followed by methylation and deacetylation yielded 1′,4,6′-tri-O-methyl sucrose. The structure of the tri-O-methyl sucrose was established by periodate oxidation and by hydrolysis to the correspondingO-methyl ethers of glucose and fructose. Acetyl group migration from C4to C6in the glucose moiety of sucrose probably occurred during the methylation reaction.Some aspects of syntheses involving sucrose are discussed.