AbstractThe use of the tertiary base 1,4‐diazabicyclo[2,2,2]octane, together with 1‐fluoro‐2,4‐dinitrobenzene in the solvent DMF, proved to be an efficient method for the introduction of the 2,4‐dinitrophenyl (DNP) group at different positions, including the anomeric centre of glucose and galactose. The introduction of the DNP ethers at the anomeric centre leads exclusively to the formation of β‐DNP ethers. The latter derivatives can be easily converted with potassium carbonate in DMF into the α‐DNP ethers. The X‐ray analysis of 2,4‐dinitrophenyl‐2,3,4,6‐tetra‐O‐acetyl‐α‐D‐gluco‐pyranoside is discussed. The DNP group can also be used as a protective group in the synthesis of a disaccharide (i.e. 8) and as a UV probe to monitor (254 nm) and analyse (HPLC) sugar intermediates.