Synthesis and Spectral Properties of 8-Anilinonaphthalene-1-sulfonic Acid (ANS) Derivatives Prepared by Microwave-Assisted Copper(0)-Catalyzed Ullmann Reaction

For decades, the dye 8-anilino-1-naphthalenesulfonic acid (ANS) has been used to study biological systems due to its environmentally sensitive fluorescent nature and propensity to bind to hydrophobic pockets of proteins. However, the syntheses of ANS and its derivatives have been low yielding, requiring harsh reaction conditions and long reaction times. We have developed efficient, mild microwave-assisted copper(0)-catalyzed Ullmann coupling conditions to synthesize ANS derivatives with yields of up to 74%. Many of these derivatives have spectral properties distinct from ANS, including improved and diminished quantum yields, different absorption and emission maxima, and complete loss of fluorescence. ANS derivatives with these unique fluorescence properties are useful tools to study biological systems.