Abstract: Sulfonylation or alkylation of phenolic hydroxyl groups are not only the key issues of the synthesis of the functional arene, but also the common strategies for the protection of the active phenolic hydroxyl groups. With the treatment of the system of alcohol-sulfonic chloride-potassium carbonate, diphenol could be converted to alkoxy phenolic sulfonate directly via synergistically non-symmetrical sulfonylation-alkylation of two phenolic hydroxyl groups. Such conversion provided a mild and straightforward approach by short synthetic steps, good regioselectivity, and the use of low-toxicity alcohols as alkylation agents. Mechanistic studies revealed that the in-situ-formed sulfonate worked as a highly active alkylating agent and was converted to a non-toxic sulfonate salt. This pathway enhanced the reactive efficiency and significantly mitigated the adverse environmental and health impacts as well.

Key words: Diphenol; Synergistically non-symmetrical sulfonylation-alkylation, Alkoxy phenolic sulfonate