Readily available aminonaphthol/aminophenol derivatives were converted to the corresponding thioethers under catalyst‐free reaction conditions. Environmentally benign aqueous medium was utilized for the transformation of aminonaphthol derivatives to the corresponding thioethers under aerobic reaction conditions. Saturated brine solution was identified as a suitable medium for the synthesis of thioethers from aminophenol derivatives. Control experiments revealed that the nature of leaving group and reaction atmosphere plays a vital role in determining the yield of the products.

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