Abstract: In this work the polar Diels-Alder reactions between 2- and 3-nitrobenzothiophenes derivatives and different dienes, such as 2-methyl-1,3-butadiene and 1-trimethylsilyloxy-1,3-butadiene are studied. Molecular solvent and protic ionic liquids are employed as reaction media. A very strong electron-acceptor group such as nitro group, push the electrophilic character of these heterocyclic compounds. Moreover, this substituent is easily extruded under thermal conditions make this reaction sequence a simple method of organic compound´s families with heteroatom rings preparation.