1,3-benzodioxole derivatives [figure 1(A, B)] have been much studied for their biological activities.1–12Nevertheless, apart from our preceding papers13, 14only few works have been done as concerns their spectroscopic behaviour and their electronic structures.15, 16All the derivatives which have been studied in our recent works display a -CH2X group [Bzd-CH2X] in para to one of the oxygens of the five membered oxygenated fused ring (X being -H, -OH, -NH2, -NH+3, -COCH3etc…). We want to study here more strongly perturbating substituents with X directly linked to the benzene chromophore [figure 1(C)] [Bzd-X].