Abstract2‐Substituted (1H)‐perimidine 1 reacts with various 2‐chloroacyl chlorides 3 to afford new ethyl 2‐oxo‐Δ2. pyrrolino‐[1,2‐a]‐(4H)‐perimidine‐3‐carboxylates 5 in good yields by a N,C‐cyclocondensation reaction sequence. The 1H, 13C NMR spectrum of some representative compounds are discussed. The reactions of 1 with trans‐cinnamoyl chloride 6 and with 3‐chloropropanoyl chloride 8 as β‐dielectrophiles have been investigated and gave directly the corresponding fused perimidines 7 with reverse regiochemistry.