A synthesis of N‐alkyl‐4‐chloro‐1H‐benzo[c][1,2]thiazine‐3‐carbaldehyde‐2,2‐dioxides is described. Reactivity of new β‐chloroaldehydes is investigated, a number of novel benzo[c][1,2]thiazine derivatives are synthesized and characterized using 1H, 13C‐NMR, MS and elemental analysis.