Abstract The syntheses of the K-imine derivatives of carcinogenic benzo [c] phenanthrene and 7, 12-dimethylbenz-[a] anthracene are described. Treatment of trans-5-azido-5, 6- dihydrobenzo [c] phenanthren-6-ol (3) and trans-6-azido-5, 6-dihydrobenzo [c] phenanthren- 5-ol (5) with thionyl chloride yielded the corresponding β-chloro azides, which in turn, were reacted with lithium aluminium hydride to give 4b, 5a-dihydro-5H-benzo [3, 4]-phenanthro ...