The preparation of 6-substituted phenanthridines and their 5, g-dihydro derivatives by the organometallic alkylation of phenanthridine has been examined. It was found that not only do organolithium compounds (n-butyl-and o-tolyllithium) attack phenanthridine readily, but active Grignard reagents such as benzylmagnesium chloride can also add to the azomethine linkage. Finally, even ordinary Grignard reagents such as n- ...