AbstractThe 2 + 4 cycloaddition reaction of 1,4‐naphthoquinone and substituted styrenes was used to prepare 1‐, 2‐, 3‐, and 4‐bromobenz[a]anthracene‐7,12‐diones (BADs). The corresponding bromobenz[a]anthracenes (BAs) were prepared by aluminum tricyclohexoxide reduction of the diones. Lithiation witht‐butyllithium followed by quenching with deuterium oxide gave the specifically2H‐labeled BAs with deuterium incorporations of>95%. The 2‐, 3‐, and 4‐bromo‐7,12‐dimethylbenz‐[a]anthracenes (DMBAs) were prepared from the bromo BADs in moderate yield by the classical Grignard procedure. Lithium aluminum deuteride reduction gave the2H‐DMBAs. An alternate synthesis from 3,4‐dihydrobenz[a]anthracene 1‐(2H)‐one was used for the pre