Synthesis of 1-chloroestradiol

The synthesis of the previously unknown 1-chloroestradiol (1), is reported. Addition of N-chlorosuccinimide/NaI in dioxane to 4-amino-estradiol 3-methyl ether (2), resulted in exclusive chlorination of the 1-position. Subsequent deamination and demethylation afforded 1 in good yields.