Synthesis of Salts of 1,2,5,6- and 1,4,5,8-Naphthalenetetramine

1,2,5,6-Naphthalenetetramine (1a), its 1,4,5,8-isomer (2a), and their salts are valuable precursors for synthesizing nitrogen-containing arenes and other targets of interest. We describe how salts of tetramines 1a and 2a can be made from simple protected derivatives of 1,5-naphthalenediamine (2d) by sequences of regioselective dinitration, deprotection, and reduction. Various shortcomings of previously reported syntheses of tetramines 1a and 2a can thereby be avoided. In addition, we report structural studies that may help clarify the mechanism of nitration and resolve an earlier controversy about the regioselectivity observed in nitrations of derivatives of 1,5-naphthalenediamine (2d).