Hünlich base: (re)discovery, synthesis, and structure elucidation after a century

Org Lett. 2013 Mar 15;15(6):1418-20. doi: 10.1021/ol400357t. Epub 2013 Mar 7.

Abstract

After almost 100 years, the structure of the product of the reaction between 2,4-diaminotoluene and formaldehyde was elucidated: derivative 3, which we call the Hünlich base, was synthesized on a multigram scale and its enantiomers were easily separated in preparative amounts. Furthermore, transformation of the NH2 groups to the corresponding bis-iodides and bis-azides is presented. The latter was also used for desymmetrization by click chemistry.