Hofmann Degradation of β-Hydroxy Ammonium Salts. α- and β-Hydroxylaudanosine, 7-Hydroxyglaucine, and 13-Hydroxyxylopinine

Article abstract of DOI:10.1021/jo00147a020

The four related β-hydroxy ammonium methiodide salts of α-hydroxylaudanosine (2a), β-hydroxylaudanosine (2b), 7-hydroxyglaucine (5a), and 13-hydroxyxylopinine (8a) have been subjected to Hofmann degradation.Although precedent dictates that such materials should form either epoxides or ketones, these are not found.Only products of (a) fragmentation and elimination (from 2a and 2b), (b) dehydration and elimination (from 5a), and (c) elimination and oxidation (from 8a) are obtained.The results are accounted for by consideration of the molecular geometries of theβ-hydroxy ammonium salts as experimentally determined from single-crystal X-ray studies and the geometric requirements for epoxide and ketone formation.