PREPARATION OF N-ARYL-2-HYDROXYPROPIONAMIDES FROM HYDROXY AROMATIC-COMPOUNDS USING A ONE-POT SMILES REARRANGEMENT PROCEDURE

Acylation of hydroxy aromatic compounds with 2-bromo-2-methylpropianam ide followed by Smiles rearrangement of the resulting 2-aryloxypropion amide in a one-pot procedure produced the corresponding 2-hydroxy-2-me thyl-N-arylpropionamides which can be converted to arylamines by hydro lysis. Particularly important applications of this new process were th e conversions of estrone (6) and estradiol (14) to the corresponding 3 -aminoestratriene derivatives 8 and 15, respectively. In addition, an improved Semmler-Wolff procedure is described for the conversion of 19 -nortestosterone (22) to 3-aminoestra-1,3,5(10)-trien-17 beta-ol hydro chloride (26). (C) 1997 Elsevier Science Ltd.