N-ARYL-O-(ALPHA-AMINOACYL)HYDROXYLAMINES - MODEL REACTIONS FOR THE ACTIVATION OF MONOCYCLIC AROMATIC-AMINES INTO ULTIMATE CARCINOGENS WITH ALPHA-AMINO-ACIDS

N‐Aryl‐O‐(α‐aminoacyl)hydroxylamines: Model Reactions for the Activation of Monocyclic Aromatic Amines into Ultimate Carcinogens with α‐Amino Acids The rearrangement of the new α‐aminohydroxamic acids 15 and 18 to the likewise new N‐(α‐aminoacyloxy)arylamines [“N‐(acyloxy)arylamines”] 19 and 20, respectively, is observed in amine‐catalyzed model reactions. N‐(acyloxy)arylamines such as 19 and 20 are indicated to be ultimate carcinogens of aromatic amines which are able to react with bionucleophiles such as the DNA bases. The formation of 19 and 20 was proven by trapping these reactive intermediates with the model nucleophile N‐methylaniline (21) to give the hydrazines 22 and‐depending on the substitutent in 19 and 20‐the so‐called ortho amination products 23. Analogous reactions of the aceto‐and pivalohydroxamic acids 24 and 25 lead also to the adducts 22 and 23, respectively, in comparable yields. These results demonstrate that the O‐α‐aminoacylation as shown here may be similarily used in model reactions for the activation of carcinogenic aromatic amines as the O‐acetylation. Copyright © 1990 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim