138235-75-3Relevant academic research and scientific papers
Nucleophilic Aromatic Substitution on Ester Derivatives of Carcinogenic N-Arylhydroxamic Acids by Aniline and N,N-Dimethylaniline
Novak, Michael,Rangappa, Kanchugarakoppal S.,Manitsas, Rebecca K.
, p. 7813 - 7821 (2007/10/02)
Decomposition of N-(pivaloyloxy)-2-(acetylamino)fluorene (1b) and N-(sulfonatooxy)-4-(acetylamino)biphenyl (2a) in MeOH occurs predominately via N-O bond cleavage to yield oxazoles (5, 6, 23), methoxy adducts (7, 8, 24, 25, 26), and rearrangement products
Nucleophilic Substitution on the Ultimate Hepatacarcinogen N-(Sulfonatooxy)-2-(acetylamino)fluorene by Aromatic Amines
Novak, Michael,Rangappa, Kanchugarakoppal S.
, p. 1285 - 1290 (2007/10/02)
The kinetics and products of the reactions of the title compound 1 with aniline (5) and N,N-dimethylaniline (6) were investigated in MeOH.Addition of 5 (0.1-0.4 M) to a solution of 1 in MeOD-d4 has no effect on the overall rate of decomposition of 1 but generates a number of adducts (20-24) in moderate to high yield.The yields of all solvolysis products, except the rearranged O-sulfates 18 and 19, are suppressed by the addition of 5.The kinetic and product data are consistent with an SN1 mechanism (Scheme IV) in which 18 and 19 are generated by internal return from a tight ion pair, but all other products are generated by nucleophilic attack on a free nitrenium ion or solvent separated ion pair.The reaction of 6 with 1 shows similar characteristics to that of 5 with the exception that 6 reduces 1 in moderate yield to generate 2-(acetylamino)fluorene (25).This reduction occurs in competition with reaction to generate adducts (26, 27) similar to those obtained with 5.Kinetic and product data indicate that 25 is generated by reaction of 6 with a nitrenium ion intermediate.The differences in the behavior of 5 and 6 may be explained by cyclic voltammetry results which show that 6 is oxidized in MeOH more readily than 5 by about 2.5 kcal/mol.The reaction of 1 with 5 and 6 is considerably different from the rections of the same amines with the N-aryl-O-pivaloylhydroxylamines, which were previously shown to proceed via an SN2 mechanism.This change in mechanism may be attributed, in part, to increased steric hindrance at the nitrogen of 1 due to the N-acetyl group.
