Reactions of halo‐ and dihaloadamantanes with nitromethane anions by the SRN1 mechanism

Abstract

AbstractThe reactions of 1‐bromo‐, 2‐bromo‐, 1,3‐dibromo‐ and 1,4‐dibromoadamantane with −CH2NO2 anions were studied in DMSO and in liquid ammonia. The photostimulated reaction of 1‐haloadamantane (1‐AdX, X = Br, I) or 2‐AdBr with −CH2NO2 anions gave good yields of the substitution product 1‐AdCH2NO2 and 2‐AdCH2NO2, respectively, in the presence of the enolate anions of acetone (entrainment conditions). On the other hand, 1‐adamantanol was the main product of the reaction performed in DMSO without irradiation, but not in liquid ammonia. 1,3‐Dibromo and 1,4‐dibromoadamantane reacted with −CH2NO2 anions under irradiation in the presence of the enolate anions of acetone. The first compound gave the disubstitution product 11, and the second the monobromo‐substitution products 15 and 16, together with the disubstitution product 17. Compounds 15 and 16 were shown to be intermediates in the formation of 17. Copyright © 2003 John Wiley & Sons, Ltd.