Mechanism and Linear Free Energy Relationships in the Kinetics of Formation of Bicyclo[3.3.1]nonane Derivatives from 1,3,5-Trinitrobenzene, Phenyl-Substituted 1-Benzyl-1-(ethoxycarbonyl)-2-propanones, and Triethylamine

The kinetics and mechanism of cyclization of the anionic sigma complex obtained from the reaction of 1,3,5-trinitrobenzene (TNB) and 1-benzyl-1-(ethoxycarbonyl)-2-propanone (BEP) in the presence of triethylamine (NEt3) have been studied in CH3CN-CH3OH (50% v/v). The order of the reaction has been found to be zero in TNB and BEP, unity in NEt3, and negative and nonintegral in triethylammonium chloride. The rate has been observed to increase slightly with an increase in the concentration of the added salt (tetraethylammonium chloride). The rate constants for the formation of bicyclic adducts from phenyl-substituted BEP and TNB in the presence of triethylamine have been correlated with sigma values. (C) 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 467-473, 2011