Part I: Derivatives of 7-azabicyclo[2.2.1]heptane. Part II: Base catalysed hydrogen:deuterium exchange of benzyl sulfoxides.

Abstract

Part I. The synthesis of 7-azabicyclo[2.2.1]heptane (ABH) has been accomplished via two new synthetic routes both of which provide improved yields over any previous synthesis. The spectral and chemical properties of several N-substituted ABH derivatives have been studied and the rotation barriers for 7-acetyl-7-azabicyclo-[2.2.1]heptane and 7-nitroso-7-azabicyclo[2.2.1]heptane have been determined. Chlorination of the trichloroacetyl derivative of ABH and subsequent removal of the trichloroamide group gave a mono-chloro derivative whose structure was proven to be exo-2-chloro-7-azabicyclo[2.2.1]heptane. The solvolytic behavior of this derivative was briefly examined. A new reaction of trichloroacetyl chloride with triethylamine was discovered and was shown to produce a beta-acylenamine. A probable mechanism was proposed after an extensive investigation of the reaction. Part II. The rates of hydrogen:deuterium exchange for the diastereotopic methylene protons in the benzyl group of three benzyl sulfoxides have been determined using mass spectrometry. The variation in rates with changes in structure were found to be small.