Cocaine is thermally labile and, in a series of remarkable thermal reactions, is cleanly partitioned among benzoic acid, N-methylpyrrole and methyl 3-butenoate.
Unimolecular thermal behavior occupies a position of fundamental importance among those reactions that describe the chemistry of a molecular system. All organic molecules have thermal chemistry and few reactions can rival the conceptual simplicity of adding thermal energy to a molecular system until a chemical transformation occurs. The thermal chemistry of a molecular system can often provide important information with respect to structure-reactivity relationships as well as being of value in organic synthesis.l Because of complications arising from bimolecular reactions, the unimolecular thermal chemistry is best studied by taking advantage of the conditions of very high dilution of the gas phase. However, the dif&ulty with using the gas phase for molecules with a high degree of complexity is that heat is usually required for their evaporation. The application of heat to many compounds, even under conditions of high vacuum, often results in their decomposition into intractable tars before evaporation occurs. We have discovered that this problem can be considerably alleviated by using a solvent to co-sublime the substrate at low temperatures. 2 We now report the application of this method to some tropane alkaloids.
An important member of the tropane alkaloids is (-)-cocaine 1 whose abuse has created a number of complex and interacting social, economic, political and medical problems resulting in an urgent need