Temperature-dependent benzoic acid elimination mechanisms in pyrolysis of (-)-cocaine

The thermal elimination of benzoic acid from (-)-cocaine is shown to be temperature-dependent. In the temperature range of 200-500 °C only a trans-elimination is observed leading to methylecgonidine. Above ca. 500 °C a second mechanism, the cis-elimination, comes up yielding a novel alkaloid methylisoecgonidine which has been characterized by means of mass spectrometry. At 600 °C the cis-elimination predominates. The trans-elimination is postulated a two-step process consisting of a 1,7- and a 1,5-hydrogen shift. The chemistry of cocaine base smoking is explained using the theory of chemical activation.