Abstract

The Anderson test for codeine entails the interaction of codeine with concentrated nitric acid and heating to dryness. These drastic conditions give rise to a long series of reactions that is provided for the first time. The initial steps are salt formation, codeine nitrate, followed by nitration of the aromatic ring at the activated position, C-2. Then occurs a molecular rearrangement analogue to the transformation of morphine to apomorphine. This implies a series of reactions that include dehydration of the allylic alcohol, double bond migration, 1,3-chain migration, cyclohexadiene formation, ring opening of the dihydro-furane ring followed by formation of a dihydro-phenanthrene structure. The last stage involves methylamine evolution after two C─N fissions and alkalinization of the reaction medium in order to obtain the free amine.

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