Ion trap MSn genealogical mapping - approaches for structure elucidation of novel products of consecutive fragmentations of morphinans

The analysis of data within multi-generational, genealogical, electrospray ionization/MSn fragmentation maps is discussed in reference to the structur e elucidation of morphinans, an important class of pharmacological compound s. Various general approaches to separate and understand observed processes are discussed. These include: (1) Simple synthetic schemes incorporating d euterium and C-13 into morphinans to study later-generation, O-methyl group migration; (2) labeling to understand 'intense' signals for even-electron to odd-electron ion 'switching' events; (3) gas phase 'synthesis' of propos ed MS3 ions via an independent route, using chemical ionization (CI) MS/MS of naphthalenes and analysis via a bench-top El/Cl ion trap; (4) a useful s ynthetic paradigm for generating proposed carbonium ion structures at MS4 v ia electrospray ionization (ESI) of easily synthesized amines; (5) the anal ysis of an oxidation product and correlation of MSn data of a switched, odd -electron species with electron ionization and low-pressure, low-energy cha rge exchange data; and (6) a new way of summarizing MSn data. Copyright (C) 2000 John Wiley & Sons, Ltd.