Norbornanediazonium ions

H shifts compete effectively with capture by solvent. For the parent 2-nor-bornyl cation the kc/ku ratio is ca. 1 in formic acid, ca. 2 in acetic acid, and ca. 6 in aqueous acetone50, 516. The decomposition of 2-norbornanediazonium ions in aqueous sodium hydroxide, however, proceeds with less than 4% 6,2-H shift528). Tertiary, secondary shifts, e.g. (749) - (756)505), occur more readily than secondary, secondary shifts do. Steric effects also play some role there is more 6,2—H... 

After this general discussion of the nucleophilic substitution of norbornane derivatives, we will concentrate on the deamination of exo- and eAzrfo-2-norbornyl-amine. The acetolysis of norbornanediazonium ions was first studied by Corey et al. (1963) and by Berson and Remanick (1964). Their results could not be interpreted easily either by Winstein s or by Brown s hypothesis, as seen, for example, in Bartlett s annotated reprint collection (1965), in which he emphasized the need for fully resolved reagents and for better separation methods. 

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