Eliminations and Rearrangements in Deamination of Open-Chain Amines

More recently, Kirmse and his coworkers found two other deamination reactions where product studies indicated the intermediate formation of radicals, namely the nitrous acid decompositions of 2-aminobutylnitrile (Bunse and Kirmse, 1993) and of the epimeric 2-aminonorbornyl-2-carbonitrile (Kirmse et al., 1993b). Like 2-amino-2-methylpropylnitrile (7.59), these compounds are characterized by a CN group at the same C-atom as the NH2 group. 

4 Eliminations and Rearrangements in Deamination of Open-Chain Amines 

We start this section with a short discussion of conformational control, because conformations of alkylamines and alkanediazonium ions are important factors for the deamination mechanisms. The distribution and configuration of products is often a function of the relative population of conformers. If two conformers yield two different products basically two cases have to be distinguished  

1) The activation energies of the forward and backward conformational equilibration are small relative to the activation energies of the reactions leading from each conformer to the respective product the ratio of the two products is independent of the relative population of the two conformers. 

This is consistent with an intimate diazonium ion-acetate ion pair, which loses N2 before it can stereomutate. 

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