Pyridine will add to carbon 3 in electrophilic reactions, such
as Bromine addition. However in a nucleophilic reaction, such as
seen in the Chichibabin reaction, carbon #2 and #4 are substituted
such as if NH2 - attacked. Draw out the resonance forms and you
will see this, or consult any Organic text under heterocyclic
Chemistry.In a C3 attack, the electrophile will destabilize the C2
and C4 position, to a great extent since N lacks an octet in one of
these resonance forms.In a nucleophilic addition, addition at C2 or
C4 allows the negative charge to be shared by Nitrogen thus is
preferred to the C3 attack. Hope that helps. Dr Jim Romano CEO
Romano Scientific CEO Orgoman.com Class of 1991 NYU