Solutions to Problems Chapter 1 1-1-8: dipolar resonance stecture has aromatic character in both rings and would be expected to inake a major contribution to the overall structure Od -~ Od 5, The “extra” polarity associated with the second resonance structure woud Soaihate 10 the molecular structure but would not be accounted for by standard group dipoles, © TREE ae thee major Factors contibuing to the overall dipole moments: (1) {he o-bond dipole associated withthe C—O and C—N bonds: (2) the w-bona dipole associated with delocalization of wr electrons from the heteroatom to the direction of the overall dipole moment, The AIM charges have been caleulated. electom ON sacions ay os ¢ i te oe ee ond O>N bona a ae Voce | unshared: 30 7008 aes os Aint chargos a09 2 Savas Pons 13.8 . The nitrogen is the most basic atom, Proven 4 Protonation on oxygen preserves the resonance interaction with the nitrogen unshared electeon pair. oH oH CHC. one! Ney NH Protonation on nitrogen limits conjugation to the diene system, Protonation 62.2) preserves a more polar and more stable conjugated iminium system, Protonation on C(3) gives a less favorable cross-conjugated system, ® —~QoOg oof i 4 Protonation on the ring nitrogen preserves conjugation with the exocyclic nitrogen unshared electrons, t i i Nt 4 ‘charge can be delocalized charge is localized on ‘exocyete nitrogen ‘The dipolar resonance structure containing cyclopentadienide and pyridinium tings would be a major resonance contributor. The dipole moments and bond lengths would be indicative. Also, the inter-ting “double bond” would have a reduced rotational barrier, ‘The dipolar oxyeyclopropenium structure contributes to longer C=O bond and lan increased dipole moment, The C=O vibrational frequency should be shifted toward lower Frequency by the partial single-bond character. The compound should have a larger p&, for the protonated foun, reflecting increased electron density at oxygen and aromaie stabilization of the cation9 ° o A- Pr ph pr Sp © There would be a shift in the UV spectrum, the IR C=O stretch, and NMR ‘chemical shifts, reflecting the contribution from a dipolar resonance structure. i ° oe Coe prefer planar geometry because of the resonance stabilization, The barrier to rotation is associated with MO terminology, the orbital with the orbital provides a stabilized Aslocalized orbital. The nonplanar form leads to isolation of the nitrogen ‘unshared pair from the C=O system, Boom — 85 a ah B09 Non, oe So b. The delocalized form is somewhat more polar and is preferentially stabilized in solution, which is consistent with the higher barrier that is observed © Amide resonance is reduced in the aziridine amide because of the strain associated with sp? hybridization at nitrogen, 2, sen] i ‘The bieyelie compound cannot align the unshared nitrogen electron pair with the carbony! group and therefore is less stable than a normal amide. 1-5. a The site of protonation should be oxygen, since it has the highest negative charge density