Past exam of the chemistry A course of the University of Cambridge 2023 Paper 1 A5 b i Solution 2026-10-20
Pyrazine belongs to , the D2h point group. With the printed axes, its three twofold axes are ; it also has an inversion centre and the three coordinate mirror planes. The nitrogen atoms occupy sites 1 and 4 on the axis. Interchanging carbon and nitrogen is not a molecular symmetry operation, so the sixfold benzene symmetry is lost.
Past exam of the chemistry A course of the University of Cambridge 2023 Paper 1 A5 b iv Solution 2026-10-20
The six electrons give the Hückel method energyThe appropriate localized reference contains two C=N bonds and one C=C bond. Three C=C bonds would incorrectly replace the nitrogen one-centre parameters. For one isolated C=N pair, the dimensionless matrix iswhose eigenvalues are . Since , the occupied bonding molecular orbital has energy . Two doubly occupied C=N bonds and one doubly occupied C=C bond consequently giveTherefore the signed delocalization energy isThe positive stabilization is , smaller than the benzene value in the stated model but still stabilizing.
Pyrazine is aromatic: its planar cyclic conjugated system contains six electrons and has a filled set of three bonding molecular orbitals. Each ring nitrogen contributes one electron; its in-plane lone pair is outside this system. The heteroatoms change orbital energies and coefficients without interrupting cyclic conjugation or the count. Aromaticity does not require the stabilization to equal benzene's.
The cyclic amino sugar equilibrates with its open-chain -amino aldehyde. Two such units condense head-to-tail: each amino group adds to the other unit's aldehyde, followed by dehydration to the cyclic bis-imine/dihydropyrazine system. Formula accounting identifies the observed intermediate:This corresponds to , so the accumulating intermediate has lost two waters but has not yet acquired the fully aromatic pyrazine oxidation state. The unchanged portions of both carbon chains become the substituents on opposite ring carbons.
Dehydrogenative aromatization gives B, retaining both hydroxylated side chains and releasing H: the intermediate loses two hydrogen atoms to reach , mass 320. A competing elimination of the hydroxyl group immediately adjacent to the ring in one side chain, with loss of a ring-adjacent proton, gives an exocyclic unsaturated intermediate. Proton transfers shift that unsaturation into the ring and leave a deoxygenated side-chain methylene. This dehydrative aromatization gives A, formally , rather than requiring a separate unexplained reducing agent. Both pathways gain aromatic stabilization, while only the dehydrogenative branch requires H release. The acid/base proton-transfer steps can proceed through several tautomeric representations; mass balance distinguishes the two net branches.