Selectively excited o-toluidine and α-methylbenzylamine have been studied with quasi-classical trajectory procedures to determine the extent and timescales of intramolecular energy flow. The initial excitation is in the stretching mode of the para-CH bond, and its flow is initiated by interaction with an argon atom. Energy flow to the NH stretching mode is the dominant relaxation pathway, and its effectiveness is enhanced strongly by the methyl-NH interaction. Energy flow characteristics in both molecules are similar, but the flow is more effective in o-toluidine than in α-methylbenzylamine because the methyl group bonded to the benzene ring exerts stronger perturbation on the energy-flow pathway than the group bonded to the side chain. The relaxation of the initially excited CH completes on a timescale of several picoseconds, but the main part of energy flow to the NH occurs on a subpicosecond scale. In o-toluidine, carbon-carbon overtone modes lead to ring-CC bonds gaining and transporting more energy than high-frequency CH bonds, but they all gain far less energy than the NH stretching mode.