Atomic force microscopy (AFM) has been used to study the effect of pressure on the structural and frictional properties of self-assembled monolayers of n-octadecanethiol on Au(111). Sharp microfabricated silicon nitride tips (tip radii 100-300 Angstrom) were used. At low load, the periodicity of the thiol layer is imaged. At higher load, the layer is observed to become disordered. At a critical contact pressure of similar to 2.3 GPa, a transition from the thiol overlayer to the Au(111) substrate periodicity is observed in the lattice resolution images. This transition is gradual and reversible. During the transition, frictional forces first increase and then decrease as the tip-sample separation decreases by a distance approximately equivalent to the thickness of the thiol layer.