ATOMIC FORCE MICROSCOPY AND SOLID-STATE REARRANGEMENT OF BENZOPINACOL

Article abstract of DOI:10.1002/poc.610080805

The solid-solid chemical reaction of benzopinacol (1) with p-toluenesulphonic acid monohydrate (2) to give a quantitatively proton-catalysed pinacol rearrangement with formation of triphenylacetophenone (3) in the absence of a solvent was studied preparatively and mechanistically using atomic force microscopy (AFM) measurements and known crystal structure data.The reaction rate is dramatically enhanced if the water of reaction is continuously removed.AFM reveals that no reaction occurs on (001) of 1 whereas (100) exhibits distance dependent craters and volcano-like mounds over areas extending to 1.5 mm from the contact edge of the crystal with 1 undergoing phase rebuilding while reacting.A mechanism resembling the formation of membrane potentials is seen for the first time in crystals.This it appears that catalytic protons migrate without their counterions from one molecular compartment to the next by proton consumption at its inside and proton liberation at its outside, which is the inside of the next compartment.The uppermost molecular layer determines reactivity or non-reactivity.On (001) of 1 the hydroxyl groups occur with their hydrogens up.Hence no AFM features are found and crystals of 2 do not become adhered to 1.However, on (100) the hydroxyl hydrogens point down (free electron pair up).Protonation is possible, chemical reaction is indicated by the formation of the AFM features and crystals of 2 adhere firmly to the surface of 1 after reaction.