Gas-Phase and Solution Studies of Three Resorcin[4]Arene Derivatives Using Electrospray Time-of-Flight Mass Spectrometry

Electrospray ionisation mass spectrometry (ESI-MS) has been used to study the relative gas-phase proton and alkali metal (Li, Na, K and Cs) binding affinities of three different resorcin[4]arenes using the kinetic method. Collision-induced dissociation (CID) was used to study the fragmentation of resorcin[4]arene heterodimer sandwich complexes, allowing the relative binding affinity order to be established. All the alkali metal cations have the same gas-phase binding affinity order with the resorcin[4]arene host molecules. At collision energies of ≥ 13 eV, one of the [resorcin[4]arene + Metal]+, (Metal = Li, Na, K) ions fragmented through break-up of the resorcin[4]arene, whilst the other host resorcin[4]arene remained intact, causing an apparent change in binding affinity at high collision energy. This effect was not observed with caesium, since all complex ions dissociated readily under CID by displacement of the caesium cation. The binding affinity for the protonated resorcin[4]arenes was found to be different from the alkali metal cation binding affinity because of the higher proton affinity of the nitrogen-containing resorcin[4]arenes. It is shown that resorcin[4]arenes containing an oxazine ring can be converted into a ring-opened derivative via an Eschweiler–Clarke reaction in the presence of formic acid. A second ring-opening process also occurs, including a hydrolysis reaction that results in apparent losses of 12 mass units from the intact resorcin[4]arene. Both these reactions occur in solution before mass spectrometric investigation and cannot be achieved by CID. This observation was confirmed by inducing the Eschweiler–Clarke reaction in a model benzoxazine compound.