Probing the Pyrolysis of Guaiacol and Dimethoxybenzenes Using Collision-Induced Dissociation Charge-Remote Fragmentation Mass Spectrometry.

The dissociation of lignin model compounds has been examined using mass spectrometry and collision-induced dissociation charge-remote fragmentation (CID-CRF). The model compounds guaiacol and - and -dimethoxybenzene containing a remote sulfonate (SO) charge group undergo CID by dissociation without the involvement of the anionic group. The first dissociation for all three compounds is loss of methyl radical to form phenoxy radicals. Subsequent dissociation pathways depend on the specific structures being examined The dissociation pathways are compared to those observed upon gas-phase pyrolysis that have been reported previously. While the pathways are largely similar, there are some important differences that are explained by changes in dissociation barriers due to the effect of adding the charged group. This work shows that CID-CRF is an effective approach for tracking the thermolysis of lignin model compounds while eliminating secondary reactions that normally convolute such studies.