IDENTIFICATION OF CYCLOBUTANE-TYPE DIMERS OF SUBSTITUTED CINNAMIC-ACIDS BY GAS-CHROMATOGRAPHY MASS-SPECTROMETRY

Substituted cinnamic acids were dimerized, under fluorescent or UV light, as a glassy coating on a vial then subsequently analysed by GC/MS. Mass spectrometric analysis of the dimers formed by each acid allowed the assignment of the dimer as a truxillic or truxinic structure since these structures had distinctive fragmentation patterns; the breakdown of the truxillic acids involves a McLafferty rearrangement before fragmentation occurs, whereas the truxinic acids, which have both carboxy groups on one side and both aromatic groups on the other, fragment asymmetrically to give characteristic stilbene and dicarboxylate fragments. It is apparent from the results of the dimerization of the cinnamic acids that, under the conditions used here, if the monomeric acid had the capacity for hydrogen bonding using the ring substituent as well as the carboxy group, the dimerization products would be overwhelmingly truxillic in structure. However, if only the carboxy group could hydrogen bond, the products would be almost exclusively truxinic in structure.