GC–MS and GC–IR of regioisomeric 4-N-bromodimethoxybenzyl derivatives of 3-trifluoromethylphenylpiperazine

Abstract

The seven regioisomeric N-bromodimethoxybenzyl derivatives of 3-TFMPP were synthesized via reductive amination of the seven commercially available bromodimethoxybenzaldehydes. The capillary GC elution profiles for these compounds generally follow the degree of methoxy group substituent crowding on the aromatic ring. The electron ionization mass spectra show a series of major fragment ions common to all seven regioisomeric compounds. The base peak in the EI mass spectra for many of the seven regioisomers occurs at m/z 229 and is the result of contributions from two isobaric fragments, the trifluoromethylphenylpiperazine cation as well as the 79Br bromodimethoxybenzyl cation. Several low intensity ions are related to the specific regioisomeric substitution patterns for the bromodimethoxybenzyl moieties and provide some differentiation for this set of seven compounds. These unique ions allow the seven compounds to be divided into sub-groups and in some cases allow specific isomer identification from only the EI-MS data. The 950 cm−1 to 550 cm−1 lower portion of the fingerprint region in the vapor phase infrared spectra can be used to identify each of the bromodimethoxybenzyl regioisomers after EI-MS fragmentation patterns provide focus on the individual structural sub-groups of compounds in this study.