Recognition and resolution of isomeric alkyl anilines by mass spectrometry

Two MS techniques have been used to recognize and resolve a representative isomeric pair of N-alkyl and ring-alkyl substituted anilines. The first technique (1) uses MS/MS to perform ion/molecule reactions of structurally-diagnostic fragment ions (SDFI) whereas the second (2) uses traveling wave ion mobility spectrometry (TWIMS) of the pair of protonated molecules followed by on-line collision-induced dissociation (CID), that is, MS/TWIMS-CID/MS. Isomeric C(7)H(7)N(+) ions of m/z 106 (1' from 4-butylaniline and 2 from N-butylaniline) are formed as abundant fragments by 70 eV EI of the anilines, and found to function as suitable SDFI. Ions 1' and 2 display nearly identical unimolecular dissociation chemistry, but contrasting bimolecular reactivity with ethyl vinyl ether, isoprene, acrolein, and 2-methyl-1,3-dioxolane. Ion 2 forms adducts to a large extent whereas 1' is nearly inert towards all reactants tested. The intact protonated anilines are readily resolved and recognized by MS/TWIMS-CID/MS in a SYNAPT mass spectrometer (Waters Corporation, Manchester, UK). The protonated N-butyl aniline (the more compact isomer) displays shorter drift time and higher lability towards CID than its 4-butyl isomer. The general application of SDFI 1' and 2 and other homologous and analogous ions and MS/TWIMS-CID/MS for absolute recognition and resolution of isomeric families of N-alkyl and ring-alkyl mono-substituted anilines and analogues is discussed.