Mass spectral studies of meso-dialkyl, alkyl aryl and cycloalkyl calix(4)pyrroles under positive and negative ion electrospray ionization conditions.
A series of meso-dialkyl, alkyl aryl and cycloalkyl calix(4)pyrroles (1-15) are studied under positive and negative ion electrospray ionization (ESI) conditions. The positive ion spectra show abundant [M + H](+) and [M + Na](+) ions and the negative ion spectra show the [M + Cl](-) (the Cl(-) ions from the solvent) and [M - H](-) ions. The collision induced dissociation (CID) spectra of [M + H](+), [M + Na](+), [M + Cl](-) and [M - H](-) ions are studied to understand their dissociation pathway and compared to that reported for M(+) under electron ionization (EI) conditions. The beta-cleavage process that was diagnostic to M(+) is absent in all the CID spectra of the ions studied under ESI. Dissociation of all the studied ions resulted in the fragment ions formed by sequential elimination of pyrrole (A) and/or dialkyl/alkyl aryl/cycloalkyl (B) groups involving hydrogen migration to pyrrole ring at each cleavage of A--B bond, which clearly reveals the arrangement of A and B groups in the calix(4)pyrroles. The source of hydrogen that migrates to pyrrole ring during A--B bond cleavage is investigated by the experiments on deuterated compounds and [M + D](+) ions; and confirmed that the hydrogen attached to pyrrole nitrogen, hydrogen on alpha-carbon of alkyl group and the H(+)/Na(+) ion that added during ESI process to generate [M + H](+)/[M + Na](+) ions involve in the migration. The yields of [M + Na](+) ions are found to be different for the isomeric meso-cycloalkyl compounds (cycloheptyl, and 2-, 3- and 4-methyl cyclohexyl) and for normal and N-confused calix(4)pyrroles. The isomeric methyl and 3-hydroxy/4-hydroxy phenyl calix(4)pyrroles show specific fragmentation pattern during the dissociation of their [M - H](-) ions.
Bhaskar
G
G
National Centre for Mass Spectrometry, Indian Institute of Chemical Technology, Hyderabad, India.
Prabhakar
S
S
Ramanjaneyulu
G S
GS
Vairamani
M
M
Srinivasu
V N V
VN
Srinivas
K
K