A carbonylative coupling approach to alkyl stationary phases with variable embedded carbamate groups for high-performance liquid chromatography

A highly efficient carbonylative coupling method for the preparation of alkyl stationary phases with variable numbers of carbamate groups was established. The effectiveness of such method was verified through elemental analysis, X-ray photoelectron spectroscopy and solid-state C-13 nuclear magnetic resonance spectroscopy of three as-synthesized stationary phases bearing different alkyl chains and different numbers of carbamate groups (octadecyl/one carbamate group, C18C; docosyl/three carbamate groups, C22C(3); triacontyl/two carbamate groups, C30C(2)). The comparative evaluation of these stationary phases using a great variety of analytes, including three sets of isomers of alkylbenzenes, two sets of standard mixtures of polycyclic aromatic hydrocarbons (SRM 1647e and 869b), nine polychlorinated biphenyls, fiveteen N-substituted ureas, ten sulfonylureas, five xanthines and some other phytonutrients, revealed their remarkable applicability in reversed-phase liquid chromatography. Notably, the intercalated carbamate groups rendered the resultant stationary phases compatible with 100% aqueous mobile phase. The suppression of silanol activity was positively related to the number of polar groups embedded in the bonded selector, and the smallest peak tailing factor (1.14) for amitriptyline was obtained by C22C(3). The molecular shape-related selectivity was found to be more closely related to the length of the selector's aliphatic chain, as supported by the lowest alpha(TBN/Bap) value (0.31) by C30C(2). These carbamate-embedded alkyl stationary phases constituted another class of polar-embedded stationary phases possessing a single type of functional ligand. (C) 2021 Elsevier B.V. All rights reserved.

Automated summary

A highly efficient carbonylative coupling method was established for preparing alkyl stationary phases with variable numbers of carbamate groups. The as-synthesized stationary phases showed remarkable applicability in reversed-phase liquid chromatography with a wide range of analytes, and were compatible with 100% aqueous mobile phase.