New chiral stationary phases based on (R)-1-naphthylethylamine bound to 2,4,5,6-tetrachloro-1,3-dicyanobenzene.

Chiral functionalization of 2,4,5,6-tetrachloro-1,3-dicyanobenzene (1) by regioselective nucleophilic substitution of one or two chlorine atoms by optically pure (R)-(+)-1-naphthylethylamine (NEA), or by a glycine unit as a spacer to (R)-NEA, enables the preparation of brush-type chiral selectors (2, 3, 9, 13). By the introduction of the 3-aminopropyltriethoxysilyl (APTES) group, reactive intermediates 4a/b, 5, 10a/b, and 14a/b are obtained (a/b indicate a mixture of regioisomers with APTES in 6- and 2-position). Binding of these to silica gel afforded four novel chiral stationary phases (CSPs) 6, 7, 15, and 16. HPLC columns containing CSPs with (R)-NEA directly linked to polysubstituted aromatic ring (6, 7) are not very effective in resolution of most of the 23 racemic analytes, whereas the columns with distant pi-basic subunits (15, 16) exhibited higher resolving efficacy, in particular towards the isopropyl esters of racemic N-3,5-dinitrobenzoyl-alpha-amino acids. Effective resolution of test racemates reveals the importance of the presence of the hydrogen bond donor amido group and the distance between the persubstituted benzene ring in 1 and the pi-basic naphthalene ring of (R)-NEA. Copyright 1999 Wiley-Liss, Inc.