On- and off column enantiomerization of 4,4'-bisquinolin-2-ones: A comparison of Auto-, DHPLcy2k and DCXplorer calculated thermodynamic data generated by dynamic high, performance liquid chromatography with theoretically calculated data.
Fast semipreparative HPLC enantioseparation of four axially chiral biscarbostyrils (4,4'-bisquinoline-2-ones) using ULMO as a pi-acidic Pirkle type chiral stationary phase leads to two racemizing pairs (1,2; k(obs) 1.6x10(-4) and 3.0x10(-4)s(-1) at 28 degrees C) and two stable ones (3,4). 3 was stabilized by a crown ether linkage from pos. 6 to 6', and 4 had sterically demanding bromo substituents in pos. 3 and 3'. On-column generated temperature-dependent chromatograms of 1 and 2 were fitted with Auto-DHPLCy2k and DCXplorer. For cpd 2 both programs delivered similar DeltaG values of 90 and 93kJ/mol, well comparable with the 99kJ/mol calculated with the B3LYP/6-31G (d) procedure. At temperatures of high conversion DCXplorer delivered inconsistent series of rate constants for the more tailing and less resolved tetramethoxy derivative 1. We connect this problem with an almost impossible halfwidth calculation of tailing peak pairs which are weakly resolved. However, this problem could be observed only in the case of tetramethoxy derivative 1. Stochastic generated data of Auto-DHPLCy2k could be used at a lower percentage of conversion only while the theoretical plate model did not deliver useful data at temperatures of very low conversion but fitted well high conversion chromatogram series of 1 and 2.
Uray
Georg
G
Institut für Chemie, Karl-Franzens Universität Graz, Heinrichstr. 28, 8010 Graz, Austria. uray@uni-graz.at
Jahangir
Sajid
S
Fabian
Walter M F
WM
D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D002942:Circular Dichroism; D016014:Linear Models; D008962:Models, Theoretical; D015363:Quinolones / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics
D015363:Quinolones