Probing the Stereointegrity of Tröger's Base—A Dynamic Electrokinetic Chromatographic Study

✍ Scribed by Oliver Trapp; Gabriele Trapp; Jingwu Kong; Uwe Hahn; Fritz Vögtle; Volker Schurig

• Publisher: John Wiley and Sons
• Year: 2002
• Tongue: English
• Weight: 143 KB
• Volume: 8
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/1521-3765(20020816)8:16<3629::aid-chem3629>3.0.co;2-8

✦ Synopsis

Under acidic conditions the enantiomers of Tröger's base 1 (2,8-dimethyl-6 H,12 H-5,11-methanodibenzo[b,f][1,5]diazozine) are subject to enantiomerization. During enantioselective dynamic electrokinetic chromatography using 10 mM hydroxypropyl-beta-cyclodextrin as the chiral mobile phase additive in 50 mM tris/phosphate buffer at pH 2.2, enantiomerization of Tröger's base gives rise to characteristic elution profiles featuring plateau formation and peak broadening. Introduction of a permanent positive charge attributed to quaternization in the monobenzylated derivative of Tröger's base 2 (5-benzyl-2,8-dimethyl-6 H,12 H-5,11-methanodibenzo[b,f][1,5]diazozinium bromide) decreases the enantiomerization barrier significantly. To determine the rate constants of enantiomerization the experimental chromatograms were evaluated by a direct calculation method and by using the computer simulation program ChromWin. From temperature-dependent measurements the Eyring activation parameters for 1 and 2 were determined: 1: DeltaG( not equal ) (298 K)=100.9+/-0.5 kJ mol(-1), DeltaH( not equal )=89.5+/-2.0 kJ mol(-1), DeltaS( not equal )=-42+/-10 J K(-1) mol(-1); 2: DeltaG( not equal ) (298 K)=90.2+/-0.5 kJ mol(-1), DeltaH( not equal )=91.4+/-2.0 kJ mol(-1), DeltaS( not equal )=9.8+/-10 J K(-1) mol(-1).