The Use of Anhydrous Barium Hydroxide for Selective Alkylation of Dialkyloxy-tert-butyl-calix[4]arenes.

A practical method of selective alkylation of the third hydroxyl group of disubstituted tert-butyl-calix[4]arenes using anhydrous barium hydroxide as a base was developed in this study. The use of this method in the synthesis of inherently chiral derivatives is shown herein.

Synthesis and separation of diastereomeric N-(1-phenylethyl)amides of inherently chiral hydroxydibenzoyloxy-calix[4]arene acetic acids.

A preparative method for the synthesis of optically pure N-(1-phenylethyl)amides of inherently chiral (cR)- and (cS)-dibenzoyloxy-calix[4]arene acetic acids has been developed. Their absolute stereochemical configuration was determined by X-ray diffraction analysis.

Recognition of 1-phenylethylamine enantiomers by thin solid films of inherently chiral calix[4]arene.

The enantiodiscrimination properties of stereomerically pure inherently chiral calix[4]arene acetic acids, as well as their esters and amides in relation to 1-phenylethylamine stereoisomers in liquid and gaseous phases were studied by means of proton magnetic resonance spectroscopy (1 H NMR) and quartz crystal microbalance (QCM) techniques. Series of QCM sensors with thin films of inherently chiral calix[4]arenes, immobilized on the quartz resonator surfaces by spin-coating and spreading drop methods have been fabricated. It was shown that sensors based on calix[4]arene acetic acids are able to recognize R- and S-forms of 1-phenylethylamine in gaseous phase under concentration level of 10-400 ppm.

Inherently chiral dialkyloxy-calix[4]arene acetic acids as enantiodiscriminating additives for high-performance liquid chromatography separation of d,l-amino acids.

Inherently chiral dialkyloxy-calix[4]arene acetic acids with asymmetric placement of substituents on the lower rim of the macrocycle were first studied as enantiodiscriminating additives to the mobile phase MeCN/H2 O/HCOOH (75/25/0.02 by volume) in the high-performance liquid chromatography (HPLC) separation of d,l-alanine and d,l-valine on the achiral stationary phase ZORBAX Original CN. The dependence of enantio-binding properties on the position of alkyl groups is demonstrated. The highest resolution (1.65) and enantioselectivity (1.80) were obtained for the 1,2-dipropyloxy-calix[4]arene acetic acid.