The chromatographic study of complexation of functionalized calix[4,8]arenes with aromatic aldehydes

O I Kalchenko,O I Kalchenko,S O Cherenok,A V Solovyov

doi:10.24959/ophcj.19.958

Abstract

Aim. To study the Host-Guest complexation of octakis(diphenoxyphosphoryloxy)-tetramethylcalix[4]resorcinarene ( PRA) , 5,17-bis(N-tolyl-iminomethyl)-25,27-dipropoxycalix[4]arene ( IC4A ), 5,11,17,23-tetrakis(diisopropoxyphosphonyl)-25,26,27,28-tetra-propoxycalix[4]arene ( PC4A ) and oktakis(diethoxyphosphoryloxy)-tert-butylcalix[8]arene ( PC8A ) with benzaldehyde, salicylaldehyde, p- anisaldehyde , and veratraldehyde by RP HPLC and molecular modeling methods. Results and discussion. The stability constants of Host-Guest complexes ( K A = 57 M -1 – 1649 M -1 ) strongly depend on the calixarene structure and the aromatic aldehyde nature. The enhancement of the complexing properties of calixarenes is observed in the row of PRA < IC4A < PC4A < PC8A. The volume of the calixarene molecular cavity plays the most important role in binding of aldehydes. Experimental part . The stability constants of calixarene complexes with aldehydes were determined by RP HPLC method in acetonitrile-water (80 : 20, v/v) solution. The RP HPLC analysis was performed using a LiChrosorb RP-18 column. Molecular modeling of calixarene complexes was carried out using a Hyper Chem 8.0 program. Conclusions . The Host-Guest complexation data can be used as a useful tool in design of calixarene based sensor devices for determination of the aromatic aldehydes in air or preparation of chromatographic phases for analysis of aldehydes in solutions.

Highlights

Since the aromatic aldehydes are widely used as starting materials or aromatic ingredients in pharmaceutical and cosmetics industry [18, 19], the HostGuest complexation data can be used as a useful tool in design of calixarene based sensor devices for determination of the aromatic aldehydes in air or preparation of chromatographic phases for analysis of compounds in solutions
Complexation of the calixarenes with aldehydes was studied in the acetonitrile-water solution by the RP HPLC method using the approach previously developed [20, 21]
The stability constants of calixarene complexes were calculated from the dependence of the aldehyde retention factor on the concentration of calixarenes in the mobile phase

Summary

Results and discussion

Complexation of the calixarenes with aldehydes was studied in the acetonitrile-water solution by the RP HPLC method using the approach previously developed [20, 21]. The stability constants of calixarene complexes were calculated from the dependence of the aldehyde retention factor on the concentration of calixarenes in the mobile phase. In the IC4A complex, the molecule of salicylaldehyde is included into the molecular cavity of the calixarene In this case, the aldehyde hydroxyl group forms a hydrogen bond with the OH group oxygen atom on the lower rim of the macrocycle (O-H···O distance 2.84 Ǻ). The lengths of hydrogen bonds O-H···O=P are 2.38 Ǻ for the PC4A complex and 2.87 Ǻ for the PC8A complex The UV detector was operated at 254 nm, and the flow rate was

Conclusions