Kinetics of the Stepwise Hydrolysis of Mononitrofluorescein Diacetates in Organized Solutions

doi:10.26565/2220-637X-2026-46-04

Daria Kharchenko V. N. Karazin Kharkiv National University, 4 Svobody sq., 61022 Kharkiv, Ukraine https://orcid.org/0000-0002-7134-1545
Sergey Shekhovtsov V. N. Karazin Kharkiv National University, 4 Svobody sq., 61022 Kharkiv, Ukraine https://orcid.org/0000-0002-1519-1669
Tatyana Cheipesh V. N. Karazin Kharkiv National University, 4 Svobody sq., 61022 Kharkiv, Ukraine https://orcid.org/0000-0002-9709-5602
Roman Rodik Institute of Organic Chemistry, National Academy of Sciences of Ukraine, 5 Akademika Kuharya str., 02094 Kyiv, Ukraine https://orcid.org/0000-0003-2258-6957
Vitaliy Kalchenko Institute of Organic Chemistry, National Academy of Sciences of Ukraine, 5 Akademika Kuharya str., 02094 Kyiv, Ukraine https://orcid.org/0000-0002-0325-7544

DOI: https://doi.org/10.26565/2220-637X-2026-46-04

Keywords: mononitrofluorescein, ester hydrolysis, micellar catalysis, cationic calixarenes, organized solutions, host-guest recognition

Abstract

The kinetics of the stepwise alkaline hydrolysis of three isomeric mononitrofluorescein diacetates, containing the nitro group in the residue of the phthalic acid, were investigated in water and organized aqueous solutions of cationic surfactants and a cationic calix[4]arene. The reaction follows a consecutive two-stage mechanism involving the formation of a spectroscopically distinguishable monoacetate intermediate. UV-visible spectrophotometric monitoring allowed for the separate determination of the pseudo-first-order rate constants for both hydrolytic steps. The catalytic efficiency of the organized systems was found to increase in the order: cetyltrimethylammonium bromide (CTAB) < N,N-dimethyl-N-hydroxyethyl-4-dodecyloxybenzylammonium chloride (C₁₂-Bn-Ch) < 5,11,17,23-Tetra(N,N-dimethyl-N-hydroxyethylammonium)methylene-25,26,27,28-tetradodecyloxy calix[4]arene tetrachloride (C₁₂-C4A-Ch), with acceleration factors reaching nearly three orders of magnitude for the 3'-nitro derivative. The positioning of the nitro substituent markedly influenced the relative rates of the two hydrolysis stages, with the k₂’/k₁' ratio being governed by the interplay between intrinsic electronic effects and the nature of the organized environment. These results suggest that supramolecular assemblies based on calixarene derivatives provide a highly efficient microenvironment for ester hydrolysis, likely through a synergy between specific host-guest recognition within the macrocyclic cavity and collective electrostatic effects at the aggregate interface.

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