Synthesis of Monothiacalix[4]arene Using the Fragment Condensation Approach

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F25%3A43932855" target="_blank" >RIV/60461373:22310/25:43932855 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/60461373:22810/25:43932855

Výsledek na webu

<a href="https://www.mdpi.com/1420-3049/30/15/3145" target="_blank" >https://www.mdpi.com/1420-3049/30/15/3145</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.3390/molecules30153145" target="_blank" >10.3390/molecules30153145</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Synthesis of Monothiacalix[4]arene Using the Fragment Condensation Approach

Popis výsledku v původním jazyce

The article describes a simple and scalable preparation of 2-monothiacalix[4]arene 7, the simplest representative of the mixed-bridged (CH&lt;inf&gt;2&lt;/inf&gt; and S) calix[4]arenes. The synthesis is based on the condensation of linear building blocks (bisphenols), which are relatively readily available, and allows, depending on the conditions, the use of two alternative reaction routes that provide macrocycle 7 in high yield. The dynamic behavior of the basic macrocyclic skeleton was investigated using NMR spectroscopy at variable temperatures. High-temperature measurements showed that compound 7 undergoes a cone–cone equilibrium with activation free energy ΔG# of the inversion process of 63 kJ·mol−1. Interestingly, the same barrier for the oxidized sulfone derivative 14 shows a value of 60 kJ·mol−1, indicating weakened hydrogen bonds at the lower rim of the calixarene. The same was also confirmed at low temperatures, when barriers to changing the direction of the cyclic hydrogen bond arrays (flip-flop mechanism) were determined (compare ΔG# = 44 kJ·mol−1 for 7 vs. ΔG# = 40 kJ·mol−1 for 14). © 2025 by the authors.

Název v anglickém jazyce

Synthesis of Monothiacalix[4]arene Using the Fragment Condensation Approach

Popis výsledku anglicky

The article describes a simple and scalable preparation of 2-monothiacalix[4]arene 7, the simplest representative of the mixed-bridged (CH&lt;inf&gt;2&lt;/inf&gt; and S) calix[4]arenes. The synthesis is based on the condensation of linear building blocks (bisphenols), which are relatively readily available, and allows, depending on the conditions, the use of two alternative reaction routes that provide macrocycle 7 in high yield. The dynamic behavior of the basic macrocyclic skeleton was investigated using NMR spectroscopy at variable temperatures. High-temperature measurements showed that compound 7 undergoes a cone–cone equilibrium with activation free energy ΔG# of the inversion process of 63 kJ·mol−1. Interestingly, the same barrier for the oxidized sulfone derivative 14 shows a value of 60 kJ·mol−1, indicating weakened hydrogen bonds at the lower rim of the calixarene. The same was also confirmed at low temperatures, when barriers to changing the direction of the cyclic hydrogen bond arrays (flip-flop mechanism) were determined (compare ΔG# = 44 kJ·mol−1 for 7 vs. ΔG# = 40 kJ·mol−1 for 14). © 2025 by the authors.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

MOLECULES

ISSN

1420-3049

e-ISSN

1420-3049

Svazek periodika

30

Číslo periodika v rámci svazku

15

Stát vydavatele periodika

CH - Švýcarská konfederace

Počet stran výsledku

15

Strana od-do

"27 July 2025"

Kód UT WoS článku

001549453400001

EID výsledku v databázi Scopus

2-s2.0-105013297852