New synthetic approach to aminoethoxy derivatives of p-(tert-butyl)calix[4]arene

Abstract

A new procedure has been proposed for the synthesis of mono-and bis(2-aminoethoxy)-p-(tertbutyl)calix [4]arenes from the corresponding mono-and bis[2-(1,3-dioxoisoindol-2-yl)ethoxy]-p-(tert-butyl)-calix[4]arenes.Modification of calixarenes at the lower rim via introduction of amino groups linked to the phenol fragments of the macrocycle through carbon chains with different lengths could give rise to various complexones capable of binding cations, anions, and neutral species, as well as to biologically active substances.A known procedure for the synthesis of 2-aminoethoxy derivatives of p-(tert-butyl)calix [4]arene (І) is based on reaction of the latter with bromoacetonitrile in the presence of potassium carbonate under the conditions ensuring formation of disubstituted products, followed by reduction of the cyano groups with lithium tetrahydridoaluminate [1][2][3]. Derivatives of 2-alkylisoindole-1,3-diones were used to obtain analogous compounds in which the aminoalkoxy fragment includes more than two carbon atoms. In such a way both diand tetra-substituted aminoalkoxy calix[4]arenes were synthesized [4,5]. We have found no published data on the synthesis of aminoethoxy derivatives of p-(tertbutyl)calix[4]arene with the use of N-(2-bromoethyl)-phthalimide as alkylating agent. Therefore, we made an attempt to develop a procedure for the preparation

Bifunctional Receptor Based on Calix[4]arene with Chromone Groups as An Efficient Colorimetric Sensor for Co2+, Cu2+, CN− and F−

“…The designed chemosensors L1, L2 and L3 were synthesized via a five-step route as depicted in scheme 1-3, some of the precursors of which have already been reported. [29,[39][40][41][42][43][44][45][46] Desired products (L1-L3) were obtained for the reaction of isothiocyanates compounds with hydrazine hydrate, followed by the reaction of condensation with 3-formylchromone. Details of the synthetic routes of the receptors (L1 and L2) modified in the lower rim are outlined in scheme 1 and 2.…”

Supramolecular Handshakes: Characterization of Urea‐Carboxylate Interactions Within Calixarene Frameworks

“…The synthesis of the calix[4]arene derivative 1 (Scheme 2) began with the introduction of two ethyl‐phthalimido groups to the distal positions of p ‐ tert ‐butylcalix[4]arene ( P ) at the lower rim [73–76] . To the other two hydroxyl groups of calix[4]arene, simple tertiary amides were attached via nucleophilic substitution with 2‐bromo‐ N,N ‐diethylacetamide, according to a known procedure [77] .…”

“…The synthesis of the calix [4]arene derivative 1 (Scheme 2) began with the introduction of two ethyl-phthalimido groups to the distal positions of p-tert-butylcalix [4]arene (P) at the lower rim. [73][74][75][76] To the other two hydroxyl groups of calix [4]arene, simple tertiary amides were attached via nucleophilic substitution with 2-bromo-N,N-diethylacetamide, according to a known procedure. [77] Phthalimido groups on the resulting calix [4]arene P3 (Figures S1 and S2) were then removed using hydrazine to obtain diamine compound P4 (Figures S3 and S4).…”

Synthesis and Anticonvulsant Evaluation of New Calix[4]arene Derivatives Containing Gamma-Aminobutyric Acid Moieties

“…Ñ öåëüþ ââåäåíèÿ â ìîëåêóëó êàëèêñàðåíà çàìåñòèòåëÿ, ñîäåðaeàùåãî N-êîíöåâóþ àìèíîêèñëîòó, áûëè ñèíòåçèðîâàíû èñõîäíûå ìîíî-I è äèçàìåùåííûå II (àìèíîýòîêñè)-n-òðåò-áóòèëêàëèêñ [4]àðåíû ïî ìåòîäèêå [14]. Ñîåäèíåíèÿ III è IV áûëè ïîëó÷åíû ïðè âçàèìîäåéñòâèè àìèíîñîäåðaeàùèõ êàëèêñ [4]àðåíîâ ñ Boc-çàùèùåííîé àìèíîêèñëîòîé (ïðîìåaeóòî÷íûå ïðîäóêòû I¢ è II¢) ñ ïîñëåäóþùèì óäàëåíèåì çàùèòíîé ãðóïïû îáðàáîòêîé òðèôòîðóêñóñíîé êèñëîòîé (ñõåìà 1).…”