An Efficient Synthesis of Bis(calix[4]arenes), Bis(crown ether)-Substituted Calix[4]arenes, Aza-Crown Calix[4]arenes, and Thiaza-Crown Calix[4]arenes

Abstract

The easy transformation of 5,11,17,23-tetra-tert-butyl-25,27bis(aminoethoxy)-26,28-dihydroxycalix[4]arene(2) into 5, 11,17,23-tetra-tert-butyl-26,28-dihydroxy-25,27-bis(2-isothiocyanoethoxy)calix[4]arene (3) and 5,11,17,23-tetra-tertbutyl-25,27-bis(chloroacetamidoethoxy)-26,28-dihydroxycalix[4]arene (4) has been exploited for the development of an efficient and expeditious synthesis of a variety of calix[4]3587 calix[4]arenes]. The functionality of compounds 2 and 3 allowed the formation of intramolecular bridges, leading to capped calix[4]arenes (compounds 5, 10, and 14) as well as to the construction of double calix[4]arene units by means of spacers containing thiourea or amide-sulfur groups (compounds 6 and 15, respectively). In addition, the bis(isothiocyanate) derivative 3 gave access to a high-yield preparation of heteroditopic bis(crown ether) calix[4]arenes (7−9) from commercial amino crown ethers.

Bifunctional Receptor Based on Calix[4]arene with Chromone Groups as An Efficient Colorimetric Sensor for Co 2+ , Cu 2+ , 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.…”

Bifunctional Receptor Based on Calix[4]arene with Chromone Groups as An Efficient Colorimetric Sensor for Co 2+ , Cu 2+ , 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.…”

Thiosemicarbazone- and Thiourea-Functionalized Calix[4]arenes in cone and 1,3-alternate Conformations: Receptors for the Recognition of Ions

“…Hydrazinolysis of diphtalimide (12) or (17) gave the derivative diamine (13) or (18) in a cone or 1,3-alternate conformation as required [55]. Then, ( 13) and (18) were transformed into the corresponding diisothiocyanate precursors ( 14) and ( 19) by a modified procedure described by Santoyo-Gonzalez [57]. Finally, the reaction of the triazolopyridine derivatives with terminal amino groups obtained by Belén et al [34][35][36] with calixarene isothiocyanate in conical and 1,3-alternate conformations in methanol, catalyzed by triethylamine, gave receptors (IV) and (V) based on calix [4]arene.…”

A Novel Ditopic Receptor and Reversal of Anion Binding Selectivity in the Presence and Absence of Bound Cation

“…The Boc protecting groups were removed using trifluoroacetic acid, and the resulting diamine was reacted with thiophosgene to give bisisothiocyanate 4 in 62% yield. Slow addition of m -xylylenediamine to a solution of 4 in pyridine, gave the desired cyclic receptor 1 , which was purified by column chromatography and obtained in 40% yield as a white solid.…”

Bifunctional Receptor Based on Calix[4]arene with Chromone Groups as An Efficient Colorimetric Sensor for Co 2+ , Cu 2+ , 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.…”

Thiosemicarbazone- and Thiourea-Functionalized Calix[4]arenes in cone and 1,3-alternate Conformations: Receptors for the Recognition of Ions

“…Hydrazinolysis of diphtalimide (12) or (17) gave the derivative diamine (13) or (18) in a cone or 1,3-alternate conformation as required [55]. Then, ( 13) and (18) were transformed into the corresponding diisothiocyanate precursors ( 14) and ( 19) by a modified procedure described by Santoyo-Gonzalez [57]. Finally, the reaction of the triazolopyridine derivatives with terminal amino groups obtained by Belén et al [34][35][36] with calixarene isothiocyanate in conical and 1,3-alternate conformations in methanol, catalyzed by triethylamine, gave receptors (IV) and (V) based on calix [4]arene.…”

A Novel Ditopic Receptor and Reversal of Anion Binding Selectivity in the Presence and Absence of Bound Cation

“…The Boc protecting groups were removed using trifluoroacetic acid, and the resulting diamine was reacted with thiophosgene to give bisisothiocyanate 4 in 62% yield. Slow addition of m -xylylenediamine to a solution of 4 in pyridine, gave the desired cyclic receptor 1 , which was purified by column chromatography and obtained in 40% yield as a white solid.…”

Bifunctional Receptor Based on Calix[4]arene with Chromone Groups as An Efficient Colorimetric Sensor for Co 2+ , Cu 2+ , 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.…”

Thiosemicarbazone- and Thiourea-Functionalized Calix[4]arenes in cone and 1,3-alternate Conformations: Receptors for the Recognition of Ions

“…Hydrazinolysis of diphtalimide (12) or (17) gave the derivative diamine (13) or (18) in a cone or 1,3-alternate conformation as required [55]. Then, ( 13) and (18) were transformed into the corresponding diisothiocyanate precursors ( 14) and ( 19) by a modified procedure described by Santoyo-Gonzalez [57]. Finally, the reaction of the triazolopyridine derivatives with terminal amino groups obtained by Belén et al [34][35][36] with calixarene isothiocyanate in conical and 1,3-alternate conformations in methanol, catalyzed by triethylamine, gave receptors (IV) and (V) based on calix [4]arene.…”

A Novel Ditopic Receptor and Reversal of Anion Binding Selectivity in the Presence and Absence of Bound Cation

“…The Boc protecting groups were removed using trifluoroacetic acid, and the resulting diamine was reacted with thiophosgene to give bisisothiocyanate 4 in 62% yield. Slow addition of m -xylylenediamine to a solution of 4 in pyridine, gave the desired cyclic receptor 1 , which was purified by column chromatography and obtained in 40% yield as a white solid.…”