Regioselective alkylation of the lower rim ofp-tert-butylthiacalix[4]arene withN-(p-nitrophenyl)-α-bromoacetamide

p-tert-Butylthiacalix[4]arenes functionalized by N-(4’-nitrophenyl)acetamide and N,N-diethylacetamide fragments: synthesis and binding of anionic guests

“…The regioselective synthesis of p - tert -butylthiacalix[4]arenes partially substituted at the lower rim, is an important challenge because it allows the sequential functionalization of the macrocyclic platform with the necessary substituents. It was shown in acetonitrile using the weak base Na 2 CO 3 that p - tert -butylthiacalix[4]arene 2 , 1,3-disubstituted at the lower rim, is formed with a low yield of 50% [ 42 ]. We estimated the effect of various reagent ratios for increasing the yield of the major product.…”

“…Previously, our scientific group showed that 2-bromo- N -(4’-nitrophenyl)acetamide is the regioselective alkylating reagent for p - tert -butylthiacalix[4]arene. In these reactions, derivatives of thiacalix[4]arene variously substituted at the lower rim form 1,2-, 1,3-di- and trisubstituted macrocycles [ 42 ], depending on the nature of the alkali metal carbonates and solvent. In this paper, we describe the regioselective synthesis of p - tert -butylthiacalix[4]arene monosubstituted at the lower rim by N , N -diethylacetamide fragment and its further functionalization with the N -(4’-nitrophenyl)acetamide moiety.…”

Pentakis-Amidothiacalix[4]arene Stereoisomers: Synthesis and Effect of Central Core Conformation on Their Aggregation Properties

“…Pentakis-amidothiacalix [4] [4]arene (10). In the round bottom flask equiped with magnetic stirrer and reflux condenser, 1 g (0.86 mmol) of 5,11,17,23-tetra-tert-butyl-25,26,27-tribenzoxy-28-[2'-(N-phthalimide)ethoxy]-2,8,14,20-tetrathiacalix[4]arene 9, 1.07 ml (21.49 mmol) of hydrazine hydrate, 25 ml of tetrahydrofurane and 25 ml of ethanol were mixed.…”

“…[1][2][3][4][5][6] Thiacalixarene is a readily available macrocyclic platform with great potential for further functionalization. [7][8][9][10][11][12][13][14][15][16] The ability to partial functionalization of the macrocycle [17][18][19] as well as the existence of different spatial isomers make thiacalixarenes essential blocks in the synthesis of selfassembled supramolecular systems, e.g., one-dimensional fibres [20] (supramolecular polymers), two-dimensional sheets [21,22] (vesicles or self-assembled monolayers on surfaces) and three-dimensional solids (metal-organic frameworks). [23] Besides supramolecular polymerization [20] realized with thiacalixarenes and calixarenes via various endoreceptoric/ exoreceptoric binding motifs, the possibility of development of new structures by combination of various cyclophanebased binding sites, i.e., multicyclophanes where the central core and peripheral groups have different recognition patterns, is of great interest.…”

Thiacalix[4]arene’s Lower Rim Derivatives: Synthesis and Supramolecular Properties

“…[60] Scheme 3. 72: R=CH 3 ; [62] 73: R=CH 2 COOEt; [63] 74: R=CH 2 COOH; [63] 75: R=CH 2 C 6 H 5 ; [64] 76: R=CH 2 CN; [65] 77: R=CH 2 CONHC 6 H 4 NO 2 ; [66] 78: R=(CH 2 ) n Y; [67] 79: R=(CH 2 ) n СH 3 (n=3, 7, 13); [68] 80: R=(CH 2 ) 2 SMe; [69] 81: R=(CH 2 ) 2 SBz; [69] 82: R=(CH 2 ) 3 Set; [69] 83: R=diynyl=CH 2 C≡C-C≡C-C 6 H 5 ; [70] 84: R=CH 2 COC 6 H 5 ; [71] 85: R=C 3 H 7 .…”