The preparation and properties of a new lipophilic sodium selective ether ester ligand derived from p-t-butylcalix[4]arene

Arduini, Arturo; Pochini, Andrea; Reverberi, Sara; Ungaro, Rocco; Anreetti, Giovanni D.; Ugozzoli, Franco

doi:10.1016/s0040-4020(01)87626-2

Cited by 272 publications

(141 citation statements)

References 35 publications

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“…The yields of the octasubstitution reactions compare favorably with the yields reported for tetrasubstitution of calix [4]arenes. Yields of esters reported in the literature range from 68 to 88% (7,13,14). The yield of octa-a-(diethyl amide) was found to be higher than the yield of the esters, which is also in agreement with the literature (15).…”

Section: Synthesissupporting

confidence: 88%

Cation binding and conformation of octafunctionalized calix[4]resorcinarenes

Fransen¹,

Dutton²

1995

Can. J. Chem.

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Abstract:The preparations of four calix [4]resorcinarene esters and two calix [4]resorcinarene amides are reported. The logarithms of association constants have been determined by the picrate extraction method for a variety of metal cations, including alkali metal, alkaline earth, lanthanum, and silver cations. Strong binding toward silver ion, and selectivity amongst the alkaline earth cations, was observed for the octa-a-(diethyl acetamide) 3c. Flattened cone conformations have been established for both C-undecylcalix[4]resorcinarene octa-a-(methyl acetate), 3a, and octa-a-(diethyl acetamide), 3c, in chloroform solutions at 200 K. Dynamic nuclear magnetic resonance was used to identify rapid conformational interconversions of both 3a and 3c corresponding to pseudorotation between flattened cone conformations. The silver complex of 3c also exhibits pseudorotation; however, the activation barrier was observed to increase from 42 W mol-I in the free ligand to 49 kJ mol-' in the complex. The NMR data indicate that the metal cation binding occurs in a symmetrical fashion using two pairs of binding sites that are disposed across the macrocyclic ring from one another. Considering these data it is concluded that four carbonyl functions are involved in the binding of a metal cation in a 1: 1 complex with the ligand. variCtC de cations metalliques, y compris ceux de l'argent, des mCtaux alcalins et alcalino-terreux et de la sene des lanthanides. Avec I'octa-a-(diethyl acCtamide), 3c, on aobservk que lesions de l'argent sont fortement fixes et qu'il existe une grande sClectivitC parmi les cations des alcalino-terreux. On a Ctabli que, en solutions dans le chloroforme a 200 K, le C-und6cylcalix[4]r6sorcinarbne octa-a-(acetate de mCthyle), 3a, ainsi que I'octa-a-(dikthyl acCtamide), 3c, ont tous les deux des conformations coniques aplaties. On a utilisC la resonance magnetique nuclCaire dynamique pour identifier les interconversions conformationnelles rapides des deux composCs 3a et 3c qui correspondent 2 la pseudorotation entre des conformations coniques aplaties. Le complexe de l'argent avec le compose 3c prksente aussi de la pseudorotation; toutefois, on a observe que la barribre d'activation augmente de 42 W mol-I dans le coordinat libre i 49 W mol-' dans le complexe. Le donnCes de la RMN indiquent que le cation mCtallique se fixe d'une f a~o n symCtrique en utilisant deux paires de sites de fixation disposes l'un en face de l'autre de chaque cGtC du macrocycle. Sur la base de ces donnCes, on en conclut que les quatre fonctions carbonyles sont impliquees dans la fixation d'un cation mttallique dans un complexe 1 : 1 avec le coordinat.

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Section: Synthesissupporting

confidence: 88%

Cation binding and conformation of octafunctionalized calix[4]resorcinarenes

Fransen¹,

Dutton²

1995

Can. J. Chem.

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“…[24] The solvents, N-methylformamide (Sigma-Aldrich, 99 %), N,N-dimethylformamide (SigmaAldrich, HPLC Grade) and dimethyl sulfoxide (Sigma-Aldrich, HPLC Grade) were used without further purification. The salts used for the investigation of compound L complexation were LiClO4 (Sigma Aldrich 99.99 %), NaClO4 (Sigma Aldrich 98+ %), KClO4 (Merck, p.a.…”

Section: Methodsmentioning

confidence: 99%

Complexation of Alkali Metal Cations by a Tertiary Amide Calix[4]Arene Derivative in Strongly Cation Solvating Solvents

et al. 2017

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The complexation of alkali-metal cations with calix [4]arene tertiary amide derivative (L) was studied in N-methylformamide (NMF), N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO) by means of microcalorimetric and UV spectrophotometric titrations. The Gibbs energies, enthalpies, and entropies for transfer of reactants and products from N-methylformamide to other solvents were determined. Favorable enthalpic contribution to overall stability was found to be the most important for all complexation reactions, especially in the case of NaL + formation, resulting in an affinity peak of L for this cation. The complexation entropy changes were always unfavorable. The ligand dissolution was endothermic in all solvents, accompanied by positive solution entropy. The highest complex stability constants were determined in NMF, whereas in DMSO the affinity of L towards alkali metal cations was the lowest. An interesting interplay between the transfer enthalpies and entropies of the reactants and complexes was revealed and discussed in detail.

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“…The alkylation of calixarenes and resorcinarenes with ethyl-, or methyl-bromoacetate has been well documented to provide the corresponding ether-ester derivatives in high yield. 37 The direct conversion of esters into amides by aminolysis is well established, 38 and has been applied recently to a calixarene tetraester. 39 In the calixarene case, the authors indicate that the aminolysis reaction worked well for nalkylamines but did not work with benzylamine or aniline.…”

Section: H Nmr Spectrum Of Compound 15a'mentioning

confidence: 99%