Synthesis of aminomethylated calix[4]resorcinarenes

Matsushita, Yoh‐ichi; Matsui, Takanao

doi:10.1016/s0040-4039(00)60145-4

Cited by 132 publications

(43 citation statements)

References 7 publications

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“…23 Chiral calix [4]resorcarenes can be obtained by a condensation reaction of primary or secondary amines, as shown in Figure 4. 28 One chiral primary amine and three chiral secondary amines were used to prepare chiral derivatives. With primary amines, both hydrogen atoms of the amine group undergo reaction leading to the formation of an oxazine ring.…”

Section: Calix[4]resorcarenesmentioning

confidence: 99%

Calix[4]arene, calix[4]resorcarene, and cyclodextrin derivatives and their lanthanide complexes as chiral NMR shift reagents

et al. 2003

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Calix[4]arenes, calix[4]resorcarenes, and anionic cyclodextrin derivatives were examined as chiral NMR solvating agents. The calix[4]arenes were prepared by attachment of amino acids through the hydroxyl groups of the phenol rings. Chloroform-, methanol-, and water-soluble derivatives were prepared and tested with a range of substrates. Chloroform-soluble chiral calix[4]resorcarenes were prepared by attachment of chiral primary and secondary amines and examined in NMR applications with a variety of substrates. Sulfated and carboxymethylated beta-cyclodextrin are effective at causing enantiomeric discrimination in the (1)H NMR spectra of organic cations. Lanthanide ions associate at the carboxymethyl groups and cause sizeable shifts and enhancements in enantiomeric discrimination in the spectra of organic cations. The enhancements caused by the lanthanide ion are large enough that much lower concentrations of the cyclodextrin can be used as compared to conventional analyses.

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Section: Calix[4]resorcarenesmentioning

confidence: 99%

Calix[4]arene, calix[4]resorcarene, and cyclodextrin derivatives and their lanthanide complexes as chiral NMR shift reagents

et al. 2003

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“…[9] Instead of chiral amines amino acids like -proline can be used as well. [8,10] The inherently chiral 1,3-oxazine derivatives are very sensitive to acidic and basic conditions due to their N,O-acetal functions. The epimerization can be prevented by methylation of the four residual phenolic groups as described in the literature.…”

Section: Introductionmentioning

confidence: 99%

First Synthesis, Isolation and Characterization of Enantiomerically Pure and Inherently Chiral Resorc[4]arenes by Lewis Acid Cyclization of a Resorcinol Monoalkyl Ether

et al. 2003

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Cyclization of resorcinol monoalkyl ethers with aliphatic aldehydes leads to the corresponding racemic mixtures of C4‐symmetric rccc‐resorc[4]arenes. Separation of these isomers was achieved by mono‐O‐functionalization of the rccc‐2,8,14,20‐tetramethylresorc[4]arene (2) with (S)‐(+)‐10‐camphorsulfonyl chloride leading to a diastereomeric mixture of (+)‐5a and (−)‐5b. After removal of the chiral auxiliary the inherently chiral pure enantiomers (+)‐2 and (−)‐2 were obtained. Further enantiomerically pure rccc‐resorc[4]arenes were obtained by cyclization of (+)‐3‐[(2S)‐2‐methylbutoxy]phenol (6) followed by chromatographic separation. The resulting diastereomeric resorc[4]arenes (+)‐7a and (−)‐7b were examined by CD spectroscopy, showing a perfect mirror image in all solvents examined. This indicates that the resorcarene cavities of (+)‐7a and (−)‐7b are essentially enantiomers of each other. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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“…The H 8 L was synthesized by the procedure described in [3]. Isopropanol was purified additionally by distillation.…”

Section: Methodsmentioning

confidence: 99%

“…The H 8 L in 80% isopropanol was transformed into a more soluble tetrasubstituted salt by the addition of a calculated amount of hydrochloric acid. The H 8 L solutions were prepared using the weighed amounts of the compound: H 8 L: R 1 is C 11 H 23 and R 2 is CH 2 N(CH 3 …”

Section: Methodsmentioning

confidence: 99%

The Influence of Triton X-100 on Protolytic Properties of Aminomethylated Calix[4]resorcinarene and Its Interaction with Copper(II)

et al. 2005

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The influence of Triton X-100 (concentration 5 mM) on acid-base properties of aminomethylated calix[4]resorcinarene (H 8 L) containing alkyl ( R 1 = C 11 H 23 ) and dimethylaminomethyl ( R 2 = CH 2 N(CH 3 ) 2 ) substituents and interaction of H 8 L with copper(II) is studied by potentiometry and mathematical simulation of equilibria in solutions. It is found that the presence of a nonionic surfactant favors the aggregation of H 8 L (the degree of aggregation is higher than four), whereas, in 80% isopropanol at the same pH ≈ 10.2, a neutral species of the compound is only dimerized. The addition of Triton X-100 affects both the composition and stability of formed copper(II) complexes. The fraction of the highly charged tetranuclear [Cu 4 (H 4 L)] 4+ complex sharply decreases. The formation of a large amount of [Cu(H 7 L)] + complex appears to be preferable compared to [Cu(H 8 L) 2 ] 2+ complex containing two ligands in the coordination sphere (pH ≈ 5.7). An enhancement of the acidic properties of protonated species of the compound and a decrease in the apparent constants of H 8 L-copper(II) complex formation in Triton X-100 solutions compared to those in water-alcohol solutions are attributed to the formation of mixed micelles.

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Synthesis of aminomethylated calix[4]resorcinarenes

Cited by 132 publications

References 7 publications

Calix[4]arene, calix[4]resorcarene, and cyclodextrin derivatives and their lanthanide complexes as chiral NMR shift reagents

Calix[4]arene, calix[4]resorcarene, and cyclodextrin derivatives and their lanthanide complexes as chiral NMR shift reagents

First Synthesis, Isolation and Characterization of Enantiomerically Pure and Inherently Chiral Resorc[4]arenes by Lewis Acid Cyclization of a Resorcinol Monoalkyl Ether

The Influence of Triton X-100 on Protolytic Properties of Aminomethylated Calix[4]resorcinarene and Its Interaction with Copper(II)

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