• Bulletin of the Korean Chemical Society
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• v.17 no.6
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• pp.499-502
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• 1996

Two different acyl substituents were introduced at the lower rim of calix[4]arene by the two step reactions. Calix[4]arenes (1) reacted with 3,5-dinitrobenzoyl chloride to yield monosubstituted calix[4]arene (2). Second substitution was achieved by the reaction of 2 with various acyl chlorides. Aminomethylation of monobenzoylated calix[4]arene was conducted successfully in the presence of secondary amine and formaldehyde.

• Bulletin of the Korean Chemical Society
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• v.16 no.2
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• pp.153-157
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• 1995

Calix[6]arenes are selectively dialkylated at the lower rim and further functionalized by the aminomethylation and Claisen Rearrangement reactions. Dialkylation was conducted by the reaction of calix[6]arene and alkyl halides such as benzyl bromide, allyl bromide, ethyl bromoacetate, propyl bromide, and methyl iodide under the carefully controlled reaction conditions. Aminomethylation was carried out with the treatment of disubstituted calix[6]arene and secondary amine in the presence of formaldehyde. Claisen rearrangement reaction of the O-diallylcalix[6]arene produced the p-diallylcalix[6]arene.

• Journal of Radiopharmaceuticals and Molecular Probes
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• v.7 no.2
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• pp.141-146
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• 2021

With increasing interest in fluorinated compounds, nucleophilic fluorination reaction has been generally used for synthesizing fluorine-containing chemicals. However, alkali metal fluorides (MFs) generally have low solubility and reactivity in organic solvent. To overcome these problems, various phase transfer catalysts (PTCs) have been investigated. Calix-arene is known as to capture the metal cation(M⁺), and therefore in this review, we would like to introduce several kinds of calix-arene based PTCs, such as bis-tert-alcohol-functionalized crown-6-calix[4]arene (BACCA), oligo-ethylene glycol linked bis-triethyleneglycol crown-5-calix[4]arene (BTC5A), and ionic liquid functionalized calix-arene based catalyst, as well as ion-pair receptor crown-6-calix[4]arene-capped calix[4]pyrrole.

• Bulletin of the Korean Chemical Society
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• v.21 no.9
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• pp.867-874
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• 2000

Two new azobenzene crown ether calix[4]arenes, 10 and 11, were synthesized by two pathways. In the first pathway,two ethoxy nitrobenzene groups were attached to t-butylcalix[4]arenes in a 1,3 position. Subsequent reduction ofthe nitrobenzene group s by metallic zinc in an alkaline solution afforded 10 and 11 in8% and 12%,respectively. In the second pathway,an azobenzene containing two glycolic units was prepared prior connect-ing to t-butylcalix[4]arenes. The yields from the second approach (5%, 8% for 10 and 11, respectively) were lower than those from the former approach. Single crystals of 10 suitable for X-ray crystallography was ob-tained by recrystallization in methanol.Both the X-ray structure and the 1H-NMR spectrum of 10 indicated that the stereoisomer of the azobenzene moiety was trans and the calixarene platform was in cone conformation. 1H NMR spectroscopy suggested that 10 underwent an observable cis-trans isomerization in CDCl3 under room light and upon UV irradiation with cis:trans ratios of 33:67 and 36:64,respectively. Compound 6 which was the precursor of 11showed fluxional behavior and was found to have mixed conformations ofcone and partial cone with a ratio of 47:53 at -30 $^{\circ}C.$ 1H NMR spectrum of 11 suggested that 11 was initially isolated as cis azobenzene with calix[4]arene in cone conformation and underwent conformational interconversion through calix[4]arene annulas in a similar fashion to 6 upon exposing to light. The complexation studies of 10 with picrate salts of Na+ and K+ using 1H NMR spectroscopysuggested that Na+ preferred to bind the cis form of 10 while K+ preferred to bind the trans form. The stereoisomer of the azobenzene unit in 11 changed partially from cis to trans upon complexing with K+.

• Bulletin of the Korean Chemical Society
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• v.24 no.12
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• pp.1737-1741
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• 2003

Azo-functionalized calix[4]arenes as ionophores for chloride-selective electrode, 5,11,17,23-Tetra-tert-butyl-25,27-bis[(N,N-dimethyl-aniline-azo-phenylthioureido)ethyl]oxy-26,28-dihydroxycalix[4]arene (4a) and 5,11,17,23-Tetra-tert-butyl-25,27-bis[(N,N-dimethyl-aniline-azo-phenylthioureido)ethyl]oxy-26,28-dimethoxycalix[4]arene (4b) were synthesized. The PVC membrane electrode based on azo-functionalized calix[4]arene 4a with o-NPOE exhibits a linear stable response over a wide concentration range ($1.5{\times}10^{-4}-1.0{\times}10^{-1}$) with a slope of -52.0 mV/decade and a detection limit of log[$Cl^-$] = -4.02. This ionophore-based membrane exhibited improved selectivity for chloride anion compared with classical Hofmeister series.

• Bulletin of the Korean Chemical Society
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• v.14 no.6
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• pp.753-755
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• 1993

• Bulletin of the Korean Chemical Society
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• v.18 no.12
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• pp.1327-1330
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• 1997

• Bulletin of the Korean Chemical Society
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• v.25 no.1
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• pp.55-58
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• 2004

In this study we have performed ab initio computer simulations to investigate the conformational characteristics of the tetramethoxycalix[4]arenes (1 and 2). The structures of four types (cone, partial cone, 1,2-alternate, and 1,3-alternate) of conformers for each compound have been optimized using ab initio RHF/6-31G and 6-31$G^{**}$ methods. General trends in relative stabilities of tetramethyl ether derivatives of calix[4]arene 1 and p-tert-butylcalix[4]arene 2 are similar and decrease in following order: partial cone (most stable) > cone > 1,3-alternate > 1,2-alternate. The calculated results of the most stable conformation of partial cone structure agree with the reported NMR experimental observations.

• Bulletin of the Korean Chemical Society
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• v.9 no.1
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• pp.52-55
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• 1988

Starting with readily available p-tert-butylcalix[4]arene 3 tert-butyl groups are removed by $AlCl_3$-catalyzed de-alkylation reaction, and the calix[4]arene 4 formed is converted into the tetraacyl esters. These compounds undergo Fries rearrangement to yield p-acylcalix[4]arenes. p-Acetyl, p-propionyl, p-butyryl, and p-benzoylcalix[4]arene 10, 11, 12 and 14 are synthesized in 70-80% yields by treatment of the corresponding esters 5, 6, 7 and 9 with $AlCl_3$ in nitrobenzene. When the tetraisobutyryl ester 8 was treated with the same condition, only two isobutyryl groups were rearranged to the para-positions of calix[4]arene, and remaining two groups were simply cleaved.

• Bulletin of the Korean Chemical Society
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• v.25 no.12
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• pp.1911-1916
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• 2004

The conformational preference of tetrahomodioxacalix[4]arenes with three different para substituents on the phenolic ring has been investigated by using ab initio molecular orbital theory (RHF/6-31$G^{\ast}$) and density functional theory (B3LYP/6-31$G^{\ast}$). The stability order is predicted to be cone > C-1,2-alternate > partial cone > 1,3-alternate > COC-1,2-alternate. The distorted cone conformation is found to be most stable in a gas phase and the calculated results are in agreement with the reported $^1$H NMR and X-ray experimental observations. The substitution of methylene with dimethyleneoxa bridges increases the size of the annulus of the molecule, its conformational mobility, and the number of hydrogen bonding patterns. The thermodynamic stability and the conformational characteristics of tetrahomodioxacalix[4]arenes are discussed in regards of the number of phenolic hydrogen bonding patterns and the polarity of a molecule. The substituent effects on the para position of the phenolic ring are also introduced.