Calixarenes. 1. Analysis of the product mixtures produced by the base-catalyzed condensation of formaldehyde with para-substituted phenols

Gutsche, C. David; Muthukrishnan, Ramamurthi

doi:10.1021/jo00419a052

Cited by 247 publications

(181 citation statements)

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“…Solid samples were prepared as dispersions in KBr discs and liquid samples as an interspersed film between polished sodium chloride plates. 5,11,17,arene (5) [20,21]. To calix [4]arene diacid 4 [12,13] (5.50 g, 7.19 mmol) in toluene (140 ml) was added thionyl chloride (0.41 ml, 7.4 mmol) and the solution was heated at reflux temperature for 2 h. After cooling, the solution was concentrated in vacuo to give a brown solid which was used without further purification (5.72 g, 99%).…”

Section: General Methodologymentioning

confidence: 99%

“…M.pt. 264-266 ºC; R f 0.21 (5% methanol/dichloromethane); 1 H NMR (CDCl 3 ,  ppm) 7.39 (s, 2H), 7.34-7.22 (m, 10H), 6.98 (s, 4H), 6.78 (s, 4H), 4.93-4.40 (m, 12H), 3.94-3.71 (m, 4H) 3.37-3.26 (m, 4H), 2.78-2.62 (m, 2H) 5,11,17,arene (10). To a solution of 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonyl methyleneoxy-26,28-dihydroxycalix [4]arene [20,21,27] (4.0 g, 4.7 mmol) in THF (40 ml) was added sodium hydride (0.56 g, 23.5 mmol) and the mixture was stirred for 30 min at ambient temperature.…”

Section: 111723-tetra-tert-butyl-2527-di(7-benzyl-6-oxo-17-diazmentioning

confidence: 99%

“…The solid residue was dissolved in dichloromethane (30 ml), washed with 10% aqueous HCl solution (10 ml), water (3 x 10 ml), dried over MgSO 4 and concentrated in vacuo. 5,11,17,28,dimethoxycalix[4]arene was recovered from methanol as a white solid (3.12 g, 74%). M.pt.…”

Section: 111723-tetra-tert-butyl-2527-di(7-benzyl-6-oxo-17-diazmentioning

confidence: 99%

“…The resulting solid was isolated by vacuum filtration, dissolved in dichloromethane (50 ml), washed with 3M HCl (10 ml), water (3 x 10 ml), dried over MgSO 4 and concentrated in vacuo. Calix [4]arene 5,11,17,arene (11). [4]arene (12).…”

Section: 111723-tetra-tert-butyl-2527-di(7-benzyl-6-oxo-17-diazmentioning

confidence: 99%

“…Their synthesis was further improved by Zinke and Ziegler in 1944 [8,9], and then early conformational studies were published in 1955 by Cornforth [10]. Since Gutsche first published the synthesis of calix [4]arene-based macrocycles [11], the investigation of the complexation properties of these compounds has been of intense interest for a wide variety of ionic species and small organic guest molecules, through the formation of host-guest or supramolecular complexes. This area is subject to regular in-depth reviews [3][4][5][6].…”

Section: Introductionmentioning

confidence: 99%

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Bis(spirolactam) 1,3-double-armed calix[4]arene compounds and their application as extractants for the determination of heavy metal ions

Ward

Regan

et al. 2015

J Incl Phenom Macrocycl Chem

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Section: General Methodologymentioning

confidence: 99%

Section: 111723-tetra-tert-butyl-2527-di(7-benzyl-6-oxo-17-diazmentioning

confidence: 99%

Section: 111723-tetra-tert-butyl-2527-di(7-benzyl-6-oxo-17-diazmentioning

confidence: 99%

Section: 111723-tetra-tert-butyl-2527-di(7-benzyl-6-oxo-17-diazmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Bis(spirolactam) 1,3-double-armed calix[4]arene compounds and their application as extractants for the determination of heavy metal ions

Ward

Regan

et al. 2015

J Incl Phenom Macrocycl Chem

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Mono- and Binuclear Rhodium and Platinum Complexes of 1, 3, 5-Trimethyl-1, 3, 5-triaza-2σ3λ3-phosphorin-4, 6-dionyloxy-substituted Calix[4]arenes

Kunze

Neda

Freytag

et al. 2002

Z. anorg. allg. Chem.

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The reaction behaviour of 1,3,5-triaza-2σ 3 λ 3 -phosphorin-4,6-dionyloxy-substituted calix[4]arenes towards mono-and binuclear rhodium and platinum complexes was investigated. Special attention was directed to structure and dynamic behaviour of the products in solution and in the solid state. Depending on the molar ratio of the reactands, the reaction of the tetrakis(triazaphosphorindionyloxy)-substituted calix[4]arene (4) and its tert-butyl-derivative (1) with [(cod)RhCl] 2 yielded the mono-and disubstituted binuclear rhodium complexes 2, 3, and 5. In all cases, a C 2 -symmetrical structure was proved in solution, apparently caused by a fast intramolecular exchange process between cone conformation and 1,3-alternating conformation. The X-ray crystal structure determination of 5 confirmed [(calixarene)RhCl] 2 -coordination through two opposite phosphorus atoms with a P····P separation of 345 pm. The complex displays crystallographic inversion symmetry, and the Rh 2 Cl 2 core is thus exactly planar. Reaction of 1 and of the bis(triazaphosphorindionyloxy)-bis(methoxy)-substituted tert-butyl-calix-[4]arene (7) with (cod)Rh(acac) in equimolar ratio and subsequent reaction with HBF 4 led to the expected cationic monorhodium Ein-und zweikernige Komplexe des Rhodiums und Platins von 1,3,5-Trimethyl-1,3,5-triaza-2σ 3 λ 3 -phosphorin-4,6-dionyloxy-substituierten Calix[4]arenen Inhaltsübersicht. Das Reaktionsverhalten von 1,3,5-Trimethyl-1,3,5-triaza-2σ 3 λ 3 -phosphorin-4,6-dionyloxy-substituierten Calix-[4]arenen gegenüber ein-und zweikernigen Rhodium-und PlatinKomplexen wurde untersucht. Besonderes Augenmerk wurde auf die Untersuchung der Struktur und des dynamischen Verhaltens der Produkte im festen Zustand und in Lösung gelegt. Abhängig vom molaren Verhältnis der Reaktanden lieferte die Umsetzung des tetrakis(triazaphosphorindionyloxy)-substituierten Calix[4]-arens (4) und seines tert-Butyl-Analogons (1) mit [(cod)RhCl] 2 die mono-und disubstituierten, zweikernigen Rhodiumkomplexe 2, 3 und 5. In allen Fällen wurde eine C 2 -symmetrische Struktur in Lö-sung nachgewiesen, die anscheinend aus einem schnellen intramolekularen Austauschprozeß zwischen der Konus-und der 1,3-alternierenden Konformation resultiert. Die Röntgenstrukturana-lyse von 5 bestätigte die [(Calixaren)RhCl] 2 -Koordination über zwei gegenüberliegende Phosphoratome mit einem P····P-Abstand von 345 pm. Der Komplex zeigt kristallographische Inversionssymmetrie, damit ist die Rh 2 Cl 2 -Verbrückungseinheit exakt planar. Die Reaktion von 1 und dem bis(triazaphosphorindionyloxy)-bis(methoxy)-substituierten tert-Butyl-Calix[4]aren (7) mit (cod)-Rh(acac) in äquimolarem Verhältnis und anschließender Umsetcomplexes 6 and 8, involving 1,3-alternating P-Rh-P-coordination. The cone conformation in solution was proved by NMR spectroscopy and characteristic values of the 1 J(PRh) coupling constants in the 31 P-NMR-spectra. Reaction of equimolar amounts of 4 with (cod)Rh(acac) or (nbd)Rh(acac) led, by substitution of the labile coordinated acetylacetonato and after a...

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Zinke Synthesis

2010

Comprehensive Organic Name Reactions and Reagents

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This reaction is a one‐pot, three‐step process to treat the mixture of p ‐substituted phenols and formaldehyde under basic conditions to give a group of molecules of high melting points that are primarily composed of cyclic arrays of four phenolic moieties joined by alternating methylene groups attached at positions ortho to the hydroxyl groups, and named these molecules cyclischen mehrkernmethylenephenolverbindungen . This reaction is generally referred to as the Zinke synthesis. This preparative method has subsequently been modified by different groups. In addition, Gutsche coined the name calix[ n ]arene to stand for these molecules. The present study focuses the structural features, modifications and applications of calix[ n ]arene. It has been pointed out that the Zinke–Cornforth procedure in some cases afford calix[4]arenes as major products, whereas Munch's modification can be applied to the synthesis of calix[6]arenes and calix[8]arenes. A lengthy multistep process has also been developed for the preparation of sophisticated calixarene molecules. It has been reported that the cations that complex with calix[ n ]arenes can be divided into two groups, alkali (or alkali‐like). The transition metal cations and the relative orientation of para and phenolic substituents also affects the selectivity of calix[ n ]arenas toward the alkali cations. It has been found that the cone conformer of calix[4]arenas shows the highest affinity for Na + , whereas the partial cone and 1,3‐alternate conformers prefer K + and Cs + . All the known modification methods on calix[ n ]arenas have been discussed, which can be divided into nine groups. Other types of calix[n]arene analogues have been prepared, such as resorcarenes, and homo‐oxacalixarenes. The asymmetric calix[n]arenes are generally obtained by three approaches. The study finds that calixarenes arising from other aldehydes rather than formaldehyde have alkyl or aryl groups at the bridges across the aromatic annulus; and according to the orientation of these substituents, there exist four kinds of stereoisomers. This reaction has very wide applications in the preparation of calix[n]arenes.

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Calixarenes. 1. Analysis of the product mixtures produced by the base-catalyzed condensation of formaldehyde with para-substituted phenols

Cited by 247 publications

References 0 publications

Bis(spirolactam) 1,3-double-armed calix[4]arene compounds and their application as extractants for the determination of heavy metal ions

Bis(spirolactam) 1,3-double-armed calix[4]arene compounds and their application as extractants for the determination of heavy metal ions

Mono- and Binuclear Rhodium and Platinum Complexes of 1, 3, 5-Trimethyl-1, 3, 5-triaza-2σ3λ3-phosphorin-4, 6-dionyloxy-substituted Calix[4]arenes

Zinke Synthesis

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