High yield synthesis of the parent C-unsubstituted calix[4]resorcinarene octamethyl ether

Falana, Olusegun M.; Al-Farhan, Emile; Keehn, Philip M.; Stevenson, Robert

doi:10.1016/0040-4039(94)88163-4

Cited by 34 publications

(15 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…(hemi)carcerands 79-81 ) highlights this design feature and provides the crystal structures of several bowl-occupied solvates. [55][56][57][58][59][60][61][62][63][64][65][66][67][68][69][70][71][72][73][74] It was noted early on that many simple cavitands essentially always crystallize from solution with included solvent, some forming highly stable solvates. For example, Cram and coworkers found that the aryl-footed cavitand H,4-CH 3 C 6 H 4 ,CH 2 strongly holds ethyl acetate and apparently could only be emptied by sublimation at 450 °C under vacuum.…”

Section: Background and Csd Searchmentioning

confidence: 99%

Many Simple Molecular Cavitands Are Intrinsically Porous (Zero-Dimensional Pore) Materials

et al. 2015

View full text Add to dashboard Cite

The guest-free crystal forms of eight related small molecule cavitands (Scheme 1; simplified nomenclature: R,R',Y) are investigated as candidate discrete molecule microcavity materials (DMMMs). Due to their rigid bowl-like molecular structures, many cavitands are incapable of efficient crystal packing in pure form, yielding zero-dimensionally porous apohost phases. By molecular modifications that eschew self-inclusion, emphasis is placed on engineering structures that exhibit uniform microcavities that are large enough to accommodate small molecules of interest (e.g., gases or volatile organic compounds). The most thermodynamically stable guest-free crystal forms of several cavitands-namely, H,H,CH 2 , H,Me,CH 2 , α-Me,H,CH 2 , Me,Me,CH 2 , Br,Me,CH 2 , Me,Et,CH 2 , Me,Et,SiMe 2 , and Me,i-Bu,CH 2 -appear to be as-close-packed-as-possible, yet exhibit relatively large microcavities (or, zero-dimensional pores) in the range of 27-115 Å 3 . Where self-inclusion is ineffective, the microcavities predictably assimilate the intrinsic cavitand molecular cavity, yet the ultimate size and shape of cavities are also strongly influenced by crystal packing. It is demonstrated that some cavitand solvates, CH 2 Cl 2 @H,Me,CH 2 , xH 2 O@Me,Et,SiMe 2 , and CH 2 Cl 2 @Me,iBu,CH 2 (84:16 rccc:rcct) maintain host crystal packings that are equivalent to their empty, intrinsically porous phases and it is argued that the intrinsic pores of DMMMs are particularly suited to selective gas enclathration and/or storage. As a proof-ofconcept demonstrations, the porous phase of Me,Et,SiMe 2 is shown to capture and temporarily hold Freon-41 (fluoromethane, bp = -78 °C) at room temperature. A single crystal of empty Me,Et,SiMe 2 is shown to uptake CO 2 gas at room temperature, allowing structure determination of xCO 2 @Me,Et,SiMe 2 , and single-crystal-to-single-crystal dehydration of xH 2 O@Me,Et,SiMe 2 demonstrates its permeability to water.

show abstract

Section: Background and Csd Searchmentioning

confidence: 99%

Many Simple Molecular Cavitands Are Intrinsically Porous (Zero-Dimensional Pore) Materials

et al. 2015

View full text Add to dashboard Cite

show abstract

“…54 New synthetic conditions for fully selective formations of the rctt chair stereoisomers of octa-O-alkyl resorcin [4]arenes (6a ± d) in acetic acid ± H 2 SO 4 or acetic acid ± HCl mixtures have been described, and it has been proposed 55 that this isomer is the thermodynamic product under Brùnsted acid catalysis, which is an unprecedented observation in resorcinarene chemistry.…”

Section: Synthesis Of Calix[4]resorcinarenesmentioning

confidence: 99%

Chemistry of calix[4]resorcinarenes

Jain¹,

Kanaiya

2011

Russ. Chem. Rev.

View full text Add to dashboard Cite

The review demonstrates the progress in the The review demonstrates the progress in the chemistry of calix[4]resorcinarenes over the last decade. chemistry of calix[4]resorcinarenes over the last decade. Special attention is paid to their synthesis, conformational Special attention is paid to their synthesis, conformational behaviour, functionalization and ability to serve as cavi-behaviour, functionalization and ability to serve as cavitands and capsules, to form monolayers and host ± guest tands and capsules, to form monolayers and host ± guest complexes. Practical applications of calix[4]resorcinarenes complexes. Practical applications of calix[4]resorcinarenes and their derivatives in various fields are surveyed. The and their derivatives in various fields are surveyed. The bibliography includes 296 references bibliography includes 296 references.

show abstract

“…Analogously, when 2,4-dimethoxybenzyl alcohol 6 was treated with trifluoroacetic acid (5% in CHCl 3 ), the unsubstituted resorcarene 7a was obtained in 95% yield (Scheme 3) [20]. Notably, compound 7a cannot be synthesized by the acid-catalyzed condensation of resorcinol and formaldehyde, since this reaction gives only polymeric products [2].…”

Section: Tetramerization Of Resorcinol Dimethyl Ether Derivatives By mentioning

confidence: 99%

Resorcarenes: Emerging Class of Macrocyclic Receptors

Botta¹,

Cassani

D’Acquarica³

et al. 2005

COC

View full text Add to dashboard Cite

The present review intends to give an overview on the synthetic methods applied for the preparation of resorcarenes and all the conformation implications due to the flexibility of the target tetramers. The flexible resorcarenes can be rigidified by intramolecular bridging of adjacent oxygens with bifunctional reagents, to give cavitands. These compounds, which feature rigid bowl shaped cavities of different size and dimensions, depending on the bridging groups employed, will be examined according to these latter. Moreover, some emphasis will be placed in resorcarenes chirality and on the ways how to introduce it: either indirectly, e.g. by tetramerization of monomers containing a chiral center, or directly, by synthesis of macrocycles featuring a Cn-type symmetry, which is defined as inherent chirality and arises from the nonplanarity of the basic metacyclophane system. Finally, the use of resorcarenes as pseudo stationary phases for the separation of isomeric compounds will be mentioned

show abstract

High yield synthesis of the parent C-unsubstituted calix[4]resorcinarene octamethyl ether

Cited by 34 publications

References 9 publications

Many Simple Molecular Cavitands Are Intrinsically Porous (Zero-Dimensional Pore) Materials

Many Simple Molecular Cavitands Are Intrinsically Porous (Zero-Dimensional Pore) Materials

Chemistry of calix[4]resorcinarenes

Resorcarenes: Emerging Class of Macrocyclic Receptors

Contact Info

Product

Resources

About