Resorcin arene resorcinol

Resorcinarene A cyclic oligomer (usually a tetramer) arising from the condensation of resorcinol and an aldehyde under acidic conditions. Other synonyms are resorcarene, calixresorcarene, calixresorcinarene, as well as resorcin-[n]-arene or calix-[n]-resorcinarene, where [n] specifies the number of monomers in the oligomer. 

Resorcin[4]arene is an easy to prepare molecule directly available by condensation between one to one stoichiometric amount of resorcinol and aliphatic aldehydes under acid catalysis in ethanol [16]. The calyx-like monomeric unit is obtained with all the OH moieties on one rim of the calyx structure when long aldehydes are employed, nonflipping of the aromatic units is possible and the molecule is conformationally stable. 

Resorcin[4]arenes, the resorcinol analogs of calix[4]arenes (also called calix[4] resorcinols), were also modified at their upper rims with amino acids or peptides at two possible positions either at oxygen atoms or at the ortho positions. Resorcinarenes substituted with amino acid amides at oxygen atoms have found applications as chiral stationary phases (CSP) in capillary gas chromatography... 

Resorcinarenes (see the companion chapter by Bruno Botta) date back nearly 150 years when Baeyer discovered that the mixing of aldehydes with resorcinol in the presence of strong acid produced a red resin [2]. Over a decade later, Michael successfully determined the correct chemical composition of the product, but proposed the incorrect structure [3]. The correct structure of resorcin[4]arene (1, Scheme 9.1) was first proposed by Niederl [4], but it was almost 100 years after Baeyer s initial work that Erdtman and Hogberg obtained a definitive structure [5]. Twelve years after that, Hogberg fully documented resorcinarene synthesis,... 

In order to confer the calixarenes the ability to form SAMs on metal surfaces, they have to be chemically modified to introduce chemical functions (e.g., thiol, thioether, disulfide) able of chemisorption on the surface. Reinhoudt published the synthesis of calix[4]arenes bearing four di- -decyl sulfide chains at the lower rims. The synthesis proceeds via first the alkylation of the calix[4]arene-25,26,27,28-tetrol with 10-undecen-l-yl tosylate followed by the anti-Markovnikov addition of 1-dodecanthiol in the presence of 9-borabicyclo[3.3.1]nonane (9-BBN) (Fig. 37.11) [64]. Similarly to calix[4]arenes, resorcin[4]arenes tetrasulfides have been produced by the condensation reaction of resorcinol and 11-undecylenic aldehyde followed by the addition of 1 -dodecanthiol to the terminal double bonds of the alkyl chains using catalytic amounts of 9-BBN [63]. 

The acid-catalyzed cocondensation between resorcinol and dodecanal (1996T2663), predominandy led to resorcin[4]arene 158 (R= C11H23). (1991JOC5527). 

The acid-catalyzed co-condensation between resorcinol and dodecanal (Timmerman et al. 1996), predominantly led to resorcin[4]arene 8a (Weinelt and Schneider 1991). 

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