Design and Syntheses of Novel Calix[4]crown: Calix[4]‐Dixanthates‐Crowns

Abstract

A series of novel calix[4]‐dixanthates‐crowns were designed and synthesized by the “1 + 1 condensation” of reacting calix[4]‐1,3‐dixanthate salts derivative (4) with polyethylene glycol ditosylates in 40–60% yields. It was found that the new calixcrowns showed outstanding complexation abilities towards soft cations. Calix[4]‐dixanthate‐crown‐4 (5b) exhibited high complexation selectivity towards Ni²⁺.     

Synthesis of Coumarin-functionalized Calix[4]arene and Selective Recognition for L-Tryptophan

We report a novel calixarene derivative using 4-bromomethyl-7-methoxycoumarin as the pre-organized unit and apply it to investigate selectively discriminate L-tryptophan from other amino acids in DMF-acetonitrile. 5, 11, 17, 23-Tetra-tert-butyl-25,27-bis-…     

Synthesis of Calix[4]resorcinarene Schiff Bases

Calix[4]resorcinarenes are cyclic tetramers in which four resorcinol units are linked via alkylmethylene bridges in the o-position to each resorcinic hydroxyl group. Their structures resemble that of p-butylcalix[n]arenes and render them of interest as host compounds in many contemporary fields of supramolecular chemistry. Therefore,     

Synthesis of Calix[4]resorcinarene Amide Derivatives

Three different synthetic routes were developed to introduce carbamoyloxy functional groups at the upper periphery of two calix[4]resorcinarenes. By treating activated esters 2a-b with excess corresponding amine such as 3-(dimethylamino)propylamine 3, ct-phenethylamine 4 and triethylenetetramine 5, six amide derivatives 6a-8b were obtained in high yield (Route 1). The pyridine-linked amide derivatives 9a-b were prepared by using acid chloride intermediate (Route 2).The amide derivatives 10a-b were obtained in moderate yields by direct alkylation of phenolic hydroxyl groups of la-b with N,N-dipropylchloroacetoamide in the presence of K2CO3/KI in acetone (Route 3).     

Synthesis of Pyridylazo-substituted Chromogenic Calix[4]arenes

Calixarenes are a versatile class of macrocyclic compounds which have attracted extensive interest due to their ability to form host-guest complexes and act as enzyme mimic, especially when appropriately functionalized1. Introduction of azo group to calixarenes can make the later to be easily detected in the process of molecular recognition, azo groups have been introduced into calixarenes by the diazo-coupling reaction of calix[4]arene with BF4- or chloride salt of substituted benzene diazon…     

Synthesis and Complexation Properties of Novel Biscalixarene Composed of Calix[4]arene and Thiacalix[4]arene Subunits

Biscalixarenes, as examples of higher order molecular architectures than normal calixarene derivatives, were studied extensively in the recent years due to they possess two calixarene cavities which have the potential for complexing with two guests in two…     

Liquid–liquid extraction and transport through membrane of amino acid methylesters by calix[n]arene derivatives

The extractability together with the transport through liquid membrane of some amino acid methylesters by using p-tert-butylcalix[4]arene as extractant or carrier was studied. In this context, p-tert-butylcalix[n]arenes (n = 6, 8) were found to act as useful carriers or extractant reagents for l-tryptophan methylester and l-tyrosine methylester. The calix[n]arene derivatives used in experiments extracted amino acids methylesters from the aqueous phase into chloroformic phase in the presence of tropaeolin 00 ([4(4′-anilinophenylazo)benzenesulphonic acid]) as counterion at . The extraction and the transport depend on the structure of calixarenes, the structure of amino acids, the pH, and the nature of anion used as ion pair for cation-receptor complexes. The properties of solvent involved in liquid membrane play an important role in membrane stability and also in selecting membrane systems. The results demonstrated that the inclusion properties of the investigated hosts are correlated with their structural properties and also they suggest further possibilities for optimal separation of amino acids derivatives.     

Ionic liquid [bmim][BF4] acts as solvent and promoter for synthesis of halo-containing N-arylphthalimides

A new synthetic process of N-arylphthalimide and halo-containing N-arylphthalimides through the reaction between phthalic anhydride and aromatic amines bearing halo groups in[bmim][BF_4]was described,ionic liquid[bmim][BF_4]acted as the dual role of solvent and promoter.     

Calix[4]arene-Based New Neutral Sensors for Fluoride

The development of new receptors which can recognize neutral and charged species has attracted considerable interest in the recent past.[1] Anions such as fluoride, chloride, phosphate and carboxylate play crucial roles in a range of biological phenomena and are implicated in many disease states.[2] Investigations on molecular and/or ionic recognition by calixarenes and their derivatives as synthetic receptors have attracted increasing attention in supramolecular chemistry because of their modifiable structure.[3] However, calix[4]arenes-based neutral receptors containing thiourea and amide groups are still rare. In this paper, we report fluoride selective optical chemosensors 4 and 5, based on calix[4]arene thiourea and amide derivatives, which only show a remarkable absorption change in the presence of fluoride ions, while have no any change upon addition of other anions (Cl- Br-, I-, AcO- and H2PO4-). The association constants are 947 and 2883 mol·L-1, respectively. The synthesis of calix[4]arene derivatives 4 and 5 is outlined in the following Scheme 1.     

Aminoalkylated Calix[4]resorcinarenes as pH Sensitive “hosts” for Charged Metallocomplexes

On the basis of RCA, pH-potentiometry and EPR-spectroscopy data aminoalkylated derivatives were proved to bind metal ion complexes both in alkaline and in acidic media. Outer-sphere coordination is the only interaction mode in these host-guest complexes.     

One-Pot Method for Synthesis of Calix[6]biscrowns

p-tert-Butylcalix[6]-1,4-2,5-biscrown-4 is a typical member of the family of calix[6]crowns. In the literature, the compound was synthesized from calix[6]arene by two steps and the overall yield based on calix[6]arene was 24%.Herein we wish to report a one-pot method to do this work. By this method the yield was up to 48% and the reaction time was greatly reduced.     

Calix[4]dithiacrown-6 and Its Platinum Complex

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Synthesis of Calix[4]arenes with Dendritic Fragments

Dendrimer5arethree-dimensional,highorderedoligomericandPOlymericcomPOundS,whicharemo1ecular-1evelcontrolofsize,shapes,surfacechentistry,toPOlogyandflexibility.'.'Calixarenesarecyclicoligomers,whichhavebeenextensive1ystudiedinordertoobtalnnewhostsbyappropriatefiJnctionalizationoftheparentmolecule.3,#Besides,calixarenesareattractivecandidatesfOrpolponctionalcoresindendriticmolecules,esPeciallybytheconvergentgroWthaPProach.'ltisinterestingthatthemoleculeofcombinationofcalixarenewithdendritic…     

Synthesis of Schiff Base Calix [4] arene Crowns

This letter reports the synthesis of Schiff base calix [4] arene crowns containing m-xylylene phenol subunit, in which calix [4] arene Schiff base crowns 2a,2b and 2c were formed by 1:1 condensation of calix [4] arene diamine 1 with dialdehydes (2,6-diformyl-4-chlorophenol 3a,2,6-diformyl-4-methylphenol 3b,2,6-diformyl-4-tert-butylphenol 3c)under high dilute condition in refluxing anhydrous ethanol in 65-70% yield.     

Functioned Calix[4]arenes as Artificial Enzymes Catalyze Aldol Condensation

Aldolcondensationcanbegenerallycatalyzedbymeansofbasesoracids.Usually,itiseasytoobtainα,β-unsaturatedketonesderivedfromthedehydrationofthealdol-typeproducts(β-hydroxyketones).Watanabeetal'successfullydevelopedthemethodtodepressthedehydrationbyusingmetal(Ⅱ)complexesofα-aminoacidesterswithcyclodextrin.Later,ZhaoHua-mingetal.2．3studiedthefunctionedcyclodextrinsasaldolasetomimicthecondensationofp-nitrobenzaldehydewithacetoneandobtainedtheaIdol-typeproductingoodyield.Recentyears,studiesonca…     

Effective Synthesis of β-Ketophosphonate Derivatives of Calix[4]resorcinolarenes

An effective method for introduction of -phosphonate fragments to a calix[4]resorcinolarene matrix is presented octa(ketophosphonate)calix[4]resorcinolarenes are prepared. The effectiveness of 2,8,14,20-tetramethyl-4,6,10,12,16,18,22,24-octa[3-(dimethoxyphosphoryl)-2-oxopropyl]calix[4]-resorcinolarene for extraction of lanthanum ions from water to chloroform in the presence of picrate ions, accompanied by formation of a complex is demonstrated.     

Interaction and Interfacial Molecular Recognition of Calix[4] arene Derivatives Bearing Nucleobases for Complementary Nucleoside

The p-tert-butyl calix[4] arene derivatives la with uracils and 1b with adenines at the lower rim were synthesized.The Interaction between 1a and 1b in CDCl3 solution was demonstrated by ^1H NMR spectra.The interfacial molecular recognitions of la and 1b for the complementary nucleosides in aqueous subphases were investigated by Langmuir-Blodgett technique.     

Alkylations of Resorcarenes and Calix[4]pyrroles in Phase Transfer Catalytic Systems

Calixlnlarenesarecyclicoligomersmadeupofphenolsandformaldehyde.Thisversatileclassofcompoundshasbeenextensivelystudiedinthelastdecademainlyinordertoobtainnewcomplexingagentsbyappropriatefuntionalizationoftheparentmoleculel.ResorcarenesZandcall-c[4]pyrroles'aretwosubgroupmembersofthefamilyofcalixarensandalsoattractedincreasinginterests.Aspartofaprogrammeaimedatthesynthesisofneweasy-to-makecalixarenemolecules,wedecidedtoinvestigatethealkylationofsomecalixarensinPhaseTransferCatalysis(PTC)condi…     

Synthesis of Calix[4]arene Derivatives with NLO Properties

The new chromophore compounds with NLO properties were prepared by Knoevenagel condensation from forrnyl or diformyl calix[4/arene and isophorone derivatives in the presence of piperidine and acetic acid, respectively. In these chromophore calix[4]arenes, the ring locked trienes were employed as the conjugation bridge and electron acceptor in D-π-A units. The NMR spectra demonstrated that they existed in a cone conformation and consequently non-conjugated D-π-A units could be oriented at nearly the same direction.     

Synthesis of （p-Formylphenyl）azo Calix[4]arenes

Five novel azo calix[4]arenes were reported. The p-aminobenzaldehyde was diazotized with sodium nitrite in aqueous hydrochloride solution. Mono-, bis-, tris- and tetrakis(p-formylphenyl)azo calix[4]arenes (including proximal and distal isomers) were obtained respectively by diazo-coupling in different molar ratio to calix[4]arene(1) under pH=7.5--8.5 at 0-5℃. All (p-formylphenyl)azo calix[4]arenes were characterized by ^1H NMR, ^13C NMR, IR, MS (ESIMS) spectroscopies and elemental analysis.