Macrocyclic calixarenes

Stmctural and chemical modification of urethane containing polymer matri-ces with macrocycles - calixarenes having reactive hydrazide groups have been carried out and stmcture, physico chemical and sensor properties of polyure-thanesemicarbazides (PUS) synthesised have been studied. The polymers obtained (on the base of polypropylene glycol MM 1000 and polysiloxane diol MM 860, hexamethylene diisocyanate and calixarene dihydrazide) are identified by IR-spectroscopy, size exclusion chromatography (SEC), DSC, WAXS and SAXS methods. 

Contrary to most other synthetic macrocycles, Calixarenes are easy available since one can synthesize them using inexpensive chemicals in a one-pot ... 

In this chapter, a review of our recent SFE work is provided, covering the design and application of new fluorinated macrocyclic calixarenes and the discovery of the effectiveness of linear flourinated thiourea reagents for gold complexation and extraction in unmodified SC-CO2. 

A series of novel fluorinated macrocyclic calixarene and fluorinated thiourea ligands were synthesised at UCC for used in the SFE of metal ions (Figures 1 and 5). Among the fluorinated calixarenes listed, C2-C4 were designed for gold extraction and are of particular relevance in the results presented in this paper. The synthetic methods are either published elsewhere (28,29) or in preparation for detailed publication. 

Figure 1 Chemical structures of the macrocyclic calixarenes synthesised and studied in this research work.

Isothiocarbazide- and/or oxime-based macrocycles, calixarenes, metallamacrocycles... 

The highest reported binding constant to date for a mono-macrocyclic calixarene or calixarene analogue receptor and Cgo is 3.48 x 10 which was ascribed to the Ag(I) A-heterocyclic carbene-bridged calixarene 48 synthesized by Quin et al. [72]. This binding constant for the 1 1 complexation was determined by fluorescence quenching titration study of in acetonitrile at 298 K (Fig. 33.33). 

Owing to the unique host-guest properties of calixarene macrocycles, calixarene-functionalized silica particles were used as cation-selective receptor colloids [81], and separator of lanthanides and actinides [82]. Calixarenes were also used for the syntheses of Ru, Pt and Pd NPs [83-85]. Furthermore, photoluminescence and charge-transfer complexes of calixarenes and calix[4]arene-based glycoclusters were grafted onto the surface of Ti02 NPs [64, 86]. 

ZINKE ZIEGLER Synthesiso1 Cahxarenes Synthesis of calixarenes (a basket-llke macrocyclic compound)... 

Many other cyclic and noncyclic organic carriers with remarkable ion selectivities have been used successfiilly as active hosts of various liquid membrane electrodes. These include the 14-crown-4-ether for lithium (30) 16-crown-5 derivatives for sodium bis-benzo-18-crown-6 ether for cesium the ionophore ETH 1001 [(R,R)-AA -bisd l-ethoxycarbonyl)undecyl-A,yVl-4,5-tctramcthyl-3,6-dioxaoctancdiamide] for calcium the natural macrocyclics nonactin and monensin for ammonia and sodium (31), respectively the ionophore ETH 1117 for magnesium calixarene derivatives for sodium (32) and macrocyclic thioethers for mercury and silver (33). 

In contrast, porphyrinogens 16 (Fig. 5) possess only 16 Ti-electrons and as a consequence the delocalization over the whole macrocycle is absent. The conformations of porphyrinogens are not planar any more and can approximate to the conformations known for calix[4]arenes (vide supra). Compounds 16 (Fig. 5) may, therefore, be considered as heteroatomic calixarene derivatives, of which some have additional heteroatoms in the bridging positions [15, 28-30]. 

A new type of calixarene-capped calixpyrrole (9) has been generated (32 %) in one-step from p-fe/t-butylcalix[4]arene tetramethylketone as the template <96TL7881>. A cylindrical calix[4]-fois-cryptand, in which the central calix[4]arene possesses two 1,3-altemating diaza-tetraoxa macrocycles on each face, has been synthesized <96TL8747>. A series of substituted l,4-(2,6-pyridino)-bridged calix[6]arenes has prepared and studied <96LA1367>. 

A huge group of macrocycles which contain 2,6-disubstituted phenols are the calixarenes [51]-[53]. Their conformation has been investigated intensively (Gutsche, 1989, 1991). In most conformations, however, the phenolic rings are oriented almost vertically in relation to the plane of the macrocydic ring. Therefore the OH functions are not oriented in an intra-annular fashion. Nevertheless the pK values of calixarenes [51] differ from those of other comparable phenols. The reason for this is the... 

Calixarenes, which are macrocyclic compounds, are one of the best building blocks to design molecular hosts in supramolecular chemistry [158]. Synthesis of calix[4]arenes, which have been adamantylated, has been reported [105, 109]. In calix[4]arenes, adamantane or its ester/carboxylic acid derivatives were introduced as substituents (Fig. 29). The purpose of this synthesis was to learn how to employ the flexible chemistry of adamantane in order to construct different kinds of molecular hosts. The X-ray structure analysis of p-(l-adamantyl)thiacalix[4]arene [109] demonstrated that it contained four CHCI3 molecules, one of which was located inside the host molecule cavity, and the host molecule assumed the cone-like conformational shape (Fig. 30). 

Metalated container molecules can be viewed as a class of compounds that have one or more active metal coordination sites anchored within or next to a molecular cavity (Fig. 2). A range of host systems is capable of forming such structures. The majority of these compounds represent macrocyclic molecules and steri-cally demanding tripod ligands, as for instance calixarenes (42), cyclodextrins (43,44), and trispyrazolylborates (45-48), respectively. In the following, selected types of metalated container molecules and their properties are briefly discussed and where appropriate the foundation papers from relevant earlier work are included. Porphyrin-based hosts and coordination cages with encapsulated metal complexes have been reviewed previously (49-53) and, therefore, only the most recent examples will be described. Thereafter, our work in this field is reported. 

Three macrobicycles 40b (216), 40h (212), and 40k (211) were characterized by X-ray crystallography. Fig. 31 displays the structure of 40h. The compounds adopt a highly folded conformation, reminiscent of calixarenes (23) and related Schiff-base macrocycles (181). 

Interestingly, the macrocycles can adopt two different conformations A and B (Fig. 34), which are reminiscent of the partial cone and cone conformations of the calixarenes. A detailed... 

Macrocycles containing isoxazoline or isoxazole ring systems, potential receptors in host—guest chemistry, have been prepared by multiple (double, triple or quadruple) 1,3-dipolar cycloadditions of nitrile oxides, (prepared in situ from hydroxamoyl chlorides) to bifunctional calixarenes, ethylene glycols, or silanes containing unsaturated ester or alkene moieties (453). This one-pot synthetic method has been readily extended to the preparation of different types of macrocycles such as cyclophanes, bis-calix[4]arenes and sila-macrocycles. The ring size of macrocycles can be controlled by appropriate choices of the nitrile oxide precursors and the bifunctional dipolarophiles. Multiple cycloadditive macrocy-clization is a potentially useful method for the synthesis of macrocycles. 

The examples summarized in Table 5 and in Sect. 5 of this review illustrate the applicability of RCM to the preparation of various macrocyclic perfume ingredients [30], pheromones [30], antibiotics [31-35], crown ethers [36], cyclic peptides [37],catenanes [38] and capped calixarenes [39]. 

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