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DESIGN and SYNTHESIS of CALIXARENE 745 Vol Journal of Scientific & Industrial Research AGRAWAL at al: DESIGN AND SYNTHESIS OF CALIXARENE 745 Vol. 68, September 2009, pp. 745-768 Design and synthesis of calixarene Y K Agrawal* J P Pancholi and J M Vyas Institute of Research and Development, Gujarat Forensic Sciences University, Sector 18A, Gandhinagar 382 007, India Received 06 October 2008; revised 01 June 2009; accepted 16 June 2009 Calixarenes are versatile macromolecules in the field of supramolecules because of its synthetic feasibility and extensive analytical applications. This paper reviews synthesis of calixarenes and related derivatives containing heterocycles, polymers, crown-ethers, and fullerenes. Various analytical applications of calixarenes are discussed. Keywords: Calixarenes, Crown-ethers, Fullerenes, Polymers Introduction upper rim substitution of calixarene is carried out by de-t- Calixarene is a macrocycle or cyclic oligomer based butylation of p-tert-butyl group followed by subsequent 21-24 on a hydroxyl alkylation product of phenols and reaction. Substitution of hydroxamic acid group and bromination25 is reported. Similarly, p-bromination of aldehydes1. Calixarenes have hydrophobic cavities that calix[4]arenemethylether26 and bromination of tetra- can hold smaller molecules or ions and belong to the methoxycalix[4]arene is also reported27. Ipso- class of cavitands known as host-guest chemistry. In bromination28 has been carried out under a variety of 2 1940s, Zinke & Ziegler discovered base-induced reaction parameters. Optimized conditions give p- reaction of p-alkylphenols with formaldehyde, which bromocalixarenes and methylene bridge brominated yields cyclic oligomers. Then, synthesis of cyclic calix[n]arene directly28. Single step, one-pot procedure oligomers was reported3. Calixarenes can be used as is also given (Scheme 1) for conversion of p-tert- ion sensitive electrodes or sensors4, optical sensors5, butylcalix[n]arenes (Table 1) to their p-acyl derivatives; chiral recognition devices for solid phase extraction, thus (2) and (3) has been prepared29. Ipso-substitution is 30 as a stationary phase and modifiers6. Several books7- also possible with more than one substitution (Table 2) . 12 and reviews13-17 covered synthesis, properties and Calixarenes having larger cavity size like calix[8]arenes can also be ipso substituted31. applications of calixarenes. Some studies18-20 reported Calixarenes of varying cavity size can form variety structures and properties of calixarene. This review of host-guest type of inclusion complexes similar to presents five types of calixarenes. cyclodextrins. However, calixarene host molecules have a unique composition that include benzene groups, which I. Modified Calixarenes provide À-À interaction and hydroxyl groups for hydrogen There are two places (phenolic hydroxyl groups bonding, which is generally water insoluble. Shinkai et al and p-positions) for modification of calixarenes. synthesized water-soluble calixarenes having sulfonate Methylene bridges may be substituted with aromatic groups32. Calixarene cavity is capable for molecular system of phenolic units as a whole or may lead to recognition in solution, and can be applid in remediation replacement of OH-function by other groups. Functional of contaminated groundwater and industrial effluents. groups introduced in a first step may be further modified Intercalation of water-soluble p-sulfonated calix[4]arene by subsequent reactions including migration. Usually (CS4) in interlayer of Mg-Al and Zn-Al lactate dehydrogenase (LDHS) (M2+/Al = 3) by co-precipitation *Author for correspondence method33 showed adsorption ability for benzyl alcohol E-mail: [email protected] (BA) and p-nitrophenol (NP) in aqueous solutions, which 746 J SCI IND RES VOL 68 SEPTEMBER 2009 Table 1—Substitutions for p-acyl derivatives prepared from p-t-butylcalixarene R1 R2 R3 R4 (3) R4 (4) OH H CO-C6H5 CO-C6H5 CO-C6H5 OH t –Bu CO-C(CH3)3 CO-C(CH3)3 CO-C(CH3)3 OMe t –Bu CO-CH3 t-Bu CO-4-NO2C6H4 CO-CH3CH2 t-Bu Table 2—ipso-substitution group for calix[4]arene are also larger in Zn-Al/CS4/LDH than in Mg-Al/CS4/ LDH because of effective use of parallel arranged cavity Compound R R R R 1 2 3 4 only in Zn-Al/CS4/LDH. CS4/LDHs have possibility as new organic-inorganic hybrid adsorbents. 1 H H H H Makha & Rasston34 synthesized water soluble 2 H H H Me calixarenes using p-phenyl calix[n]arene and sulfonate 3 H COMe H Me derivatives (Scheme 2), which have exciting possibilities 4 H H H COMe as a phase transfer catalyst in transport processes. To 5 Me COMe H H increase size of a hydrophobic cavity, calix[n]arenas 6 Me H H COMe (Scheme 3) consist of different bulky groups. Functional 7 Me H H CoMe groups present in adamantine fragment (9) and (10) SO3H R 1 H2CO H2SO4 OR3 OH n=4,5,6,8 KOH ClSO3H AlCl n RCOCl 3 n n n n OH OH OH R2 (5) (6) n= 4, 8, 6 R4 R4 (4) (1) (2) (3) Scheme 2 Scheme 1 R R OH CF3COOH CH3 + R CH n CH 3 OH 3 + n CH CH3 3 CH3 n-1 OH OH OH (7) (8) (9) (10) Scheme 3 AGRAWAL at al: DESIGN AND SYNTHESIS OF CALIXARENE 747 R1CH2BR K2CO3, Na2CO3,CH3CN O OH OH O R1 (12) R1 OH OH OH HO R2CH2BR Na2CO3 CH3CN OH OH OH O R1= p-MeC6H4 R2= m-MeC6H4 R2 (11) (13) Scheme 4 NH2 NO2 SnCl2, 2H2O CH2Cl2, r.t., 3h EtOH, reflux HNO3 HOAc O O O O O O O O O O O O R R R R R R R R R R R R (16) (14) (15) NO2 NO2 NO2 NO2 CH2Cl2, r.t., 3h + HNO3 HOAc O O O O O O O O R R R R R R R R (18) (17) R=CH2CH2CH3 R=CH2(CH2)8CH3 S nCl2, 2H2O EtOH, reflux SnCl2, 2H2O EtOH, reflux NH NH NH2 NH2 2 2 O O O O O O O O R R R R R R R R (19) (20) Scheme 5 748 J SCI IND RES VOL 68 SEPTEMBER 2009 K2CO3 O OH OH O Br(CH2)3Br OH OH OH HO (22) Br Br (21) OH K2CO3 CH CN N 3 O OH OH O O O N N (23) Scheme 6 should provide possibility for further modification and possesses multiple chromogenic donors (Scheme 7) and conformational organization of molecule35-37. Self- is useful for alkali metal ions Na+, K+, Rb+ and Cs+. Bis assembly of tetradentate ligand 5,5-bipyrimidine with and tetrakistetrazole derivatives of calix[4]arene (32) c-methyl calix[4]resorcinarene is reported38,39. It have ability to bind cations of transition metals modulates volume and periphery of cavity in a predictable (Scheme 8). Result of structural investigation of fashion by changing size, flexibility and composition of macrocycle and its complex with palladium dichloride is spacer between pyrimidyl units. also reported49-51. Introduction of bulky substituents as m-methyl Separation of amino acids is a key technology for benzyl groups incorporate and remove protective groups downstream processing in bio-industrial complex. Tabaksi in synthesis of calixarenes with three different et al52 carried out a reaction of p-tert-butylcalix[4]arene substituents in molecule. In presence of sodium and and p-h-calix[4]arene with (S)-(-)-1-phenylethylamine potassium carbonates, reaction of calixarene with p and (37) (Scheme 9), which forms useful host molecule for m-methyl benzyl bromides gives compounds (12) and quantitative extraction of ±-amino acid methyl esters and (13) that affect composition, current conformations, and ±-phenylethylamines in a liquid–liquid extraction system. yield of products (Scheme 4)40-43. Calix[4]arene Specified applications of calixarenes can be possible by nucleoside base (19) and (20) receptors provide ion substitution of selected groups either on upper or lower pairing complex44 (Scheme 5). Novel bis (8- rim. Several picoline binding groups at upper or lower hydroxyquinoline)calix[4]arene (23) is a versatile building rim of calix[n]arenes (39) (n = 4, 6, 8) have been block of supramolecular chemistry (Scheme 6). This synthesized for extraction of actinides (Scheme 10)53. ligand is specially designed for photo physical applications Fluorescence chemosensors, calix[4]arene containing in metalo-supramolecular chemistry45-47. Liu et al48 tetraamide derivative (43) (Scheme 11)54, exhibit high – synthesized bis(azo-phenol)calix[4]arenes (27), which selectivity for H2PO4 over a wide range of anions; AGRAWAL at al: DESIGN AND SYNTHESIS OF CALIXARENE 749 t- t-Bu t-Bu t-Bu t- t-Bu t-Bu t-Bu Bu Bu t- t-Bu t-Bu t-Bu Bu ClCH CN 2 LIAlH4 anhydrous acetone O OH OH O anhydrous THF O OH OH O OH OH HO NC OH CN H2N NH2 (25) (24) (26) OHC OH N anhydrous THF N R t- t-Bu t-Bu t-Bu Bu O OH OH O N N CH OH CH HO N N N N (27) Scheme 7— (THF, Tetrahydrofuran) – 61 selectivity for H2PO4 is more than 2700-fold higher than arranged on calix[4]arene skeleton . Compound (54) for F–. (Scheme 14) recognizes Na+ and Ag+ simultaneously as Fluorescence-labeled calix[4]arene substituted with well as quantitatively and captures an anionic guest. - peptides serve as a useful platform to produce artificial Ability of (54) to recognize anions including CF3SO3 - + + receptors using peptides and various types of other and BF4 remarkably increases using Na and Ag . Yang building blocks55.Upper rim, c-linked and cbz-protected et al62 and Tilki et al63 synthesized oxo-calixarenes (57), cone calix[4]arene bis-l-alanyl derivative have been (58) (Scheme 15), which have unique applications in synthesized to prepare self-assembled nanotubes in solid molecular recognition studies and for enhancement of Ag+ state through a two-dimensional network of hydrogen and Hg+ ion selectivity by minimizing side arm effect.
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