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Selective Extractionof Fe3+ by a Polymeric Calix [41 arene HASALETTIN DELICOZ, MUSTAFA TAVASLI, and MUSTAFA YlLMAZ SelCukUniversity, Department of Chemistry, 42079, Konya,Turkey SYNOPSIS A polymeric compound containing more than one calixarene molecule was synthesized by reacting the oligomer (2) wi25,26,27-tribenzoyloxy-28- hlid[oxarene. After basic hydrolysis of3a,the polymeric calixarene(3b)was utilized for selective extraction of some metal cations from aqueous phase to organic phaseIt was found thatthe compound (3b) was selective toward Fe3+ from an aqueous solutioncontainingCuz+, Ni2+,Coz+ and Fe3+ cations. The mechanism of the extraction process was discusse1994 John Wiley Sons, Inc. Keywords: calixarene polymeric calix4[1arene solvent extractiontransition metalions INTRODUCTION In our previous work" we examined the selective extraction of Fe3+ion from an aqueous phase into Calix [n]arenes are oligo-phenols in which n mol of the organic phase by using p-tert-butylcalix [4 1- phenols are connected by n mol of methylene groups arene, calix arene, tetra-methyl-p-tert-butylca- to form cyclic compounds. These serve as host in- lix [41arene-tetra ketone, and tetraethyl-p-tert-bu- clusion compounds, ' selectively complexing metal tylcalix [41arene-tetra-acetate. ions, and catalyzing chemical reactions.' In the present work we prepared a polymeric ca- In contrast to a number of reports on the binding lix [41arene with the treatment of 25,26,27-triben- of alkali metal ions3 and lanthanides ions,4reports zoyloxy-28-hydroxycalix [41arene and the oligomer on the binding of transition metal ions have been (2 ). Itsbinding properties with Fe3+ion are com- limited. pared with its monomeric analog. Yoshida et al.5 found that p-tert-butyl ca- lix [61arene can extract Cu2+ ion from ammonia- c1 I alkaline solution into the organic solvent. Shinkai et al. have reportedthe synthesis of water soluble calixarenes, and a polymer-bound analog of this material is described in a patent, which states that the hexakis (carbethoxymethyl) ether of p- sulfonatocalix [61arene fixed on crosslinked chlo- romethylated polystyrene is used for selective ex- traction of uranyl ionUO;' from aqueous phase into the organic phase.6 C1 0 L bR 1, Recently,calixarenescontaining dimethyl-amino, I I diphenylphosphino, and vic-glyoxime groupsg on C.u-2 CH2 the upper rim (p-position of calix [ n]arene) have CH~-CIH-O-CH~-CH-O+,-CH~-CH-CH/O\ been found to bind some transition metal ions. ~~ 0 * To whom allcorrespondence shoulbe addressed J0 1994 John Wiley & Sons, Inc.t ACCC 0887-624X/94/152961-042,2961-2964 (1994) 3b: R = H 2961 2962 DELIGOZ, TAVASLI, AND YILMAZ EXPERIMENTAL Solvent Extraction A 5-mL solution of chloroform containing 1 or 3b Calix [41arene (1 ) and 25,26,27-tribenzoyloxy-28- (5.3.10-4 M) and a 25-mL aqueous solution con- hydroxycalix [ 41arene were synthesized by the pub- taining metal salt ( 1.06.10-4M) were placed in a lished method.''-'2 The oligomer (2) l3was synthesized by the treat- flask. The aqueous solution was buffered topH 2.2 (0.01 M NaN03/HN03, p = 0.1 with KCl), or to ment of toluene and epichlorohydrinin the presence pH 3.8, 4.5, and 5.4 (0.01 M CH3COONa/ of BF3 *0 (C2H5)2. BFs -0 (C2H5), (1.8 g) was stirred slowly in toluene (27.6 g, 0.3 mol,the mixture was CH3COOH, p = 0.1 with KCl). The mixture was shaken for 12 h at 25°C. The extractabilitywas not heated at 40"C, and epichlorohydrin (9.25 g, 0.11 affected by further shaking, indicatinthat equilib- mol) was added dropwise into the mixture for 2 h. rium has been attained within 12 h. The extracta- After the addition was completed, 40% NaOH (0.12 mol) was added to the reaction mixture, which was bility (Ex% ) was determined from the decrease in the metal concentration in the aqueous phase: heated at 50-60°C for6 h. After cooling, the mixture was poured into water. The organic phase was sep- arated and washed with water, and the product was dried up inuucuo. Yield 90%; IR( KBr) vc-0-c 1260 and 1140 cm-l, vc-c~ 760 cm-'. Found C, 45,07%; H, 5.64%;C1,33.28%.Calcd.for (C40H62011C110 C),. where (metal)blankand (metal )watedenote the metal 44.94%; H, 5.85%; C1, 32.74%; Osmometric Mw concentrations in the aqueous phase, after extrac- (CHCl3,37"C), 1074. tion with pure chloroform solution containing ex- Treatment of2 with 25,26,27-tribenzoyloxy-28- tractants. hydroxycalix [41arene (3a).A 2.7 g (3.67 mmol) sample of 25,26,27-tribenzoyloxy-28-hydroxycalix- arene was dissolved in 20 mL of THF/toluene RESULTSAND DISCUSSION (9 : 1) and treated with 0.1 g (3.33 mmol) of 80% NaH followed by a solution of 2 (0.4 g, 37 mmol) In our previous work, selective extraction of Fe3+ in 5 mL THF. The mixture was heated at reflux for cation from aqueous phase to organic phase was 1 h and concentrated to ca.5 mL, treated with 15 mL methanol, the precipitate being collected by fil- achieved with calix [41arene and some of its deriv- atives." tration, and washed with H20, and dried in uucuo. In the present work a polymeric calixarene was Yield 88%; mp 130°C. IR(KBr) YO-H 3450 cm-', vc=o 1770cm-', VC-0-c 1280 and 1180 cm-', vc--cI synthesized by combining calix [41arene ( 1 ) with the oligomer(2 ).This was accomplished by reacting 760 cm-'. 'H-NMR (CDC13) 6: 1.1 (s), 1.4-1.7 25,26,27-tribenzoyloxy-28-hydro [4ylaene ix (broad), 3.4-3.8 (broad), 6.9-7.8 (m) . Found C, 74, 41%; H, 5.14%; C1, 4.21%. Calcd. for with the oligomer(2) in the presence of NaH. Based on the chlorine analysis of this product, it was ob- (C285H23704&15). C, 74.84%; H, 5.23%; C1,3.99%. served that the compound ( 1) did not attachto each consecutive (CH2-C1) groups in a regular array. Hydrolysisof 3a Instead, the attachment followed a single-step al- A solution of 0.8 g (0.175 mmol) of 3a in 20 mL of ternating sequence. THF/toluene (9: 1) was treated with a solutionof The polymericcalixarene (3a) thus obtained was 2.5 g of NaOH in 10 mL H20 and 20 mL ethanol, hydrolyzed with ethanolic NaOH solution in order and the mixture was refluxed for 18 h. The reaction to remove the benzoyl groups prior to use for the was completed when no carbonyl band was detected extraction process. With the hydrolyzed compound the extraction of Fe3+cation from aqueous phase to in the product. The solvent was removed on a rotary evaporator, andthe residue was trituratedwith di- organic phase (chloroform) was possible in a sig- lute HC1. The precipitate was washed with water, nificantly largerratio even at pH 2.2 (Table I). and dried inuucuo. Yield 93%;mp (dec.) 252-260°C. Extraction of Fe3+with calix 41 arene, which was IR(KBr) vOPH 3350 cm-', ~~-0-c 1280 and 1230 7%, has increased to 82% when the polymeric ca- cm-'. Found C, 72.00%; H, 6.02%; C1,6.21%.Calcd. lix arene was employed (Fig. 1 ). for (C180H177031C1C 5,);71.78%; H, 5.93%;C1,5.81%. Only trace amounts of other metal cations such SELECTIVE EXTRACTION OF Fe3+ 2963 Table I. Extraction of Metal Cationswith Ligands" Metal Cations Extracted(W) Ligand Fe 3+ Ni'+ Co2+ cu2+ PH 1 8.4 t1.0 <1.0 4.6 2.2 1 56.0 <LO t1.0 7.3 3.8 1 57.5 t1.0 t1.0 8.9 4.5 1 90.0 <1.0 <1.0 9.6 5.4 3b 82.0 <1.0 <1.0 3.7 2.2 3b 93.0 <1.0 <1.0 6.5 3.8 3b 94.0 4.0 <LO 9.2 4.5 3b 96.0 <1.0 <1.0 9.8 5.4 *Aqueous phase [Metanitrat= 1.06.10M'I. Organic phase [chloroform, (l=g5.3.10-4 MI. pH: 2.2 (0.M NaN03/HN03, =0.1with KCI), pH 3.8, 4.5, and(0.0M CH3COONa/ CH3COOH, p = 0.1 with KCI), at 25OC for 24 h. as CU", Co2+, and Ni2+ were transferred from a compound similar to compound (1) was formed. aqueous to organic phase at pH 2.2. Furthermore, Formation ofsuch a complex was evident from the the extracted quantities of these cations remained changing color of solution into brown, and the ap- unaffected with increasing pH. pearance of an absorption maximum at 534 nm. The UV spectrum of compound ( 1 ) in DMF did The plot of the ratio between the amount of Fe3+ not exhibit an absorption maximum above 300 nm, in aqueous phase to that in organic phase against while the absorption maximum of its Fe3+complex pH was linear with a slope of one (Fig. 2), which appeared at 534 nm. The metal/ligand ratio deter- indicates that one proton was separated from the mined at this wavelength by the Job method was ligand. 1 :1. An extraction equilibrium constant [K,, Jcalcu- The compound (3b), before hydrolysis did not lated with the following equation was 22. coordinate with Fe3+in DMF, while after hydrolysis Fe3+ + H4L + [H3L]Fe2+ + H+ The compound 2 (oligomer ) was reacted with p- tert-butylphenol. In extraction experiments per- formed with this compound, it was observed that Fe3+cation was extracted onlyin traceamounts from the aqueous phase into organicphase. Based on the above results we have concluded 0 2 L 6 pii Figure 1. pH dependence for the Fe3+ extraction. Aqueous phase [metal nitrate = 1.06.10- M4I. Organic 2 3 4 5pH phase [chloroform,(ligand) = 5.3.10-MI; 25OCfor 24 h.(0) Ligand 1and (0) Ligand 3b. Figure 2. Relations between pH and logD (in CHCl3). 2964 DELIGOZ, TAVASLI, AND YILMAZ that calix arene unit plays a very important role 7. C. D. Gutsche and K. C. Nam., J. Am. Chem. Soc., in the extraction process. 110,6153 (1988). 8. F. Hamada, F. Fukugaki, K. Murai, G. W. Orr, and J. L. Atwood, J. InclusionPhenom., 10 (1),57 (1991) . REFERENCES 9. M. Yilmaz and H. Deligoz, Synth. React. Znorg.Met.- Org. Chem., 23 ( 1), 67 (1993). 10. M. Yilmaz and H. Deligoz, MacromolecularReports, 1. C.D. Gutsche, Prog. MacrocyclicChem., 3,93 (1988). 2. C. D. Gutsche, Calirarenes, Royal Society of Chem- 31(1-2), 137 (1994). istry, Cambridge, 1989. 11. C.D. Gutsche, J. A.Levine, and P. K. Sujeeth, J. Org. Chem., 50,5802 (1985). 3. F. Arnaud-Neu, E. M. Collins, M.Deasy, G. Ferguson, 12. C. D. Gutsche and L. G. Lin., Tetrahedron, 42 (16), S. J.Harris, B. Kaitner, A.J. Lough,M. A.McKenvey, E. Maarques, B. L. Ruhl, M. J. Schwing-Weill, and 1633 (1986). 13. R. A. Kurbanova, A. V. Rahimov, N. R. Bektaqi, ve E. M. Seward, J. Am. Chem.Soc., 11 1,8681 ( 1989). K. A. Aslanov, Azerbaycan Kimya Dergisi, 1, 84 4. S. K. Chang and I. Cho, J. Chem. Soc., PerkinTrans. ( 1988). I.,2,211 (1986). 5. I. Yoshida, S. Fujii, K. Ueno, S. Shinkai, and T. Mat- suda, ChemistryLetters, 1535, ( 1989). 6. S. Shinkai, Y. Shiramama, H. Satoh, 0. Manabe, T. Arimura, K. Fujimoto, and T. Matsuda, J. Chem.Soc., Received January 31, 1994 Perkin Trans. 11,1167 (1989). Accepted May 25,1994
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