CALIXARENE DERIVATIVES FOR THE COMPLEXATION OF CESIUM AND THALLIUM CATIONS

Mikio Ouchi

Centre for General Education University of Hyogo 2167 Shosha, Himeji, Hyogo 671-2280 Japan Email:ouchi@eng.u-hyogo.ac.jp

ABSTRACT The synthesis and cation-binding properties of a series of Calixarene derivatives possessing alkyl chain groups, ester groups and crown ether rings have been investigated. The syntheses of Calix[4]arene crown ethers and Calix[6]arene derivatives possessing alkyl chain, ester group and crown ether ring have been described. In order to evaluate their monovalent cation binding abilities, solvent extraction of alkali metal and heavy metal picrates between water and dichloromethane has been carried out in order to reveal the effect of substituents, number of aromatic rings and size of crown ether ring. The extractability of metal picrates has been measured. The results showed that introduction of crown ether ring increased the thallium (I) and cesium cation binding ability and selectivity toward other monovalent cations (sodium, potassium and silver). Calix[6]arene-crown ether possessing ester group showed the highest cation-binding ability for thallium (I) and cesium cation in the compounds used in this study. INTRODUCTION Molecular design of organic compounds for application in the areas of supramolecular chemistry has been a subject in organic chemistry. The chemistry of Crown Ethers has been one of the most pioneering topics since Pedersens work in 1967 (Pedersen, 1967). We have also explored the synthetic approach for the molecular design of crown ethers toward cation-binding ability, especially benzo-type crown ethers (Ouchi et al., 2006). The result showed that aromatic ring electrons and the symmetry of the crown ether molecule gave monovalent heavy metal cation selectivity (silver and thallium) over alkali metal cations (sodium and potassium). Calixarenechemistry is also the subject on heavy metal cation binding for separation science chemistry. The calixarene structure itself can behave as a soft donor group through its phenyl group electrons, and this has been demonstrated by the inclusion of heavy metals, e.g. silver and thallium (I), within the cavity of the calix[4]arene derivatives (Couton et al., 1999). Our recent work on calix[4]arene derivatives bearing alkyl, benzyl, and crown ether groups also support the result (Ouchi et al.,2008, 2009). Taking into account our results on crown ethers and calix[4]arene compounds, the present study deals with larger size calixarene derivatives, Calix[6]arene derivatives. The studies on the cation-binding ability of Calix[6]arene derivatives has been reported, and the results showed the low cation-binding ability for alkali metal cations. In this study, syntheses of Calix[6]arene derivatives possessing alkyl, ester, and crown ether groups (1-8) and their cation-binding abilities (sodium, potassium, cesium, silver and thallium) have been evaluated by solvent extraction of metal picrates in order to discuss

M.Ouchi the complexation phenomena. The results have been compared with those of Calix[4]arene derivatives (9-12) possessing alkyl, ester and crown ether groups.

MATERIALS AND METHODS Reagents. N,N-dimethylformamide (DMF) and benzene were distilled from sodium hydride (NaH). Commercially available reagents were used in the following syntheses without further purification unless noted otherwise. Analysis. Melting points were measured with MEL-TEMP II (Laboratory Devices. Inc.) apparatus and are uncorrected. The analytical data including the experimental methods of the compounds (1-12) will be reported elsewhere. Syntheses. The parent Calix[6]arene 1 was prepared from the base-catalysed (KOH) condensation of p-tert-butylphenol with formaldehyde in 55% yield. Calix[6]arene with six ester groups 2 was prepared from 1 and ethylbromoacetate in DMF in 71% yield. Calix[6]arene-crown-4 3 was prepared from 1 and trietylene glycol ditosylate in the presence of potassium carbonate in acetonitrile in 59% yield. Then Calix[6]arenecrown-4 5 possessing four ester groups was prepared from 3 and ethylbromoacetate in the presence of NaH in DMF in 39% yield. Calix[6]arene-crown-5 4 was prepared from 1 and tetraethylene glycol ditosylates in acetonitrile in the presence of potassium carbonate as a base at reflux temperature for seven days according to the similar procedure previously reported (Ouchi et al., 2008). The compound was purified by column chromatography over silica-gel with ethylacetate-hexane eluent. Calix[6]arene derivatives possessing n-propyl, iso-propyl, or benzyl groups 6-8 were prepared from 1

M.Ouchi and the corresponding reagents (1-iodopropane, 2-iodopropane, or benzyl chloride) in DMF in the presence of NaH in 70, 75, and 61% yield respectively. The parent Calix[4]arene 9 was prepared from the base-catalysed (NaOH) condensation of p-tertbutylphenol with formaldehyde in 38% yield. Calix[4]arene with four ester groups 10 was prepared from 9 and ethylbromoacetate in DMF in 54% yield. Calix[4]arene-crown4 11 was prepared from 9 and triethylene glycol ditosylate in benzene in the presence of potassium carbonate in 27% yield. Likewise, Calix[4]arene-crown-5 12 was prepared from 9 and tetraethylene glycol ditosylate in benzene in the presence of potassium carbonate in 14% yield. Solvent Extraction. UV-VIS spectra were recorded on a Shimazu UV mini-1240 spectrophotometer. The general extraction procedures employed are similar to those previously described (Ouchi et al., 2006, 2009). Distilled dichloromethane and demineralized water were used. The solvents were saturated with each other before use in order to prevent volume changes of the phases during extraction. Equal volumes (5mL) of dichloromethane solution of the respective Calixarene compounds (3.0 mM) and of an aqueous solution of the corresponding metal picrate (3.0 mM) were shaken for 10 minutes at 25 degrees Celsius in a Taiyo M100L incubator. The mixture was then allowed to stand for at least 90 minutes at that temperature in order to complete phase separation. The organic phase was separated by filtration (Toyo filter paper No.2s). Since the picrates do not dissolve in dichloromethane, the molar extinction coefficients in a 1:1 mixture of dichloromethane and acetonitrile were determined. The concentration of the metal picrates in the organic phase was determined from the absorbance at 375 nm in a mixture of dichloromethane and acetonitrile. The molar extinction coefficients at the absorption maximum of 375 nm for sodium, potassium, cesium, silver, and thallium picrates are 18600, 19000, 18500, 18800 and 18900 M-1cm-1respectively. RESULTS AND DISCUSSON In the present study, little effort was made to optimize yields. The technical reason of the purification would cause the range of the yield. It took almost a week in some cases to finish the reaction by checking TLC measurement. According to the report (Casnati et al., 2001), the reaction gave several by-products. However, in the present study, we have not done this search and discussions. A wide variety of measurement techniques for evaluating the characteristics of macrocyclic compounds (e.g. crown ethers and calixarenes) have been reported. Solvent extraction has been employed as a convenient method for evaluating the cation-binding ability of calixarene compounds as well as crown ethers. The obtained data for simple measurement of percentage extractability defined as percentage picrate extracted into the organic phase were considered. The result of the preliminary extraction (the concentration of 1-12 was 3 mM), and that of picrate was 3 mM at 25 degrees Celsius is shown in Figure 1.

M.Ouchi

Under this condition, non-substituted parent Calix[6]arene 1, and Calix[4]arene 9 did not show extractabilites for cations used in this study. It is shown that by the addition of the substitution at their lower rim (at OH position) position, their cation-binding abilities vary by the effect of the coordination sites. For the substituted Calix[6]arene derivatives 2-5 and Calix[4]arene derivatives 10-12 both possessing coordination sites (ester oxygen or crown ether oxygen), their cationbinding was effected by oxygen atoms and the number of the oxygen atoms. Ester type Calix[6]arene 2, showed the higher cesium (Cs+) and thallium (I) (Tl+) extractabilities compared with those toward sodium, potassium and silver cations. Furthermore, Crown ether type Calix[6]arene 3,4,5 and Calix[4]arene 12, also showed higher extractabilities for Cs+ and Tl+. This would be explained by the contribution toward -coordination for heavy metal Tl+ complexation and also by toward crown ether type coordination for larger Cs+ according to the generally accepted size-fit concept for crown ethers. CONCLUSION In view of the molecular design of larger size Calix[6]arene derivatives, the compounds of Calix[6]arene derivatives 2-5 synthesized in this study would be promising host molecules for the larger ion Cs+ and Tl+. Since the small amount of Cs+ and Tl+ in the earth, the separation/concentration from the ground or water would be the topic in the field of analytical science. The promising characters on cation-binding ability of this kind of larger Calix[6]arene-crown ethers possessing coordination sites would be found by the cavity size of crown ether skeleton and additional coordination sites. REFERENCES Casnati, A, Ungaro, R, Asfari, Z & Vicens, J 2001, `Crown Ethers Derived from Calix[4]arenes`, Calixarenes 2001, Eds.by Asfari et al., Kluwer Academic Publishers, 2001, pp. 365-384. Couton, D, Mocerino, M, Rapley, C, Kitamura, C, Yoneda, A & Ouchi, M 1999 `Silver and Thallium Ion Complexation with Allyloxycalix[4]arenes, Aust. J. Chem., vol. 52, no. 3, pp.227-229.

M.Ouchi Ouchi, M, Kojima, M, Otoshi, Y, Yoshida, H, Yokohara, T & Shibata, H 2006 `Extraction of Metal Picrates with Benzo-21-Crown-7 and Benzo-24-Crown-8 Ethers`, Solvent Extr. Res. Dev. Jpn., vol. 13, pp. 155-160. Ouchi, M, Oima, M, Fujio, E, Yamashita, T & Shibata, H 2008 `Cation Binding Properties of Calix[4]arene Derivatives Bearing Alkyl and Benzyl Groups at the Lower Rim`, Reports of Graduate School of Engineering, University of Hyogo, no. 61, pp. 20-24. Ouchi, M, Fujio, E, Nishino T, & Yamashita, T, 2009 Solvent Extraction of Metal Picrates with Calix[4]arene-Crown Ethers, Abstract Book of CHEMECA 2009, No.530. (Perth, Australia) Pedersen, C, J 1967 `Cyclic Polyethers and their Complexes with Metal Salts`, J. Am. Chem. Soc., vol. 89, no. 26, pp. 7017-7036.

BRIEF BIOGRAPHY OF PRESENTER Dr. Mikio Ouchi is currently RACI member, and Professor of University of Hyogo (Centre for General Education), Japan. He obtained Ph.D. degree from Himeji Institute of Technology (Japan) in 1984 under the title of Molecular Design of Crown Ethers. His research interest is on supramolecular chemistry, and chemical education for undergraduate students.