SYNTHESIS OF C-METHYL-4,10,16,22-TETRAMETHOXYCALIX[4]ARENE FROM PHENOL USING BF3-METHANOL AS THE CATALYST

https://doi.org/10.22146/ijc.21840

Jumina Jumina(1*), Evi Triwulandari(2), Chairil Anwar(3)

(1) Chemistry Department, Faculty of Mathematics and Natural Sciences Gadjah Mada University, Yogyakarta
(2) Chemistry Department, Faculty of Mathematics and Natural Sciences Gadjah Mada University, Yogyakarta
(3) Chemistry Department, Faculty of Mathematics and Natural Sciences Gadjah Mada University, Yogyakarta
(*) Corresponding Author

Abstract


   C-Methyl 4,10,16,22-tetramethoxycalix[4]arene has been synthesized from phenol. The reaction performed consisted of methylation of phenol, acetylation of methyl phenyl ether, reduction of p-methoxyacetophenone, and cyclization of p-methoxy-(1-hydroxyethyl)benzene to form C-methyl-4,10,16,22-tetramethoxycalix[4]-arene using BF3-methanol as the acid catalyst.  Methylation of phenol was done by reacting phenol with solution of NaOH to generate sodium phenoxide salt. This mixture was strirred at  reflux for 0.5 hours. Dimethyl sulphate was added and the reflux was continued for 2,5 hours. The product obtained was methyl phenyl ether, which was found as  a colorless liquid in 99.0% yield. Acetylation of methyl phenyl ether was carried out in chloroform using acetic anhydride as the acetylating agent and anhydrous aluminium chloride as the catalyst. The addition of acetic anhydride and anhydrous aluminium chloride was done in two portions. The first portion was 0.967 g of acetic anhydride and 1.4 g of anhydrous aluminium chloride. The second portion was 0.54 g of acetic anhydride and 0.6 g of anhydrous aluminium chloride. The product obtained was found as a reddish yellow liquid in 69.6% yield. Reduction of p-methoxyacetophenone as the acetylation product  was  done using NaBH4 in ethanol at reflux for 2.5 hours. From this reaction, p-methoxy-(1-hydroxyethyl)benzene was obtained as a brown viscous liquid in 44.9% yield. Cyclization of p-methoxy(1-hydroxyethyl)benzene was done using BF3-methanol as the acid catalyst for two days at room temperature. The product obtained from this cyclization was found as a brown very viscous liquid in 87.3% yield. Identification of reaction products were carried out using Infra Red (IR) Spectrophotometer, Proton Nuclear Magnetic Resonance (1H NMR) spectrometer and Gas Chromatography-Mass spectroscopy (GC-MS).


Keywords


synthesis; calix[4]arene; cyclization; catalyst

Full Text:

Full Text Pdf


References

[1]   Gutsche, C.D., 1989, Calixarene, Monograph in Supramolecular Chemistry, Royal Society of Chemistry, Cambridge. 

[2]   Gutsche, C.D., 1998, Calixarene Revisited, Monograph in Supramolecular  Chemistry, Royal Society of Chemistry, Cambridge. 

[3]   Wu, T.-T, Speas, J.R., 1987, J. Org. Chem., 52, 2330-2332.

[4]   Asfari, Z., Vicens, J., 1988, Tetraheron Letters, 29, No. 22, 2659-2660.

[5]   Izatt, S.R., Hawkins, R.T., Christensen, J.J., Izatt, R.M., 1985, J. Am. Chem. Soc., 107, 63.

[6]   Cornforth, J.W., Morgan, E.D., Potts, K.T., Rees, R.J.W., 1973, Tetrahedron, 29, 1659.

[7]   Nakamoto, Y., Kozu, T., Oya, S., Ishida, S., 1985, Chem. Abstr., 105, 6301g.

[8]   Nakamoto, Y., Ishida, S., Yoshimura, Y. (Hitachi Chemical Co. Ltd.), 1987, Chem. Abstr. 108:56797f.

[9]   Jumina, Siswanta, D., Santosa, S.J., Anwar, C., Ohto, K., and Oshima, T., 2003,  Synthesis and Use of 4,10,16,22-Tetraalkoxycalix[4] arenes, p-Alkenyl-calixarenes, and p-Haloalkyl calixarenes for Trapping of Heavy Metal Cations, RUTI Annual Report for 2003.

[10] Sarjono, R.E., 1999, Sintesis Kaliksarena dari Minyak Adas dan Penggunaannya Sebagai Penjebak Kation Logam Berat, Tesis S2, Program Pasca Sarjana UGM, Yogyakarta.

[11] Vogel, A.I., 1967, A Text-Book of Practical Organic Chemistry, 3rd Edition,  Longmans, London, 761-762.



DOI: https://doi.org/10.22146/ijc.21840

Article Metrics

Abstract views : 590 | views : 1244


Copyright (c) 2010 Indonesian Journal of Chemistry

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

 


Indonesian Journal of Chemistry (ISSN 1411-9420 / 2460-1578) - Chemistry Department, Universitas Gadjah Mada, Indonesia.

Web
Analytics View The Statistics of Indones. J. Chem.