Abstract
New chiral methacrylate, (S)-2-methoxy-1,1′-binaphthyl-2′-(N-methacryloyloxyethyl)carbamate (MBiMOC), was synthesized from 2-methacryloyloxyethyl isocyanate and 1,1′-binaphthalene-2,2′-diol. Radical polymerizations of MBiMOC were performed in several solvents to obtain the corresponding chiral polymers. Specific optical rotation of poly(MBiMOC) changed by the measurement temperature, which may be attributed in part to change of conformation caused by hydrogen bonds between urethane segments. From the results of copolymerizations of MBiMOC with styrene and methyl methacrylate, monomer reactivity ratios (r1,r2) and Alfrey-Price Q-e were determined and chiroptical properties of the copolymers were affected by co-units. Three types of chiral stationary phases (CSPs), poly(MBiMOC)-coated-silica gel (CSP-I), poly(MBiMOC)-bonded-silica gel (CSP-II), and (S)-MeBinol-bonded-silica gel (CSP-III) were prepared from silica gel, MBiMOC, and (S)-MeBinol. The CSPs resolved racemates some using n-hexane/2-propanol as mobile phase for high performance liquid chromatography (HPLC). Difference in chiral resolution ability between CSP-I, CSP-II, and CSP-III was observed, suggesting that the chiral recognition ability of poly(MBiMOC) may be based on the higher-ordered structure of the polymer.
Similar content being viewed by others
Article PDF
References
S. G. Allenmark, “Chromatographic Enantioseparation”, Ellis Howood Ltd., Chichester, 1988.
For example, Y. Okamoto, CHEMTECH, 176 (1987).
Y. Tamai, P. Qian, K. Matsunaga, and S. Miyano, Bull. Chem. Soc. Jpn., 65, 817 (1992).
G. Blaschke, Angew. Chem., Int. Ed., Engl., 19, 13 (1980).
G. Blaschke, W. Broker, and E. Frankel, Angew. Chem., Int. Ed., Engl., 25, 830 (1986).
D. Arlt, B. Bomer, R. Grosser, and W. Lange, Angew. Chem., Int. Ed., Engl., 30, 1662 (1991).
Y. K. Lee, K. Onimura, H. Tsutsumi, and T. Oishi, Polym. J., 32, 1021 (2000).
S. Matsuhiro, Konbatekku, 5, 8 (1997).
H. Kamogawa, H. Kohno, and R. Kitagawa, J. Polym. Sci., Part A: Polym. Chem., 27, 487 (1989).
C. Decker and K. Moussa, Eur. Polym. J., 27, 881 (1991).
I. Francis, S. Arjen, C. Israel, and S. Johannes, J. Polym. Sci., Part A: Polym. Chem., 31, 239 (1993).
H. Albrecht and W. Wunderlich, Angew. Makromol. Chem., 145/146, 89 (1986).
S. Savaskan and B. Hazer, Angew. Makromol. Chem., 239, 13 (1996).
N. Monzner, U. K. Fischer, T. Volkel, and V. Rheinberger, Angew. Makromol. Chem., 245, 155 (1997).
T. Oishi, Y.-K. Lee, A. Nakagawa, K. Onimura, and H. Tsutsumi, Polym. J., 33, 81 (2001).
C. H. Bamford, K. G. Al-Lamee, I. P. Middleton, J. Paprotny, and R. Carr, Bull. Soc. Chim. Belg., 99, 919 (1990).
Y. Kimitsuka, K. Iwata, and H. Suzuki, Jpn. Kokai Tokkyo Koho JP 6-308108 (Nov. 4, 1994).
Y. K. Lee, K. Onimura, H. Tsutsumi, and T. Oishi, J. Polym. Sci., Part A: Polym. Chem., 38, 4315 (2000).
T. Otsu and M. Kinoshita, “Koubunshigousei Jikkenhou”, Kagaku-dojin Publishing CO., Ltd., Kyoto, Japan, 1972, pp 69–91.
Y. Okamoto, S. Honda, I. Okamoto, and H. Yuki, J. Am. Chem. Soc., 103, 6971 (1981).
Y. Okamoto, E. Yashima, M. Ishihara, and K. Hatada, Bull. Chem. Soc. Jpn., 61, 255 (1988).
F. Tüdös, T. Kelen, T. Foldes-Berezsnich, and B. Turcsanyi, J. Macromol. Sci., Chem., A 10, 1513 (1976). The monomer reactivity rations were determined by the method 6 describedin this paper.
T. Jr. Alfrey and C. C. Price, J. Polym. Sci., 2, 101 (1947).
H. J. Harwood and W. M. Ritchey, J. Polym. Sci., Polym. Lett., 2, 601 (1964).
M. Kurokawa, H. Yamaguchi, and Y. Minoura, J. Polym. Sci., Polym. Ed., 17, 2241 (1979).
R. N. Majumdar, C. Carlini, and C. Bertucci, Makromol. Chem., 183, 2047 (1982).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Lee, YK., Onimura, K., Tsutsumi, H. et al. Synthesis of Novel Chiral Polymethacrylate Bearing Urethane and 1,1′-Binaphthalene Moieties and Its Chiral Recognition Ability. Polym J 33, 411–418 (2001). https://doi.org/10.1295/polymj.33.411
Issue Date:
DOI: https://doi.org/10.1295/polymj.33.411