Abstract
Two novel monomers, N-[(±)-(2-fluorophenyl)(4-fluorophenyl)(phenyl)methyl]methacrylamide (2F4FPhMAM) and N-[(4-butyl)triphenylmethyl]methacrylamide (BuTrMAM), were synthesized and polymerized in the presence of (+)- and (−)-menthol as the chiral additive at different temperatures. The obtained polymers, P2F4FPhMAM and PBuTrMAM, are optically active. P2F4FPhMAM is not soluble in common organic solvents and no enantiomer selection was observed in the polymerization of racemic 2F4FPhMAM in the presence of the optically active additive (+)- and (−)-menthols. PBuTrMAM is soluble in THF and chloroform. The circular dichroism spectra of the polymers is similar to that of optically active poly[(triphenylmethyl)methacrylamide] with a prevailing one-handed helicity, suggesting that the present polymers also have a prevailing one-handed helicity. The tacticity of the polymers was estimated from the 1H NMR spectrum of polymethacrylamide derived in D2SO4. The polymers are almost 100% isotactic. The chiroptical properties of the obtained polymers were studied in detail.
Similar content being viewed by others
Article PDF
References
Y. Okamoto and T. Nakano, Chem. Rev., 94, 349 (1994).
Y. Okamoto and E. Yashima, Prog. Polym. Sci., 15, 263 (1990).
E. Yashima, K. Maeda, and Y. Okamoto, Nature, 399, 449 (1999).
Y. Okamoto, T. Nakano, S. Habaue, K. Shiohara, and K. Maeda, J. Macromol. Sci., Part A: Pure Appl. Chem., 34, 1771 (1997).
G. Wulff, Angew. Chem., Int. Ed., 28, 21 (1989).
G. Wulff, Chemtech., 21, 364 (1991).
P. Pino, Adv. Polym. Sci., 4, 236 (1967).
Y. Okamoto, K. Suzuki, K. Ohta, K. Hatada, and H. Yuki, J. Am. Chem. Soc., 101, 4763 (1979).
Y. Isobe, D. Fujioka, S. Habaue, and Y. Okamoto, J. Am. Chem. Soc., 123, 7180 (2001).
S. Habaue, Y. Isobe, and Y. Okamoto, Tetrahedron, 58, 8205 (2002).
Y. Isobe, Y. Suito, S. Habaue, and Y. Okamoto, J. Polym. Sci., Part A: Polym. Chem., 41, 1027 (2003).
B. Ray, Y. Isobe, S. Habaue, M. Kamigaito, and Y. Okamoto, Polym. J., 36, 728 (2004).
B. Ray, Y. Okamoto, M. Kamigaito, M. Sawamoto, K. Seno, S. Kanaoka, and S. Aoshima, Polym. J., 37, 234 (2005).
T. Nakano and Y. Okamoto, “Controlled radical polymerisation,” ACS Symposium Series No. 685, American Chemical Soceity, Washington D.C., 1998, p. 451.
T. Nakano, Y. Shikisai, and Y. Okamoto, Polym. J., 28, 51 (1996).
N. Hoshikawa, Y. Hotta, and Y. Okamoto, J. Am. Chem. Soc., 125, 12380 (2003).
M. Canle, W. Clegg, I. Demirtas, M. R. J. Elsegood, and H. Maskill, J. Chem. Soc., Perkin Trans., 2, 85 (2000).
T. Nakano, Y. Satoh, and Y. Okamoto, Polym. J., 30, 635 (1998).
Y. Okamoto, M. Adachi, H. Shohi, and H. Yuki, Polym. J., 13, 175 (1981).
Y. Okamoto, H. Hayashida, and K. Hatada, Polym. J., 21, 543 (1989).
K. Shiohara, S. Habaue, and Y. Okamoto, Polym. J., 28, 682 (1996).
S. Habaue, K. Shiohara, T. Uno, and Y. Okamoto, Enantiomer, 1, 55 (1996).
K. Shiohara, S. Habaue, and Y. Okamoto, Polym. J., 30, 249 (1998).
T. Uno, K. Shiohara, S. Habaue, and Y. Okamoto, Polym. J., 30, 352 (1998).
Y. Amano and Y. Okamoto, Polym. J., 37, 629 (2005).
K. Hatada, T. Kitayama, and K. Ute, Polym. Bull., 9, 241 (1983).
F. Toda, H. Miyamoto, S. Kikuchi, F. Nagami, and R. Kuroda, J. Am. Chem. Soc., 118, 11315 (1996).
Y. Okamoto, E. Yashima, M. Ihikura, and K. Hatada, Polym. J., 19, 1183 (1987).
Y. Okamoto, K. Suzuki, and H. Yuki, J. Polym. Sci., Polym. Chem. Ed., 18, 3043 (1980).
H. Kageyama, Y. Hayashi, S. Harada, Y. Kai, N. Kasai, Y. Okamoto, and K. Harada, Makromol. Chem., 186, 203 (1985).
A. K. M. F. Azam and Y. Okamoto, unpublished data.
T. Nakano and Y. Okamoto, Macromolecules, 32, 2391 (1999).
T. Nakano, K. Tsunematsu, and Y. Okamoto, Chem. Lett., 31, 42 (2002).
T. Nakano, M. Mori, and Y. Okamoto, Macromolecules, 26, 867 (1993).
H. Yuki, Y. Okamoto, and I. Okamoto, J. Am. Chem. Soc., 102, 6356 (1980).
Y. Okamoto, S. Honda, I. Okamoto, H. Yuki, S. Murata, R. Noyori, and H. Takaya, J. Am. Chem. Soc., 103, 6971 (1981).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Azam, A., Kamigaito, M. & Okamoto, Y. Helix-Sense-Selective Free Radical Polymerization of N-(Triphenylmethyl)methacrylamide Derivatives. Polym J 38, 1035–1042 (2006). https://doi.org/10.1295/polymj.PJ2006050
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1295/polymj.PJ2006050