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Acta Chimica Sinica >

2012 , Vol. 70 >Issue 13: 1488 - 1495

DOI: https://doi.org/10.6023/A12030010

Article

Synthesis of Several Chiral Atom Transfer Radical Polymerization Initiators and Its Helix-sense-selective Initiating Function for ATRP

  • Wang Shihai ,
  • Yang Nianfa ,
  • Yang Liwen ,
  • Gong Hang
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  • Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan, Hunan 411105, China

Received date: 2012-03-18

  Online published: 2012-06-01

Supported by

Project supported by the National Natural Science Foundation of China (Nos. 20972131, 20772102).

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Abstract

Five optically active alkyl bromides were synthesized and were used as chiral atom transfer radical polymerization (ATRP) initiators for the helically selective polymerization of 1-phenyldibenzosuberyl methacrylate (PDBSMA). In order to avoid the racemization of the primary free radical formed in initiating step, the optically active alkyl bromide initiators were designed as such a structure in which the bromine atom did not connect to the chiral center. The chiral ATRP initiators tested here are (S)-2,2'-di(bromomethyl)-1,1'-binaphthyl, (S)-2-bromomethyl-2-methyl-1,1'-binaphthyl, menthyl α-bromophenylacetate, N-menthyl α-bromophenylacetamide and (3β,5α)-cholestan-3-yl α-bromo phenylacetate. (S)-2,2'- Di(bromomethyl)-1,1'-binaphthyl, (S)-2-bromomethyl-2-methyl-1,1'-binaphthyl and menthyl α-bromophenylacetate were synthesized following the method reported by literatures. N-menthyl α-bromophenylacetamide was synthesized by adding dropwise the solution of α-bromophenylacetyl chloride in tetrahydrofuran (THF) into the mixture of menthylamine, triethylamine and THF with stirring at room temperature within 3 h and stirring at room temperature for another 8 h after the addition. (3β,5α)-Cholestan-3-yl α-bromo phenylacetate was synthesized using the method for the synthesis of menthyl α-bromophenylacetate except using (3β,5α)-cholestanol instead of menthol. The poly-PDBSMA obtained from the ATRP initiated by the optically active alkyl bromides was fractionated into THF-soluble part and THF-insoluble part. THF-soluble part was optically active. By studying the chiroptical properties of the THF-soluble part of the poly-PDBSMA and by comparing the optical rotation of the THF-soluble part of the poly-PDBSMA with that of the poly(methyl methacrylate) (poly-MMA) obtained under the same polymerization condition, we concluded that the ATRP initiated by the optically active alkyl bromides was helix-sense selective. The NMR study of poly-MMA derived from the THF-insoluble part showed that the polymer produced from the polymerization initiated by (S)-2,2'-di(bromomethyl)-1,1'-binaphthyl was isotactic, which proved further that the ATRP initiated by the optically alkyl bromines was helix-sense selective. Among the five optically active alkyl bromides, (S)-2,2'-di(bromomethyl)-1,1'-binaphthyl and (S)-2-bromomethyl-2-methyl-1,1'-binaphthyl had the best helical selectivity. The helix-sense selectivity depended on the polymerization temperature. The ceiling temperature is 70 ℃. In the range of 0-70 ℃, the helix-sense selectivity increased with the increase of the polymerization temperature.

Key words： atom transfer radical polymerization; chiral alkylbromide; helix-sense-selective; helical polymer

Cite this article

Wang Shihai , Yang Nianfa , Yang Liwen , Gong Hang . Synthesis of Several Chiral Atom Transfer Radical Polymerization Initiators and Its Helix-sense-selective Initiating Function for ATRP[J]. Acta Chimica Sinica, 2012 , 70(13) : 1488 -1495 . DOI: 10.6023/A12030010

References

[1] Yashima, E.; Maeda, K.; Lida, H.; Furusho, Y.; Nagai, K. Chem. Rev. 2009, 109, 6102.

[2] Nakano, N.; Okamoto, Y. Macromol. Rapid Commun. 2000, 21, 603.

[3] Nakano, T.; Okamato, Y. Chem. Rev. 2001, 101, 4013.

[4] Cao, H.-Q.; Cui, J.-X.; Liu, A.-H.; Wan, X.-H. Acta Polym. Sinica 2010, (2), 222 (in Chinese). (曹洪庆, 崔家喜, 刘安华, 宛新华, 高分子学报, 2010, (2), 222.)

[5] Zhu, Z.-G.; Zhi, J.-G.; Liu, A.-H.; Cui, J.-X.; Wan, X.-H.; Chen, X.-F.; Zhou, Q.-F. Acta Polym. Sinica 2007, (9), 875 (in Chinese). (朱志国, 支俊格, 刘安华, 崔家喜, 宛新华, 陈小芳, 周其凤, 高分子学报, 2007, (9), 875.)

[6] Cui, J.-X.; Cao, H.-Q.; Liu, A.-H.; Wan, X.-H. Acta Polym. Sinica 2009, (10), 1050 (in Chinese). (崔家喜, 曹洪庆, 刘安华, 宛新华, 高分子学报, 2009, (10), 1050.)

[7] Cao, H.-Q.; Liu, A.-H.; Yu, Z.-N.; Zhang, J.; Wan, X.-H.; Chen, X.-F.; Zhou, Q.-F. Acta Polym. Sinica 2007, (10), 999 (in Chinese). (曹洪庆, 刘安华, 于振宁, 张洁, 宛新华, 陈小芳, 周其凤, 高分子学报, 2007, (10), 999.)

[8] Cui, J.-X.; Liu, A.-H.; Cao, H.-Q.; Wan, X.-H.; Zhou, Q.-F. Chem. Asian J. 2010, 5, 1139.

[9] Zhang, J.; Cao, H.-Q.; Wan, X.-H.; Zhou, Q.-F. Langmuir 2006, 22, 6587.

[10] Zhang, J.; Yu, Z.-N.; Wan, X.-H.; Chen, X.-F.; Zhou, Q.-F. Macro-mol. Rapid Commun. 2005, 26, 1241.

[11] Cao, H.-Q.; Lin, W.-R.; Liu, A.-H.; Zhang, J.; Wan, X.-H.; Zhou, Q.-F. Macromol. Rapid Commun. 2007, 28, 1883.

[12] Lin, W.-R.; Zhang, J.; Wan, X.-H.; Liang, D.-H.; Zhou, Q.-F. Mac-romolecules 2009, 42, 4090.

[13] Lin, W.-R.; Zheng, C.; Wan, X.-H.; Liang, D.-H.; Zhou, Q.-F. Mac-romolecules 2010, 43, 5405.

[14] Yu, Z.-N.; Wan, X.-H.; Zhang, H.-L.; Chen, X.-F.; Zhou, Q.-F. Chem. Commun. 2003, 974.

[15] Nakano, T.; Shikisai, Y.; Okamoto, Y. Polym. J. 1996, 28, 51.

[16] Nakano, T.; Shikisai, Y.; Okamoto, Y. Proc. Jpn. Acad. Ser. B 1995, 71, 251.

[17] Gong, H.; Yang, N.-F.; Yang, L.-W. Chem. Lett. 2011, 40, 651.

[18] Matyjaszewski, T.; Xia, J.-H. Chem. Rev. 2001, 101, 2921.

[19] Kamigaito, M.; Ando, T.; Sawamoto, M. Chem. Rev. 2001, 101, 3689.

[20] Coessens, V.-M.-C.; Matyjaszewski, K. J. Chem. Educ. 2010, 87, 916.

[21] Percec, V.; Barboiu, B.; Kim, H.-J. J. Am. Chem. Soc. 1998, 120, 305.

[22] Ooi, T.; Kameda, M.; Maruoka, K. J. Am. Chem. Soc. 2003, 125, 5139.

[23] Gingras, M.; Dubols, F. Tetrahedron Lett. 1999, 40, 1309.

[24] Kinder, F.-R.; Jarosineki, M.-A.; Anderson, W.-K. J. Org. Chem. 1991, 56, 6475.

[25] Kolev, T.; Preut, H.; Koniczek, L. Acta Crystallogr. 1995, C51, 1634.

[26] Nakano, T.; Matsuda, A.; Okamoto, Y. Polym. J. 1996, 28, 556.

[27] Nakano, T.; Mori, M.; Okamoto, Y. Macromolecules 1993, 26, 867.

[28] Okamato, Y.; Suzuki, K.; Ohta, K.; Hatada, K.; Yuki, H. J. Am. Chem. Soc. 1979, 101, 4763.

[29] Hoshikawa, N.; Hotta, Y.; Okamoto, Y. J. Am. Chem. Soc. 2003, 125, 12380.

[30] Nakano, T.; Okamoto, Y.; Hatada, K. J. Am. Chem. Soc. 1992, 114, 1318.

[31] Okamoto, Y.; Suzuki, K.; Yuki, H. J. Polym. Sci.: Polym. Chem. Ed. 1980, 18, 3043.

[32] Okamoto, Y.; Nakano, T.; Yoshifumin, S. Macromol. Symp. 1995, 89, 479.

[33] Schopohl, M.-C.; Bergander, K.; Kataeva, O. Synthesis 2003, 17, 2689.
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