Quantitative ω-amination, ω-azidolysis, and ω-thiolation of poly(ethylene oxide)s through anionic mechanism

Sung Woo Kim; Abu Bakkar Siddique; Jin Wook An; Hyeon Jong Park; Hyun Jun Kim; Ho-Jung Kang; Jae Yeol Lee; Sehoon Kim; Jungahn Kim

Macromolecular Research, Vol.24, No.2, 188-195, February, 2016

DOI10.1007/s13233-016-4023-7 Export Citation

Quantitative ω-amination, ω-azidolysis, and ω-thiolation of poly(ethylene oxide)s through anionic mechanism

Sung Woo Kim, Abu Bakkar Siddique, Jin Wook An, Hyeon Jong Park, Hyun Jun Kim, Ho-Jung Kang, Jae Yeol Lee, Sehoon Kim¹, and Jungahn Kim^†

Department of Chemistry, Kyung Hee University, Seoul, 02453, Korea
¹Center for Theranostics, KIST, Seoul, 02792, Korea

E-mail:

n-Butyllithium-initiated ring-opening polymerization of ethylene oxide with potassium t-butoxide in the mixture of benzene and dimethyl sulfoxide (DMSO) at 35 °C yielded corresponding “living” polymeric alkoxide. The molecular weight was well controlled on the basis of stoichiometric balance. Quantitative chain-end functionalizations, such as the amination, the azidation, and the thiolation of polymeric alkoxide, were performed. The yields were almost quantitative (over 98 mol%). The resulting products were characterized by the combination of 1H NMR spectroscopy, UV/Visible spectroscopy, FTIR, MALDI-TOF MS analysis, and size exclusion chromatographic analysis.

Keywords:poly(ethylene oxide);molecular weight control;chain-end functionalizations;amination;azidation;thiolation

[References]

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Swierczynski D, Zalewska A, Wieczorek W, Chem. Mater., 13, 1560 (2001)
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Harris JM, Chess RB, Nat. Rev. Drug Discovery, 2, 214 (2003)
Duncan R, Nat. Rev. Drug Discovery, 2, 347 (2003)
Sharpe M, Easthope SE, Keating GM, Lamb HM, Drugs, 62, 2089 (2002)
Satchi-Tainaro R, Duncan R, Barnes CM, Adv. Polym. Sci., 193, 1 (2006)
Lutz JF, Hoth A, Macromolecules, 39(2), 893 (2006)
Cheng TL, Cheng CM, Chen BM, Tsao SA, Chuang KH, Hsiao SW, Lin YH, Roffler SR, Bioconjugate Chem., 16, 1225 (2005)
Shim WS, Lee JS, Lee DS, Macromol. Res., 13(4), 344 (2005)
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Richards DH, Szwarc M, J. Chem. Soc.-Faraday Trans., 55, 1644 (1959)
Pierre LES, Price CC, J. Am. Chem. Soc., 78, 3432 (1956)
Esswein B, Moller M, Angew. Chem.-Int. Edit., 35, 623 (1996)
Quirk RP, Kim J, Kausch C, Chun M, Polym. Int., 39, 3 (1996)
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Price CC, Carmelite DD, J. Am. Chem. Soc., 88, 4039 (1966)
Bawn CEH, Ledwith A, McFarlane N, Polymer, 10, 653 (1969)
Hiki S, Kataoka K, Bioconjugate Chem., 21, 248 (2010)
Quirk RP, Yoo T, Lee Y, Kim J, Lee B, Adv. Polym. Sci., 153, 68 (2000)
Jeon HJ, Go DH, Choi S, Kim KM, Lee JY, Choo DJ, Yoo HO, Kim JM, Kim J, Colloids Surf. A: Physicochem. Eng. Asp., 317, 496 (2008)
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Balachandran V, Karthick T, Perumal S, Nataraj A, Ind. J. Pure Appl. Phys., 51, 178 (2013)
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[Referenced By]

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[3] Croce F, Curini R, Martinelli A, Persi L, Ronci F, Scrosati B, Caminiti R, J. Phys. Chem. B, 103(48), 10632 (1999)

[4] Swierczynski D, Zalewska A, Wieczorek W, Chem. Mater., 13, 1560 (2001)

[5] Xiong HM, Liu DP, Zhang H, Chen JS, J. Mater. Chem., 14, 2775 (2004)

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[7] Duncan R, Nat. Rev. Drug Discovery, 2, 347 (2003)

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[10] Lutz JF, Hoth A, Macromolecules, 39(2), 893 (2006)

[11] Cheng TL, Cheng CM, Chen BM, Tsao SA, Chuang KH, Hsiao SW, Lin YH, Roffler SR, Bioconjugate Chem., 16, 1225 (2005)

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[13] Quirk RP, Anionic Synthesis of Polymers with Functional Groups, in Comprehensive Polymer Science, Aggarwal SL, Russo S, Eds., Pergamon Press, Oxford, 1992, Suppl. Vol., Chap. 5, pp 82-106.

[14] Quirk RP, Kim J, Macromonmers and Macroinitiators, in Ring-opening Polymerization; Mechanisms, Catalysis, Structure, Utility, Brunelle DJ, Ed., Hanser, New York, 1993, Chap. 9, pp 263-293.

[15] Slomkowski S, Duda A, Anionic Ring-Opening Polymerization, in Ring-opening Polymerization; Mechanisms, Catalysis, Structure, Utility, Brunelle DJ, Ed., Hanser, New York, 1993, Chap. 3, pp 87-128.

[16] Hsieh HL, Quirk RP, Anionic Polymerization: Principles and Practical Applications, Marcel Dekker, New York, 1996, Chap. 24, pp 685-710.

[17] Richards DH, Szwarc M, J. Chem. Soc.-Faraday Trans., 55, 1644 (1959)

[18] Pierre LES, Price CC, J. Am. Chem. Soc., 78, 3432 (1956)

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[24] Gilman H, Cartledge FK, J. Organomet. Chem., 2, 447 (1964)

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[39] Singh PND, Mandel SM, Robinson RM, Zhu Z, Franz R, Ault BS, Gudmundsdottir AD, J. Org. Chem., 68, 7951 (2003)

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