Synthesis of (S)-BINOL-Terminated Poly(ethylene glycol) Polyrotaxane Including α-Cyclodextrin

被引：0
作者：
Onimura, Kenjiro [1 ]
Kawashima, Masayuki [1 ]
Yamabuki, Kazuhiro [1 ]
Isobe, Yukio [1 ]
Oishi, Tsutomu [1 ]
机构：
[1] Yamaguchi Univ, Grad Sch Sci & Engn, Dept Appl Chem, Ube, Yamaguchi 7558611, Japan
来源：
KOBUNSHI RONBUNSHU | 2008年 / 65卷 / 02期
关键词：
Polyrotaxane; Cyclodextrin; Supramolecule; Binaphthol; Optically Active Polymer;
D O I：
10.1295/koron.65.196
中图分类号：
O63 [高分子化学（高聚物）];
学科分类号：
070305 ; 080501 ; 081704 ;
摘要：
a,omega-Dimesyl-terminated poly(ethylene glycol) (PEG-Ms2) and alpha,omega-ditosyl-terminated PEG (PEG-Ts2) were prepared from PEG (PEG(1000); M-n = 1000 and PEG(4000); M-n = 4000) and methanesulfonyl chloride or p-toluenesulfonyl chloride. alpha,omega-Ditosyl-terminated PEG4000 pseudorotaxane (PEG(4000)-TS2-pseudorotaxa-alpha-cyclodextrin (alpha-CD) was prepared from PEG(4000)-TS2 and alpha-CD in H2O. (S)-(-)-1,1'-Bi (2-naphthol) ((S)-BINOL) was added to the pseudorotaxanes in the presence of sodium hydride to give PEG-rotaxa-alpha-CDs end-capping (S)-BINOL (PEG-BINOL2-rotava-alpha-CD). The purified PEG(4000)-BINOL2-rotaxa-alpha-CD was isolated in 38% yield. For a PEG4000-TS2, the average number of alpha-CD's per chain is 29, which corresponds to 64% coverage. After end-capping reaction, the average number of alpha-CD's per chain is 14, which corresponds to 31% coverage. The threading level in the polyrotaxane is limited by the coverage of the poly-pseudorotaxane and by the competition between the end blocking reaction and dethreading. In DMF a rapid dethreading occurs.
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页码：196 / 198
页数：3
相关论文
共 13 条
[1]   PREPARATION AND CHARACTERIZATION OF INCLUSION COMPLEXES OF POLY(PROPYLENE GLYCOL) WITH CYCLODEXTRINS [J].
HARADA, A ;
OKADA, M ;
LI, J ;
KAMACHI, M .
MACROMOLECULES, 1995, 28 (24) :8406-8411
[2]   THE MOLECULAR NECKLACE - A ROTAXANE CONTAINING MANY THREADED ALPHA-CYCLODEXTRINS [J].
HARADA, A ;
LI, J ;
KAMACHI, M .
NATURE, 1992, 356 (6367) :325-327
[3]   Inclusion complexation between comblike PEO grafted polymers and α-cyclodextrin [J].
He, LH ;
Huang, J ;
Chen, YM ;
Liu, LP .
MACROMOLECULES, 2005, 38 (08) :3351-3355
[4]   Inclusion interaction of highly densely PEO grafted polymer brush and α-cyclodextrin [J].
He, LH ;
Huang, J ;
Chen, YM ;
Xu, XJ ;
Liu, LP .
MACROMOLECULES, 2005, 38 (09) :3845-3851
[5]   A novel synthesis of chiral rotaxanes via covalent bond formation [J].
Kameta, N ;
Hiratani, A ;
Nagawa, Y .
CHEMICAL COMMUNICATIONS, 2004, (04) :466-467
[6]   Solid-state end-capping of pseudopolyrotaxane possessing hydroxy-terminated axle to polyrotaxane and its application to the synthesis of a functionalized polyrotaxane capable of yielding a polyrotaxane network [J].
Kihara, N ;
Hinoue, K ;
Takata, T .
MACROMOLECULES, 2005, 38 (02) :223-226
[7]   Preparation and characterization of polypseudorotaxanes based on block-selected inclusion complexation between poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) triblock copolymers and α-cyclodextrin [J].
Li, J ;
Ni, XP ;
Zhou, ZH ;
Leong, KW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (07) :1788-1795
[8]   Catalytic asymmetric synthesis and optical resolution of planar chiral rotaxane [J].
Makita, Yoshimasa ;
Kihara, Nobuhiro ;
Nakakoji, Naohisa ;
Takata, Toshikazu ;
Inagaki, Shinji ;
Yamamoto, Chiyo ;
Okamoto, Yoshio .
CHEMISTRY LETTERS, 2007, 36 (01) :162-163
[9]   Cyclodextrin-based catenanes and rotaxanes [J].
Nepogodiev, SA ;
Stoddart, JF .
CHEMICAL REVIEWS, 1998, 98 (05) :1959-1976
[10]   One-pot synthesis of γ-cyclodextrin polyrotaxane:: Trap of γ-cyclodextrin by photodimerization of anthracene-capped pseudo-polyrotaxane [J].
Okada, M ;
Takashima, Y ;
Harada, A .
MACROMOLECULES, 2004, 37 (19) :7075-7077
12