Studies on Asymmetric Synthesis, Structure, and Function of Optically Active Poly(methacrylamide) Derivatives
Studies on Asymmetric Synthesis, Structure, and Function of Optically Active Poly(methacrylamide) Derivatives
批准号:
17550116
负责人:
OKAMOTO Yoshio
金额:
$2.43万
依托单位:
依托单位国家:
日本
项目类别:
Grant-in-Aid for Scientific Research (C)
财政年份:
2005
资助国家:
日本
项目状态:
已结题
起止时间:
2005 至 2006
中文摘要
1.在(+)-薄荷醇或(-)-薄荷醇的存在下,N-[(4-丁基)三苯甲基]甲基丙烯酰胺(N-[(4-butylphenyl)dibenzosuberyl]methacrylamide)和N-[(4-丁基)三苯甲基]甲基丙烯酰胺(BuTrMAM)和甲基丙烯酰胺(BuPDBSMAM)等具有较大侧基的甲基丙烯酰胺进行自由基聚合,得到旋光性聚合物。从聚合物在D_2SO_4->;中的~1H核磁共振谱估计,聚合物的规整度接近100%全同立构。聚合物的圆二向色性(CD)谱表明聚合物具有螺旋构象,具有过量的右旋或左旋螺旋度。还进行了光学活性共聚单体N-[(R)-(+)-1-(1-萘基)乙基]甲基丙烯酰胺((+)-NEMAM)与BuTrMAM的自由基共聚合。共聚物的光学活性明显依赖于共聚单体的含量。当共聚物中(+)-Nemam含量较低时,(+)-Nemam单元有效地诱导了由BuTrMAM单体序列组成的单手螺旋性。以2,3,4,6-四-0-乙酰基-α-D-吡喃半乳糖基溴等卤代糖为引发剂,与手性阴离子引发体系进行了聚合反应。在D_2SO_4中的1H核磁共振谱表明,聚合物是高度全同立构的,并且聚合物的引发链端有糖残基。所得聚合物具有旋光性,卤代糖影响了CD光谱中的比旋光和Cotton效应。这些结果表明,由n-Bu4ZnLi2/卤代糖引发体系制备的聚合物具有螺旋构象,具有过量的右旋或左旋螺旋度。
英文摘要
1. The radical polymerization of the methacrylamides having a bulky side group, such as N-[(4-butyl)triphenylmethyl]methacrylamide (BuTrMAM) and N-[(4-butylphenyl)dibenzosuberyl]methacrylamide (BuPDBSMAM), in the presence of (+)-menthol or (-)-menthol was carried out in order to attain the helix-sense-selective polymerization leading to the optically active polymers. The tacticity of the polymers was estimated to be nearly 100% isotactic from the ^1H NMR spectra of the polymers in D_2SO_<4->. The circular dichroism (CD) spectra of the polymers suggested that the polymers have a helical conformation with an excess right-or left-handed helicity. The radical copolymerization of BuTrMAM with an optically active comonomer, such as N-[(R)-(+)-1-(1-naphthyl)ethyl]methacrylamide ((+)-NEMAM), was also carried out. The optical activity of the copolymers significantly depended on the comonomer contents. When (+)-NEMAM content was low in the copolymer, the (+)-NEMAM units effectively induced the one-handed helicity consisting of BuTrMAM monomeric sequences.2. BuTrMAM was polymerized with the chiral anionic initiator systems consisting of n-Bu_4ZnLi_2 and halogeno sugars, such as 2,3,4,6-tetra-0-acetyl-α-D-galactopyranosyl bromide. The ^1H NMR spectra in D_2SO_4 suggested that the polymers were highly isotactic, and the initiating chain end of polymers has a sugar residue. The obtained polymers exhibited an optical activity, and the halogeno sugars affected the specific rotations and Cotton effect in the CD spectra. These results indicate that the polymers prepared by the n-Bu_4ZnLi_2/halogeno sugars initiator systems have a helical conformation with an excess right- or left-handed helicity.
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DOI:
10.1295/polymj.pj2006087
发表时间:
2006-12
期刊:
Polymer Journal
影响因子:
2.8
作者:
[Naohiro Hoshikawa;C. Yamamoto;Y. Hotta;Y. Okamoto]
通讯作者:
Naohiro Hoshikawa;C. Yamamoto;Y. Hotta;Y. Okamoto
Helicity Induction in N-[(4-Butyl)triphenylmethyl]methacrylamide Sequence via Radical Copolymerization with Chiral Monomers
通过与手性单体的自由基共聚诱导 N-[(4-丁基)三苯基甲基]甲基丙烯酰胺序列的螺旋度
DOI:
--
发表时间:
2006
期刊:
Polym. J. 38(11)
影响因子:
--
作者:
[A.K.M.F.Azam, M.Kamigaito, Y.Okamoto, A.K.M.F.Azam, A.K.M.F.Azam, A.K.M.F.Azam]
通讯作者:
A.K.M.F.Azam
Helix-Sense-Selective Free Radical Polymerization of N-[(Triphenylmethy1)methacrylamide Derivatives
N-[(三苯基甲基)甲基丙烯酰胺衍生物的螺旋选择性自由基聚合
DOI:
--
发表时间:
2006
期刊:
Polym.J. 38(10)
影响因子:
--
作者:
[A.K.M.F.Azam, M.Kamigaito, Y.Okamoto]
通讯作者:
Y.Okamoto
DOI:
10.1002/pola.21902
发表时间:
2007-04
期刊:
Journal of Polymer Science Part A
影响因子:
--
作者:
[A. Azam;M. Kamigaito;Y. Okamoto]
通讯作者:
A. Azam;M. Kamigaito;Y. Okamoto
Helix-Sense-Selective Radical Polymerization of N-(TriphenylmethyDmethacrylamides and Properties of the Polymers
N-(三苯基甲基D甲基丙烯酰胺)的螺旋选择性自由基聚合及其聚合物的性能
DOI:
--
发表时间:
2006
期刊:
Polym.J. 38(12)
影响因子:
--
作者:
[N.Hoshikawa, C.Yamamoto, Y.Hotta, Y.Okamoto]
通讯作者:
Y.Okamoto
共 10 条
Advances in Theory and Design Principles of Counting AlgorithmsBased on Polyhedral Combinatorics
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批准号:21700009
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项目类别:Grant-in-Aid for Young Scientists (B)
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资助金额:$2.66万
-
财政年份:2009
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负责人:OKAMOTO Yoshio
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Algorithmic exact approach to game theory on graphs and networks
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批准号:18710130
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Helix-Sense-Selective Radical Polymerization of Methacrylamides
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批准号:14350485
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项目类别:Grant-in-Aid for Scientific Research (B)
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Development of New Chiral Packing Material for HPLC Based on the Structure Control of Polysaccharide Derivatives and Their Immobilization onto Silica Gel
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批准号:13355033
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Development and Application of Precise-Stereocontrolled Polymerization of Novel Acrylic Monomers
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批准号:11450355
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项目类别:Grant-in-Aid for Scientific Research (B)
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财政年份:1999
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High-Performance Separation Systems Based on Kinetic Molecular Recognition
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批准号:10208103
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项目类别:Grant-in-Aid for Scientific Research on Priority Areas (B)
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资助金额:$1.41万
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High-Performance Chiral Separation Systems Based on Polysaccharide Derivatives
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批准号:10208206
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项目类别:Grant-in-Aid for Scientific Research on Priority Areas (B)
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资助金额:$27.78万
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Teaching Materials of Geophysical Observation-Earthquakes and Geomagnetism-
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批准号:09680207
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Development of Efficient Chiral Packing and Their Recognition Mechanism
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批准号:08559008
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资助金额:$9.22万
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Studies on Stereocontrol of Free-Radical Polymerization
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项目类别:Grant-in-Aid for Scientific Research (B)
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资助金额:$4.74万
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Molecular Recognition in Organic Crystals
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批准号:06242101
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资助金额:$76.03万
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Development of Practical Resolution System
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批准号:05559009
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资助金额:$7.1万
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财政年份:1993
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Studies on systhesis, structure, and chiral recognition ability of helical, optically active polymers
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Studies on Advanced Synthesis and Application of Polymers Capable of Material Recognition
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批准号:03303010
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负责人:OKAMOTO Yoshio
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Development of Highly Efficient System for Optical Resolution
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批准号:02555184
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负责人:OKAMOTO Yoshio
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Synthesis of Polysaccharide Derivatives Having Optical Resolving Ability and Their Application for Liquid Chromatography
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批准号:61470108
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负责人:OKAMOTO Yoshio
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海外基金