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http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/47312完整後設資料紀錄
| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 鄭淑芬 | |
| dc.contributor.author | Chia-Ming Yang | en |
| dc.contributor.author | 楊嘉銘 | zh_TW |
| dc.date.accessioned | 2021-06-15T05:54:34Z | - |
| dc.date.available | 2012-08-20 | |
| dc.date.copyright | 2010-08-20 | |
| dc.date.issued | 2010 | |
| dc.date.submitted | 2010-08-17 | |
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/47312 | - |
| dc.description.abstract | L-Proline包括其衍生物已被大量應用在不對稱Aldol加成反應。異相觸媒具有容易從反應物中分離、可以重複使用等優點。我們將L-proline的結構修飾成帶有SH官能基，與帶有Vinyl官能基的中孔洞材料SBA-15 (Vinyl-SBA-15)，利用AIBN當作起始劑，進行thiol-ene自由基加成反應而可將proline結構固定在中孔洞材料內表面上，達到將proline異相化的目的。有機化合物Cis-4-mercapto-L- proline (SH-proline)乃由 trans-4-hydroxy-L-proline經一系列修飾而得；含Vinyl官能基的SBA-15乃由三區塊共聚物(P123)作為模板試劑，將tetraethyl orthosilicate (TEOS)、vinyltrimethoxysilane (VTMS)在酸性環境下進行水解與共縮合反應，XRD顯示孔洞具有良好排列的二維六角堆積結構。氮氣吸脫附恆溫曲線圖顯示材料的BET比表面積、孔洞體積、與孔徑在SH-proline鍵結在SBA-15表面上後下降，表示有機物存在孔洞中；硫的K-edge光譜圖顯示材料有C-S-C鍵的存在，顯示SH-proline與Vinyl-SBA-15是以共價鍵鍵結，13C CP/MAS NMR光譜圖亦顯示材料含有proline結構，SEM與TEM圖顯示材料的外觀與孔洞性不隨proline的引入而改變。將含有proline結構的SBA-15觸媒應用在不對稱Aldol加成反應時，我們發現觸媒經不同pH水溶液前處理、反應溶劑及溫度對反應的轉化率及鏡像選擇率有重大的影響。 | zh_TW |
| dc.description.abstract | L-Proline is known as an organocatalyst for asymmetric Aldol reaction. For the purpose of easy separation and reuse of the catalyst, L-proline was immobilized onto mesoporous silica to form heterogeneous catalyst through thiol-ene addition using AIBN as the initiator. Cis-4-mercapto-L- proline (SH-proline) was synthesized from trans-4-hydroxy-L-proline. Vinyl group functionalized SBA-15 (briefly termed vinyl-SBA-15) was prepared by co-condensation of tetraethyl orthosili- cate (TEOS) and vinyltrimethoxysilane (VTMS) using P123 copolymer as the pore directing agent in strong acidic environment. XRD patterns showed that the materials contained well-ordered mesopores arranged in 2-D hexagonal arrays. N2 sorption data showed their surface area, pore volume, and pore diameter decreased after L-proline was immobilized. Sulfur K-edge XANES spectra showed the existence of C-S-C bond. 13C CP/MAS solid state NMR showed the existence of proline structure. SEM and TEM images showed the morphologies and mesoporosity didn’t change after poline was immobilized. The SBA-15 immobilized L-proline materials were used as catalysts in the asymmetric Aldol reaction. The pH value of pre-treatment solution, reaction solvent, and temperature were found to affect the chiral selectivity drastically. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-15T05:54:34Z (GMT). No. of bitstreams: 1 ntu-99-R97223180-1.pdf: 2809437 bytes, checksum: 965798542e1fa267d97cbe0bb0888cee (MD5) Previous issue date: 2010 | en |
| dc.description.tableofcontents | 第一章 緒論……………………………………………………………1
1-1 介孔材料的簡介…………………………………………………1 1-2 介孔材料的表面修飾………………………………………………5 1-3 不對稱合成…………………………………………………………7 1-4 L-Proline在不對稱Aldol加成反應的發展及反應機制…………7 1-5 Thiol-ene自由基加成反應………………………………………13 1-6將同相觸媒異相化…………………………………………………14 1-7 文獻上將proline異相化的例子…………………………………16 1-8 研究目的……………………………………………………………19 第二章 實驗部分………………………………………………………20 2-1 藥品…………………………………………………………………20 2-2 材料製備……………………………………………………………22 2-3丙酮對4-nitrobenaldehyde的不對稱加成反應…………………25 2-4產物及反應物的分析………………………………………………26 2-5介孔材料的鑑定與方法……………………………………………28 第三章 結果與討論……………………………………………………33 3-1 不同外觀的介孔洞材料的結構鑑定………………………………33 3-2 固定有機對掌試劑於孔洞材料及其鑑定…………………………47 3-3 觸媒催化活性………………………………………………………54 第四章 結論……………………………………………………………65 參考文獻…………………………………………………………………66 | |
| dc.language.iso | zh-TW | |
| dc.subject | 碳碳鍵生成 | zh_TW |
| dc.subject | 脯氨酸 | zh_TW |
| dc.subject | 異相觸媒 | zh_TW |
| dc.subject | 不對稱 | zh_TW |
| dc.subject | 二氧化矽 | zh_TW |
| dc.subject | asymmetric | en |
| dc.subject | proline | en |
| dc.subject | SBA-15 | en |
| dc.subject | heterogeneous | en |
| dc.subject | Aldol | en |
| dc.title | 製備L-proline官能基化的SBA-15及其在不對稱Aldol加成反應的應用 | zh_TW |
| dc.title | Preparation of L-Proline Functionalized SBA-15 as Catalysts for Asymmetric Aldol Addition | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 98-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 蔡蘊明,劉緒宗 | |
| dc.subject.keyword | 脯氨酸,異相觸媒,不對稱,二氧化矽,碳碳鍵生成, | zh_TW |
| dc.subject.keyword | proline,asymmetric,heterogeneous,SBA-15,Aldol, | en |
| dc.relation.page | 68 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2010-08-18 | |
| dc.contributor.author-college | 理學院 | zh_TW |
| dc.contributor.author-dept | 化學研究所 | zh_TW |
| 顯示於系所單位： | 化學系 | |
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