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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 林英智(Ying-Chih Lin) | |
| dc.contributor.author | yung-ching Wang | en |
| dc.contributor.author | 王永慶 | zh_TW |
| dc.date.accessioned | 2021-06-16T23:29:31Z | - |
| dc.date.available | 2012-08-01 | |
| dc.date.copyright | 2012-08-01 | |
| dc.date.issued | 2012 | |
| dc.date.submitted | 2012-07-30 | |
| dc.identifier.citation | References:
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/65198 | - |
| dc.description.abstract | 利用釕金屬錯合物[Ru]Cl ([Ru] = Cp(PPh3)2Ru)與含四環之有機炔類1，在甲醇溶液中反應，可得釕亞乙烯錯合物2。假若將有機物1在參鍵旁邊延伸一個亞甲基形成有機物5，在同樣條件下，則與[Ru]Cl進行分子內環化反應生成釕卡賓錯合物6。錯合物2 與乙腈反應，釋放出烯炔有機物7。釕乙腈錯合物[Ru]MeCN+也可催化1的脫水反應得到7。再將7作環氧化反應得到含四環並環氧基之有機物 8。釕錯合物[Ru]Cl與8在二氯甲烷溶液中進行四環擴環反應，可得釕錯合物10。但是相同反應在甲醇溶液中，則可進行進一步環化反應得到含兩個五環稠環釕錯合物12a。此外，10在酸性甲醇溶液中也可以經環化反應轉化為12a。但是若無酸的存在，10在甲醇溶液中會脫氫離子得到11。錯合物10在二氯甲烷和氟硼酸溶液中反應，可進行氟加成反應得到錯合物13。單晶繞射確定了兩個釕錯合物6與12a的固態結構。 | zh_TW |
| dc.description.abstract | Reactions of [Ru]Cl ([Ru] = Cp(PPh3)2Ru) with three alkynyl compounds 1, 5, and 8, each containing a cyclobutyl group, are explored. For 1, the reaction gives the vinylidene complex 2, with a cyclobutylidene group via a dehydration at CδH and CγOH. With an additional methylene group, 5 reacts with [Ru]Cl to afford the cyclic oxacarbene complex 6. The reaction proceeds via a vinylidene intermediate followed by an intra-molecular cyclization reaction by a nucleophilic addition of the hydroxyl group onto Cα of the vinylidene ligand. Deprotonation of 2 with NaOMe produces the acetylide complex 3 and alkylations of 3 by allyl iodide, methyl iodide and ethyl iodoacetate generate 4a-c, respectively, each with a stable cyclobutyl group. Dehydration of 1 is catalyzed by the cationic ruthenium acetonitrile complex at 70ºC to form the 1,3-enyne 7. Epoxidation reaction of the double bond of 7 yields the oxirane 8. Ring-expansion of the cyclobutyl group of 8 is readily induced by the acidic salt NH4PF6 to afford the 2-ethynyl substituted cyclopentanone 9. The same ring expansion is also seen in the reaction of [Ru]Cl with 8 in CH2Cl2 affording the vinylidene complex 10, also obtainable from 9 and [Ru]Cl. But, in MeOH, the same reaction of [Ru]Cl with 8 affords the bicyclic oxacarbene complex 12a via an additional cyclization reaction. Transformation of 10 to 12a is readily achieved in MeOH/HBF4, but, in MeOH alone, the acetylide complex 11 is produced from 10. In the absence of MeOH, cyclization of 10, induced by HBF4, is followed by a fluorination to afford complex 13. Crystal structures of 6 and 12a’ are determined by singel crystal diffraction analysis. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-16T23:29:31Z (GMT). No. of bitstreams: 1 ntu-101-R99223167-1.pdf: 6446094 bytes, checksum: 6607a006199d841fa3516caebadf1e77 (MD5) Previous issue date: 2012 | en |
| dc.description.tableofcontents | Contents
Numbering and Structure of Compounds Ⅰ Reaction Scheme Ⅳ Abstract Ⅶ 中文摘要 Ⅸ Contents Ⅹ Introduction 1 Results and Discussion Formation of Vinylidene Complex 6 Formation of Vinylidene Complex by Alkylation 7 Formation of Cyclobutylidenemethylene Compound 11 Reactions of the alkylidene-epoxide cyclobutane 14 Conclusions 24 Experimental Section 25 References 40 AppendixⅠ 44 AppendixⅡ 61 | |
| dc.language.iso | zh-TW | |
| dc.subject | 釕 | zh_TW |
| dc.subject | 卡賓 | zh_TW |
| dc.subject | 環丁烷 | zh_TW |
| dc.subject | 擴環反應 | zh_TW |
| dc.subject | 含氧三環 | zh_TW |
| dc.subject | 環化反應 | zh_TW |
| dc.subject | cyclobutane | en |
| dc.subject | ruthenium | en |
| dc.subject | carbene | en |
| dc.subject | oxirane | en |
| dc.subject | ring-expansion | en |
| dc.subject | cyclization | en |
| dc.title | 含環丁烷及丙炔基之化合物與釕金屬錯合物反應之研究 | zh_TW |
| dc.title | Reactions of Ruthenium Complexes with Propargylic Compounds Containing a Cyclobutyl Group | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 100-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 葉名倉(Ming-Chang Yeh),邱靜雯(Ching-Wen Chiu) | |
| dc.subject.keyword | 釕,卡賓,環丁烷,擴環反應,含氧三環,環化反應, | zh_TW |
| dc.subject.keyword | ruthenium,carbene,cyclobutane,ring-expansion,oxirane,cyclization, | en |
| dc.relation.page | 115 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2012-07-31 | |
| 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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