完整後設資料紀錄
DC 欄位語言
dc.contributor.author朱見和en_US
dc.contributor.authorJean- Ho Chuen_US
dc.contributor.author鍾文聖en_US
dc.contributor.authorWen-Sheng Chungen_US
dc.date.accessioned2014-12-12T02:21:32Z-
dc.date.available2014-12-12T02:21:32Z-
dc.date.issued1998en_US
dc.identifier.urihttp://140.113.39.130/cdrfb3/record/nctu/#NT870500017en_US
dc.identifier.urihttp://hdl.handle.net/11536/64796-
dc.description.abstract4-取代金剛酮 (13、57、29) 於取代基為 -OCH2CH2O-、-SCH2CH2S- 及 =CH2 時,進行還原反應以及 4-取代金剛烯 (56、58) 於取代基為 -OCH2CH2O- 及 -SCH2CH2S- 時,進行 1,3-偶極環化加成及carbene 加成反應,其結果皆顯示反應的面向選擇性主要決定於立體阻礙效應 (steric effect) ;但是在 4-取代金剛烯 (56、29) 之環氧化加成反應中,當反應試劑為 mCPBA 時,影響反應面向選擇性的因素除了立體阻礙效應外,氫鍵 (hydrogen bonding) 更是扮演著重要角色;而化合物 29 於進行 1,3-偶極環化加成及 carbene 加成反應時,可能影響反應面向選擇性的因素有:取代基電子效應 (electronic effect)、Mlinaric-Majerski 所提的 C=O 隔空穩定三角形 C2 反應中心說法及立體阻礙效應,在此三因素相互作用下,最後反應面向選擇性偏好由順式面 (syn-face) 加成。 利用 beta-環糊精 (beta-cyclodextrin,簡稱 beta-CD) 與化合物 29 錯合,在還原試劑 NaBH4 作用下,引導反應面向由順式面進行加成。實驗結果顯示在水中之還原產物比例為 E-:Z-60 = 45:55;而在 beta-CD 水溶液中可達到 E-:Z-60 = 32:68。另外以 1H-NMR 滴定的方式,可以證實化合物 29 與 beta-CD 錯合物的存在。 Adamantylidenefulvene (51) 與 benzonitrile oxide 進行1,3-偶極環化加成反應,結果顯示至少有四種加成產物生成;且影響反應位向選擇性 (regioselectivity) 及產物之立體化學 (stereochemistry) 選擇性的因素,主要是立體阻礙效應及靜電場效應 (electrostatic effect)。 化合物 51、75、76 與 DMAD 進行 Diels-Alder 反應,結果顯示反應之面向選擇性仍然受 5-取代基的推拉電子效應影響而有所不同,但是效應並不明顯。zh_TW
dc.description.abstractThe facial selectivity of the reduction of 4-substituted adamantane-2-ones (13, 57, 29) and both the 1,3-dipolar cycloaddition and the carbene addtion reactions of 4-substituted 2-methyleneadamantanes (56, 58) are determined mainly by steric effect as the substituent was varied from -OCH2CH2O-, -SCH2CH2S-. The facial selectivity is not only determined by steric effect but also by hydrogen bonding in the epoxidation of 4-substituted 2-methyleneadamantanes (56, 29) with mCPBA. On the other hand, the facial selectivity is affected by electronic effect, the through space stabilization of trigonal C2 reaction center and steric effect in 29 where the carbonyl is the substituent. It favors the syn-face attack product. In the reduction (NaBH4) of 29, product ratios Z-:E-60 can be modified from 45:55 (in H2O) to that of 32:68 by inclusion in beta-CD solution. 1H-NMR spectra provide evidences for the inclusion complex of 29 with beta-CD. The 1,3-dipolar cycloaddition of 51 with benzonitrile oxide gives more than four isomeric adducts. The regioselectivity of the 1,3-dipolar cycloaddtion and the stereochemistry of adducts are determined mainly by both steric effect and electrostatic effect. The Diels-Alder reaction of 51, 76, and 75 reacted with DMAD gives two isomeric adducts and the face selectivity is slightly affected by electronic effect.en_US
dc.language.isozh_TWen_US
dc.subject面向及位向選擇性研究zh_TW
dc.subjectfacial and regio selectivityen_US
dc.title2,4-雙取代金剛烷衍生物及 2,5-雙取代 Adamantylidenefulvenes 之面向及位向選擇性研究zh_TW
dc.titleStudy of Facial and Regio Selectivity on 2,4-Disubstituted Adamantanes and 2,5-Disubstituted Adamantylidenefulvenesen_US
dc.typeThesisen_US
dc.contributor.department應用化學系碩博士班zh_TW
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