臺灣博碩士論文加值系統

第一部分
5-取代-2-硝基亞甲基金剛烷和丙烯醇
反應之立體化學探討
中文摘要
5-取代-2-金剛酮（5-Substituted adamantan-2-ones）1-X和硝基甲烷（nitromethane）、乙二胺（ethylenediamine）反應生成產物5-取代-2-硝基亞甲基金剛烷（5-substituted-2-nitromethylene-adamantanes）2-X；而在此一系列中的取代基（-X）有六種：分別為-H、-F、-Cl、-Br、-I和-Ph。2可從zu-face或en-face進行親核性加成反應得到3-X（X＝F、Cl、Br、I和Ph），而兩者異構物的比例幾乎是固定（約3：2），此一結果可用靜電場作用理論（the electrostatic field influence）來解釋。
第二部分
5-取代-2-亞甲基金剛烷和N-methylnitrone反應之立體化學探討
中文摘要
5-substituted adamantan-2-enes 4-X，在此一系列中的取代基（-X）有六種：分別為-H、-F、-Cl、-Br、-I和-Ph。4從zu-face或en-face進行1,3-dipolar得到cycloaddition異構物8-X（X = F、Cl、Br、I和Ph），其產物的比例幾乎是固定（約3：2）。此一結果可用靜電場作用理論（the electrostatic field influence）討論之。

Part I
Face selectivity in the reactions of allylalcohol with 5-substituted-2 -nitromethyleneadamantanes
Abstract
Reactions of 5-substituted adamantan-2-ones 1-X with nitromethane and ethylenediamine generated 5-substituted-2—nitromethylene -adamantanes 2-X. A variety of substituents such as hydro, fluoro, chloro, bromo, iodo and phenyl groups were used in this system. The ratios of the different isomeric products 3-X generated from the zu-face or en-face by the nucleophilic addition of 2 were nearly 3:2. All experimental results can be explained by the electrostatic field influence theory.
Part II
Face selectivity in the reactions of 5-substituted-2-methylene-adamantanes with N-methylnitrone
Abstract
A variety of substituents of 5-substituted adamantan-2-enes 4-X were used: hydro, fluoro, chloro, bromo, iodo and phenyl groups. The ratios of the different isomeric products 8-X generated from the zu-face or en-face by the 1,3-dipolar cycloaddition of 2 were nearly 3:2. It was discussed in terms of the electrostatic field influence.

頁數
第一部分、5-取代-2-硝基亞甲基金剛烷
和丙烯醇反應之立體化學探討 1
中文摘要 2
英文摘要 3
前言 4
結果和討論 11
實驗部份
一般介紹 15
藥品和起始物 17
實驗方法 18
光譜資料 19
參考資料 22
譜圖 26
第二部分、5-取代-2-亞甲基金剛烷和
N-methylnitrone反應之
立體化學探討 77
中文摘要 78
英文摘要 79
前言 80
結果和討論 84
實驗部份
一般介紹 88
藥品和起始物 90
實驗方法 91
光譜資料 92
參考資料 94
譜圖 96

第一部分
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12. 此一部份由於和本實驗室張永俊學長共同合作，所以部份實驗數據為求本篇論文的完整性而加以引用。
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第二部分
1. Tsai, T. L.; Chen, W. C.; Yu, C. H.; le Noble, W. J.; Chung, W. S. J. Org. Chem. 1999, 64, 1099
2. Frederickson, M. Tedrheron. 1997, 53, 403
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4. Herrera, R.; Nagarajan, A.; Morales, M. A.; Me´ndez, F.; Jime´nez-Va´zquez, H. A.; Zepeda, L. G.; Tamariz, J. J. Org. Chem. 2001, 66, 1252
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8. Geluk, H. W. Synthesis 1972, 374.
9. Kaselj, M.; Gonikberg, E. M.; le Noble, W. J. J. Org. Chem. 1998, 63, 3218.
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