氮雜丙烯啶類化合物是一類非常重要的化合物,同時,也是自然界中存在的最小的一類含氮不飽和的三元環(huán)狀化合物。這類化合物存在于許多具有生物活性的天然產(chǎn)物中,大部分的氮雜丙烯啶類的化合物是從金色鏈球菌中提取分離出來的。例如,米勒和其合作者于1970年從鏈霉菌中分離出azirinomycin,此化合物為含有2H-azirine環(huán)的天然產(chǎn)物的第一個例子,發(fā)現(xiàn)其對革蘭氏陽性和革蘭氏陽性菌均表現(xiàn)出廣泛的體外抗菌活性。由于氮雜丙烯啶的三元環(huán)結(jié)構(gòu)中存在較大的環(huán)張力,是許多有機(jī)合成中的重要中間體。近些年來,越來越多的化學(xué)家們致力于氮雜丙烯啶類化合物的合成方法學(xué)研究。目前,合成氮雜丙烯啶類化合物的方法不是特別多,經(jīng)過查閱文獻(xiàn)調(diào)研以后,得知已報道的主要合成方法主要有以下幾種:（1）經(jīng)典的Neber反應(yīng):以對甲苯磺酸肟為底物,在堿性條件下奪取肟的α位的氫,產(chǎn)生碳負(fù)離子,接著碳負(fù)離子進(jìn)攻分子內(nèi)的氮,隨著對甲苯磺酸根的離去,生成2H-氮雜丙烯啶產(chǎn)物。（2）疊氮類化合物通過光解或加熱得到2H-氮雜丙烯啶:乙烯基疊氮底物在加熱或光照條件下,發(fā)生分子內(nèi)的環(huán)合過程,生成2H-氮雜丙烯啶產(chǎn)物。（3）氮雜環(huán)丙烷類的衍生物通過消除... 

【文章來源】：天津大學(xué)天津市211工程院校985工程院校教育部直屬院校

【文章頁數(shù)】：140 頁

【學(xué)位級別】：碩士

【文章目錄】：
中文摘要
ABSTRACT
Chapter 1 Research background
    1.1 Introduction
    1.2 The compounds of 2H-azirine existing in nature
    1.3 The methods of synthesizing 2H-azirines
        1.3.1 The classic Neber reaction （route a）
        1.3.2 The azirination of vinyl azides through pyrolysis or photolysis (routeb)
        1.3.3 Through intramolecular elimination or swern oxidation of aziridinederivatives. (route c)
        1.3.4 Intramolecular rearrangement of isoxazole or phosphoisoxazole (routed)
        1.3.5 Intramolecular reactions of carbene with nitriles or nitrene withalkynes. (route e and f)
        1.3.6 Cyclization of β-mono-substituted enamines under the reaction ofhypervalent iodine oxidants. (route g)
        1.3.7 Wolff rearrangement of α-diazo oxime ethers.(route h)
    1.4 Application of 2H-azirine compounds in organic synthesis
        1.4.1 Reactions in which N atoms participates
        1.4.2 Reactions in which N-C2 participates
        1.4.3 Reactions in which C2-C3 participates
        1.4.4 Reactions in which N-C3 participates
    1.5 Important fluorinated drugs
    1.6 Fluorination reaction mediated by hypervalent iodine reagents
    Conclusion
Chapter 2 Project design
    2.1 Introduction
    2.2 Project design and feasibility analysis
    2.3 Research contents
Chapter 3 Results and discussions
    3.1 Introduction
    3.2 The optimization of the reaction conditions
    3.3 Investigation of the scope of substrate application
    3.4 Application of the product for further transformation
    3.5 Reaction mechanism
    3.6 Summary
Chapter 4 Experimental reagents and instruments
    4.1 Source and specification of reagents
    4.2 Analytical instruments and methods
Chapter 5 Experimental sections
    5.1 Preparation of Substrates
    5.2 The Preparation of Iodosylbenzene
    5.3 Preparation of Fluorinated 2H-Azirine 2
Chapter 6 Structure characterization of the prepared compounds
    6.1 Spectral Data of Substrates
    6.2 Spectral Data of Products
References
Notes on publications and participation in scientific research
Appendix 1: Copies of ~1H-NMR,~(13)C-NMR and ~(19)F-NMR Spectra
Appendix 2: X-ray Structure and Data of 2d
Acknowledgement



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