The Chemistry of Vinyl, Allenyl, and Ethynyl Azides
The Chemistry of Vinyl, Allenyl, and Ethynyl Azides
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乙烯基、烯基和乙炔基叠氮化物的化学
DOI：
10.1002/9780470682517.ch5
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发表时间：
2010
期刊：
影响因子：
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通讯作者：
K. Banert
中科院分区：
文献类型：
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作者：
K. Banert
乙烯基叠氮化物1的母体化合物早在Forster和Newman制备并表征该化合物（Scheme 5.1）时就已为人所知。然而，在乙烯基叠氮化物的第一个例子发表后，这些化合物被忽视了大约五十年。也许，1的多步合成和同源相邻叠氮代卤烷的脱氢卤化可能导致乙烯基和烯丙基叠氮化合物的混合物的假设阻碍了1型标题化合物的研究。此外，关于1的爆炸特性的报告2可能是对乙烯基叠氮化物的储备的原因。这些化合物确实比烷基叠氮化物更敏感，但在大多数情况下比酰基叠氮化物更稳定。因此，如果碳原子数不超过氮原子数的三倍，那么大量的叠氮化物不应作为纯物质处理，而应在溶液中处理。1923年已知的合成乙烯基叠氮化物的唯一替代方法是在β-位置上带有一个吸电子基团的乙烯基卤化物的亲核取代。然而，该方法最初主要用于图5.2所示的叠氮醌的生成。3-5对于在β-位置上有电子受体的其他卤化乙烯，在产生叠氮化物之后，通常会迅速释放二氮并形成五元芳杂环。例如，在1958年，硝基的处理
The parent compound of vinyl azide 1 has been known for about hundred years when Forster and Newman prepared and characterized this compound (Scheme 5.1). 1 However, after publication of this first example of vinyl azides, these compounds were ignored for approximately fifty years. Perhaps, the multi-step synthesis of 1 and the assumption that dehydrohalogenation of homologous vicinal azidohaloalkanes may lead to mixtures of vinyl and allyl azides detained the investigation of the title compounds of type 1. Furthermore, the report 2 on the explosive properties of 1 could be responsible for the reservedness against vinyl azides. These compounds are indeed more sensitive than alkyl azides but more stable than acyl azides in most cases. Thus, great amounts of vinyl azides should be handled not as a pure substance but in solution if the number of carbon atoms does not exceed that of the nitrogen atoms by a factor of three. The only alternative method for the synthesis of vinyl azides already known in 1923 was the nucleophilic substitution of vinyl halides bearing an electron-withdrawing group in the β-position. However, this method was used at first mainly for the generation of azidoquinones as depicted in Scheme 5.2. 3–5 In the case of other vinyl halides with an electron acceptor in the β-position, the generation of vinyl azides is often followed by rapid liberation of dinitrogen and formation of a five-membered aromatic heterocycle. In 1958, for example, treatment of nitro