Synthesis and Chemistry of 1,3,5,7-Tetranitrocubane Including Measurement of Its Acidity, Formation of o-Nitro Anions, and the First Preparations of Pentanitrocubane and Hexanitrocubane

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• 作者：Kirill A. Lukin ; Jianchang Li ; Philip E. Eaton ; Nobuhiro Kanomata ; Jü ; rgen Hain ; Eric Punzalan ; and Richard Gilardi
• 刊名：Journal of the American Chemical Society
• 出版年：1997
• 出版时间：October 15, 1997
• 年：1997
• 卷：119
• 期：41
• 页码：9591 - 9602
• 全文大小：466K
• 年卷期：v.119,no.41(October 15, 1997)
• ISSN：1520-5126

文摘

Nitro groups on alternate corners of cubane enhance theacidity of cubyl hydrogen (pK_a ~21) andprovidesufficient activation for ready anion formation. The sodium saltof 1,3,5,7-tetranitrocubane reacts easily withelectrophiles and leads thereby to yet more highly substituted cubanes,like carbomethoxy- and (trimethylsilyl)tetranitrocubane. Anions from these species are also easily formed andare useful for further substitution on the cubanenucleus. Dinitrogen tetraoxide reacts with the anion oftetranitrocubane to give 1,2,3,5,7-pentanitrocubane, thefirstcubane to contain vicinal nitro groups. The reaction probablyinvolves oxidation of the anion to the correspondingradical. Similarly, the anion of pentanitrocubane is used toprepare 1,2,3,4,5,7-hexanitrocubane, the most highlynitrated cubane made to date. Single-crystal X-ray structuralinformation is given for both penta- and hexanitrocubane.