Metacyclophanes and related compounds. 21. Nitration of [2.2]metacyclophanes
Metacyclophanes and related compounds. 21. Nitration of [2.2]metacyclophanes
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间环芬及相关化合物。
DOI：
10.1021/jo00263a036
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发表时间：
1989
影响因子：
3.6
通讯作者：
T. Yamato
中科院分区：
文献类型：
--
作者：
M. Tashiro;S. Mataka*;Takezaki Yoshinori;M. Takeshita;T. Arimura;A. Tsuge;T. Yamato
利用叔丁基作为位置保护基团，由相应的苯衍生物制备了各种[2.2]间环芳烷，并在各种条件下进行硝化。发现用发烟HNO 3 硝化8, 16-二甲基[2.2]间环芳仅得到5-硝基-8, 16-二甲基[2.2]间环芳，而不得到5, 13-二硝基-8, 16-二甲基[2.2]间环芳。通过5-碘-和5, 13-二碘-8, 16-二甲基[2.2]间环芳的硝化得到5-碘-13-硝基-8, 16-二甲基[2.2]间环芳。还发现在内部5位和/或13位具有甲氧基的[2.2]间环芳烃的硝化得到相应的四氢芘。还描述了上述反应的反应机理。尽管制备了许多[2.2]间环芳烷和相关化合物，并且这些化合物在有机化学家中值得关注，2但对其化学性质的研究却很少。最近，我们报道了3，8, 16-二甲基[2.2]间环芳烷(1a)(MCP=间环芳烷)与溴在存在或不存在铁粉作为催化剂的情况下进行溴化，得到不同类型的产物2或3，并且5, 13-二叔丁基-8, 16-二甲基[2.2] MCP (lb)的类似反应也得到不同类型的产物4或3 5.还发现，用NBS对1a和1b进行溴化，得到相应的双(溴甲基)[2.2]MCP 6a和6b（方案I）。
Various [2.2] metacyclophanes were prepared from the corresponding benzene derivatives by using the feri-butyl group as a positional protective function and their nitrations were carried out under various conditions. It was found that nitration of 8, 16-dimethyl [2.2] metacyclophane with fuming HN03 afforded only 5-nitro-8, 16-di-methyl [2.2] metacyclophane but not 5, 13-dinitro-8, 16-dimethyl [2.2] metacyclophane. 5-Iodo-13-nitro-8, 16-dimethyl [2.2] metacyclophane was obtained by nitration of 5-iodo-and 5, 13-diiodo-8, 16-dimethyl [2.2] metacyclophane. It was also found that nitration of the [2.2] metacyclophanes having methoxy groups at internal positions 5 and/or13 afforded the corresponding tetrahydropyrenes. The reaction mechanisms of theabove reactions are also described.Although many [2.2] metacyclophanes and related com-pounds were prepared and these compounds havebeen worthy of remark among organic chemists, 2 there are few investigation about their chemical natures. Recently, we reported that3 bromination of 8, 16-dimethyl [2.2] meta-cyclophane (la)(MCP= metacyclophane) with bromine in the presence or absence of Fe powder as a catalyst afforded different types of products, 2 or 3, and that sim-ilar reactions of 5, 13-di-teri-butyl-8, 16-dimethyl [2.2] MCP (lb) also gave different types of products, 4 or 5. It was also found that3 bromination of both la and lb with NBS afforded the corresponding bis (bromomethyl)[2.2] MCPs 6a and 6b (Scheme I).