NANOSCALE POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVES

描述：这项工作的目标是开发用于 一系列单分散纳米粒子的合成与表征 (N)苯衍生物(最多含127个) 烷基取代基。母体(N)苯烯具有n个苯环 融合在一个扩展的菲样结构基序中，并与 在结构上与石墨有关，因为条带与板材有关。有机食品 化学家们越来越重视化合物的合成。 分子尺寸在纳米级的单分散化合物， 它超出了传统有机化学的范围，但 包括许多具有生物重要性的分子和生物体。这个 拟议的工作应该有助于增加关于以下方面的知识 在传统的实验中可能需要进行哪些修改 的合成、提纯和分子结构验证方法 以有效地处理纳米级化合物。此外， 这项工作应该揭示光谱性质的信息趋势 (特别是电子吸收和荧光光谱)和物理 性质(特别是芳香环的溶解度和偏差 作为n的函数的(N)菲的系统)。 最终，可以发现这些类石墨化合物具有 有趣和潜在的实用特性，如电学 作为导体或作为非线性光学材料。这项工作还将 提供有价值的有机合成实验室培训和经验 这将为一些研究生和本科生的研究做准备。 生物有机化学或生物医学专业方向的学生 化学反应。所提出的综合遵循发散-收敛 一种迭代策略，其中每个四步迭代都将一个 由n环到2n+1环的菲。在第一个 迭代，2-溴-4-叔丁基甲苯分别转化为 两种化合物：环甲基取代基与NBS的反应 通过ph3p生成一种苄基三苯基膦盐，该反应 与BuLi的溴取代基，然后是DMF，生成醛。 涉及这两种化合物的Wittig反应生成二苯乙烯。 衍生物，然后光环化得到1-溴-3，5-二叔丁基-1-溴-3，5-二叔丁基-1-溴-3，5-二叔丁基- 丁基-8-甲基菲。在第二次迭代中，溴和 这种菲衍生物的甲基取代基类似 转化为生成膦盐和乙醛，并且 这两个中间体的Wittig偶联反应产生了 二苯亚乙基，光环化后生成(7)菲 用溴、甲基和四个叔丁基衍生物。 随后的迭代应该给出n=15的(N)个苯衍生物， 31、63和127。

DESCRIPTION: The objective of this work is to develop methods for the synthesis and characterization of a series of monodisperse nanoscale (n)phenancene derivatives (with n up to 127) that are solubilized by alkyl substituents. The parent (n)phenancenes have n benzene rings fused in an extended phenanthrene-like structural motif, and are related structurally to graphite as ribbons are related to sheets. Organic chemists are giving increasing attention to the synthesis of monodisperse compounds with molecular sizes in the nanoscale regime, the regime that lies beyond the range of traditional organic chemistry but includes many biologically important molecules and organisms. The proposed work should contribute to the growing body of knowledge about what modifications may be required in the conventional experimental methods of synthesis, purification, and molecular structure proof in order to deal effectively with nanoscale compounds. In addition, the work should reveal informative trends in the spectral properties (especially electronic absorption and fluorescence spectra) and physical properties (especially solubilities and deviations of the aromatic ring systems from planarity) of the (n) phenancenes as a function of n. Ultimately, these graphite-like compounds could be found to possess interesting and potentially practical properties as electrical conductors or as nonlinear optical materials. The work also will provide valuable laboratory training and experience in organic synthesis that will prepare a number of graduate and undergraduate research students for professional careers in bio-organic chemistry or biomedical chemistry. The proposed syntheses follow a divergent-convergent iterative strategy in which each four step iteration converts a phenancene with n rings to one with 2n + 1 rings. In the first iteration, 2-bromo-4-tert-butyltoluene is transformed separately into two compounds: reaction of the ring methyl substituent with NBS followed by Ph3P produces a benzylic triphenylphosphomium salt; and the reaction of the bromo substituent with BuLi followed by DMF produces an aldehyde. A Wittig reaction involving these two compounds yields a stilbene derivative, which is then photocyclized to give 1-bromo-3, 5-di-tert- butyl-8-methylphenanthrene. In the second iteration, the bromo and methyl substituents of this phenanthrene derivative are similarly transformed to produce both a phosphonium salt and an aldehyde, and the Wittig coupling of these two intermediates yields a diphenanthrylethylene that is photocyclized to give a (7)phenancene derivation with bromo, methyl, and four tert-butyl substituents. Subsequent iterations should give (n)phenancene derivatives with n=15, 31, 63 and 127.