Chemistry of Cyclophane-type Multi-bridged Compounds Containing Bridgehead Nitrogen Atom

为了研究桥头氮原子上存在非成键电子对和芳香环上存在π电子云的环烷型多桥化合物内的n-pi相互作用，我们开始合成桥头位置含氮原子的多桥环烷。首先，对1,3,5-三（卤甲基）苯与三（n -甲烷基）胺进行偶联反应，得到目标化合物。但是，三个氮原子在苯基位置的存在，阻碍了在笼化化合物中给出分子内n-pi相互作用的明确证据。然后，尝试用n -亚硝基衍生物挤压氮来消除苯基位置上的三个氮原子，但不幸的是失败了。进一步，为了消除苯基位置上另一个杂原子的影响，将得到的二硫笼化合物作为模型化合物进行了缩环反应，成功地挤压了两个硫原子。到目前为止，在苯基位置上得到了含有三个硫原子的目标三桥笼状化合物。硫原子的挤压作用正在研究中。

In order to investigate the n-pi interaction within a cyclophane-type multi-brigded compound, in which non-bonded electron pairs on the bridge-head nitrogen atom and the pi electron cloud on aromatic ring exist, we started to synthesize multi-bridged cyclophanes containing nitrogen atom at the bridgehead position. At first, coupling reactions between 1,3,5- tris (halomethyl) benzene and tris (N-tosylalkyl) amine were carried out, and the targeted compounds were obtained. But, the existence of the three nitrogen atoms at benzylic positions prevented to give the clear-cut evidence of the intramolecular n-pi interaction within the caged compound.Then, the elimination of three nitrogen atoms at benzylic positions was tried by the extrusion of nitrogens via N-nitroso derivative, but unfortunately failed. Further, in order to eliminate the influence of the another hetero atoms at benzylic positions, ring contraction reactions of the obtained dithia cage compound as a model compound were carried out and the extrusion of the two sulfur atoms successfully succeeded. Hitherto, the targeted tribridged cage compound containing three sulfur atomsat the benzylic positions was obtained. The extrusion of the sulfur atoms is under investigation.