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

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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.