Synthetic Study of [0^4] Paracyclophane Using Valence-Bond Isomerization of Dewar Benzenes

本研究设计了一种由弯曲苯环组成的新型带型分子[0^4]副环phane 1，并试图在最后一步采用杜瓦苯的价键异构化方法合成。1996年，以乙炔二羧酸二甲酯为原料，四步合成了8,10-二氯-3,5-二氧双环[5.2.2]十一烷-8,10-二烯2，并对其分子结构和化学反应性进行了研究。1997年，研究了以构筑块2为原料合成丁二烯扩展[0^6]对环番烷3的方法，并成功合成了相应的低聚（杜瓦）苯前体。还合成了3的模型化合物，其中3中的4个对苯基被亚苯基取代。

In the present study, a novel belt-type molecule, [0^4] paracyclophane 1, composed of bent benzene rings was designed and attempted to be synthesized by using valence-bond isomerization of Dewar benzenes in the final step.In 1996,8,10-dichloro-3,5-dioxobicyclo [5.2.2] undeca-8,10-diene 2 was synthesized in four steps from dimethyl acetylenedicarboxylate as a new Dewar benzene building block and its molecular structure and chemical reactivity were examined.In 1997, synthesis of butadiene-expanded [0^6] paracyclophane 3 from the building block 2 was examined and the corresponding oligo (Dewar) benzene precursor was successfully synthesized. Model compound for 3, in which four paraphenylene units in 3 are replaced by metaphenylene units, was also synthesized.