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

杜瓦苯价键异构合成[0^4]对环芳烷的研究

• 批准号: 07640698
• 负责人: OHKITA Masakazu
• 金额: $ 1.28万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07640698/
• 关键词: Dewar benzene; Cyclophanes; [0^n] Paracyclophane; Belt-type molecules; 〔O^4〕パラシクロファン

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.

1996年，8，10-二氯-3，5-二氧代双环[5.2.2]十一碳-8，10-二氧代双环[5.2.以乙炔二甲酸二甲酯为原料，经四步反应合成了10-二烯2，并对其分子结构和化学反应性进行了研究。研究了由结构单元2合成丁二烯膨胀的[0^6]对环蕃3，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个对亚苯基单元被间亚苯基单元取代。

项目成果

Masakazu Ohkita: "Reaction of C_<60> with Cyclopent-2-enone Acetals.A Convenient Access to Chiral C_<60> Derivatives" J.Chem.Soc,Chem.Commun.1769-1770 (1995)

Masakazu Ohkita：“C_<60> 与环戊-2-烯酮缩醛的反应。方便地获得手性 C_<60> 衍生物”J.Chem.Soc,Chem.Commun.1769-1770 (1995)

Masakazu Ohkita: "Direct Synthesis of 2-Norbornanone Dithioacetals from 2-Cyclopentenone Dithioacetals and Dienophils. Synthetic Application of Thernal Interconversion between Cyclic Dithioacetals and RIng-Opened Vinyl Sulfide Forms" Tetrahedron. 52. 9979

Masakazu Ohkita：“从 2-环戊烯酮二硫缩醛和 Dienophils 直接合成 2-降冰片酮二硫缩醛。环状二硫缩醛与 RIng 开环乙烯基硫醚形式之间热互变的合成应用”四面体。