Syntheses of Novel Belt-Type Molecules Using Dewar Benzenes.

使用杜瓦苯合成新型带状分子。

• 批准号: 09640620
• 负责人: OHKITA Masakazu
• 金额: $ 1.6万
• 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: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640620/
• 关键词: Dewar Benzenes; Belt-Type Molecules; Cyclophanes; Paraphenylene; Bisdiene; Dewar ベンゼン; 大環状化合物; 環状パラフェニレン; Diels-Alder反応; 原子価異性化; 超分子; ホストゲスト錯体; 人工レセプター

We have successfully synthesized and characterized novel p-phenylene-based strained macrocycles by introducing 1,4-acetal-bridged Dewar benzene as a building block. The present results demonstrate that a Dewar benzene unit can be exploited as a masked p-phenylene unit for the constraction of strained macrocyclic systems. By using other spacers and/or connection modes, a variety of p-phenylene-containing strained macrocycles with unique structures and properties may well become available based on the present building block aproach.We have also successfully developed a new bisdiene molecule that produces a Dewar benzene skeleton upon two successive Diels-Alder reactions with activated dienophiles. Dehydrogenation of the 1: 2 adducts provides the corresponding Dewar form of polyacenes. Similar bisdiene systems possessing other 1,4-bridging units may also be available based on the synthetic scheme. Therefore, the present results open a unique and versatile route to Dewar derivatives which, in turn, would be regarded as potential precursors for novel cyclophanes as well as belt-type molecules.

通过引入1，4-缩醛桥连的Dewar苯作为结构单元，我们成功地合成并表征了新型的基于对苯撑的应变大环化合物。本研究结果表明，杜瓦瓶苯单元可以作为一个掩蔽的对亚苯基单元的应变大环系统的双作用。通过使用其他的间隔基和/或连接方式，可以得到各种具有独特结构和性能的含对亚苯基的应变大环，我们还成功地开发了一种新的双二烯分子，该分子通过与活化的亲双烯体的两次连续的Diels-Alder反应产生Dewar苯骨架。1：2加合物的脱氢提供相应的杜瓦形式的多并苯。基于合成方案，也可获得具有其它1，4-桥连单元的类似双二烯体系。因此，目前的结果打开了一个独特的和多功能的路线杜瓦衍生物，反过来，将被视为潜在的前体，为新的cyclophanes以及带型分子。

项目成果

Masakazu Ohkita: "Synthesis and Reaction of 1,4-Acetal-Bridged 2,3,5,6-Tetramethylidenebicyclo[2.2.0]hexane : The First Diels-Alder Route to Dewar Benzene"J.Chem.Soc., Chem.Commun.. 1999-2000 (1999)

Masakazu Ohkita：“1,4-乙缩醛桥接 2,3,5,6-四亚甲基双环[2.2.0]己烷的合成和反应：第一条狄尔斯-阿尔德路线生成杜瓦苯”J.Chem.Soc.，Chem。

Masakazu Ohkita: "Generation, Spectroscopic Characterization, and Reactions of 3,4-Benzotropone. Distinctive Photochemical Behavior of 6,7-Benzobicyclo[3.2.0]hepta-3,6-dien-2-one in Rigid Glass at Low Temperature and in Fluid Solution"J. Am. Chem. Soc.. 1

Masakazu Ohkita：“3,4-苯甲托酮的生成、光谱表征和反应。6,7-苯并双环[3.2.0]hepta-3,6-dien-2-one在低温和低温条件下在刚性玻璃中的独特光化学行为

Masakazu Ohkita: "Synthesis and Reaction of 1,4-Acetal-Bridged 2,3,5,6-Tetramethylidenebicyclo [2 .2.0]hexane : The First Diels-Alder Route to Dewar Beazene"J. Chem. Soc., Chem. Commun.. 1999-2000. (1999)

Masakazu Ohkita：“1,4-乙缩醛桥接 2,3,5,6-四亚甲基双环 [2 .2.0]己烷的合成和反应：第一条 Diels-Alder 路线生成杜瓦苯氮烯”J。

Takashi Tsuji: "Tricyclo [4.2.2.2^<2,5>] dodeca-1,3,5,7,9,11-hexacne : generation and chemical Trapping of the 3,4-dicyans derivative" J.Chem.Soc.,Chem.Commun.22. 2151-2152 (1997)

Takashi Tsuji：“三环 [4.2.2.2^<2,5>] dodeca-1,3,5,7,9,11-hexacne：3,4-二氰衍生物的生成和化学捕获”J.Chem.Soc

Hidetoshi Kawai: "Kinetic Stabilization of[1.1]Paracyclophane System. Isolation and X-Ray Structural Analysis of a [1.1]Paracyclophane Derivative and its Interconversion with the Transannular Adduct"Chem.Eur.J.. 6(印刷中). (2000)

Hidetoshi Kawai：“[1.1]对环芳烷系统的动力学稳定性。[1.1]对环芳烷衍生物的分离和 X 射线结构分析及其与跨环加合物的相互转化”Chem.Eur.J. 6（印刷中）。 ）