Novel Kinetic Stabilization of the [1.1] Paracyclophane System and Preparation of the Naphthalenophane System

[1.1]对环芳烷体系的新型动力学稳定性及萘芬体系的制备

• 批准号: 13640521
• 负责人: KAWAI Hidetoshi
• 金额: $ 1.92万
• 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: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640521/
• 关键词: Cyclophane; Strained Compounds; Dewar benzene; Photochromic; Kinetic Stabilization; Extended Conjugation; Aromatic Compounds; Transannular Interaction; 光互変異性; 高歪み化合物

A kinetic stabilization of the [1.1]paracyclophane system was examined by structurally modifying the methylene bridges. This approach allows introductlon of a variety of substituents on the benzene rlngs of [1.1]paracyclophane. The bis (Dewar benzene) derivative, the precursor of [1.1]paracyclophane, bearing t-BuMe_2SiO groups on the bridges prepared in 21 steps. Photoirradiation to this compound at 77K resulted in the formation of labile [1.1]paracyclophane but accompanied by other byproducts. To investigate the reactivity and stability of this new type of [1.1]paracyclophanes bearing different groups in this position was also prepared.The [1.1]naphthalenophanes exhibiting extended conjugation of the [1.1]paracyclophane π-system were designed in anticipation of the enhanced transannular effect. In the course of preparation of their precursors, a novel benzo-annulation method consisting of [2+2]photocycloaddition of olefins to benzoquinone bis (ethylene ketal), deprotection of ketals and spontaneous aromatization steps was developed. Synthetic study of [1.1]naphthalenophane derivatives is now under way by this methods.

通过对亚甲基桥进行结构修饰来检查[1.1]对环芳系统的动力学稳定性。这种方法允许在[1.1]对环芳烷的苯环上引入多种取代基，双（杜瓦苯）衍生物是[的前体。 1.1]对环芳烷，在21个步骤中制备的桥上带有t-BuMe_2SiO基团。在 77K 下对该化合物进行反应导致形成不稳定的 [1.1] 对环芳烷，但同时还伴有其他副产物。为了研究这种在该位置带有不同基团的新型 [1.1] 对环芳烷的反应性和稳定性，还制备了 [1.1]。具有[1.1]对环芳烷π系统的扩展共轭性的萘芬是为了增强跨环效应而设计的。在其前体的制备过程中，开发了一种新型苯并环化方法，包括烯烃与苯醌双（乙烯缩酮）的[2+2]光环加成、缩酮的脱保护和自发芳构化步骤，目前正在通过该方法进行[1.1]萘芬衍生物的合成研究。

项目成果

H. Kawai, T. Suzuki, M. Ohkita, T. Tsuji: "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"Chemistry European Journal. 6.

H. Kawai、T. Suzuki、M. Ohkita、T. Tsuji：“[1.1]对环芳烷系统的动力学稳定。[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”化学欧洲

T. Tsuji, M. Ohkita, H. Kawai: "Preparation and Kinetic Stabilization of Highly Strained Paracyclophanes"Bulletin of the Chemical Society of Japan. 75・3(印刷中). (2002)

T. Tsuji、M. Ohkita、H. Kawai：“高应变对环芳烷的制备和动力学稳定”日本化学会通报 75・3（印刷中）。

藤本 博: "有機量子化学"朝倉書店. 196 (2001)

藤本浩：《有机量子化学》朝仓书店 196 (2001)。

M.Ohkita: "Intramolecular Diels-Alder reaction of cyclopenta-1, 3-diene derivatives generated in situ from 4-(pent-4-enyl)cyclopent-2-enore ethylene ketals"Journal of Chemical Society Perkin Transaction 1. 3. 366-370 (2002)

M.Ohkita：“从 4-(戊-4-烯基)环戊-2-烯醇乙烯缩酮原位生成环戊-1, 3-二烯衍生物的分子内狄尔斯-阿尔德反应”《化学学会期刊 Perkin Transaction》1. 3。

T.Tsuji: "Functionalization and Kinetic Stabilization of the [4]Paracyclophane System and Aromaticity of Its Extremely Bent Benzene Ring"Journal of the American Chemical Society. 125・4. 951-961 (2003)

T. Tsuji：“[4]对环芳烷系统的官能化和动力学稳定性及其极度弯曲的苯环的芳香性”美国化学会杂志 125・4（2003）。