The Chemistry of Novel[7]Annulene Compounds

新型[7]轮烯化合物的化学

• 批准号: 04640489
• 负责人: MACHIGUCHI Takahisa
• 金额: $ 1.28万
• 依托单位: Saitama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04640489/
• 关键词: [7]Annulene; [7]Annulenethione; Fulvene; Cycloaddition; Cage Molecule; [7]Annulenimine; S-Oxide; Sulfine; アヌレンチオン; アヌレンイミン; 環状付加反応

We have found the following results,1.The absorption bands of tropothione are assigned by a new method "magnetic circular-dichroism".2.[7]Annulenthione, which is valence isoelectronic with tropone, reacts concertedly with fulvene to give 1 : 1[8 + 2]cycloadducts. The product configuration is sharply different from that of the initially formed[6 + 4]cycloadduct between tropone and fulvene. The reaction mechanism are studies kinetically and by molecular orbital calculations. The obtained endo form of the[8 + 2]product is found to arise from the secondary orbital interaction in the course of the intrinsic reaction coordinate.3.Thermally stable[7]annulenthiones have been synthesized by direct thiocarbonylation of the corresponding tropones in polar solvents. The products are characterized by IR, UV-visible, and ^1H, ^<13>C, ^<14>N NMR spectroscopies.4.The reaction of 8, 8-dicyanoheptafulvene and cyclopentadienide anion affords under mild condition two unusual tetracyclic cage molecules. The structures are elucidated using various modern NMR spectroscopic techniques and deuterium-labeling experiments. The easy formation of the considerably strained molecules is ascribed to a nucleophilic addition, followed by protonation and an intramolecular Diels-Alder reaction with normal electron demand. MNDO-MO calculations suggest a possible mechanism.5.[7]Annulenthione S-oxide have been synthesized as stable dark red needles (mp 68ﾟC)in high yield. The structure and chemical behaviors of the sulfur are investigated both by X-ray analysis and ^<13>C, ^<17>O, ^<33>S NMR spectroscopies and this compound is found to be the first exmaple of a sulfine charge reversion(umpoulung).2-Amino[7]annulenimine is conveniently synthesized in high yield and is isolated in pure form.

结果表明：1.用一种新的方法“磁性圆二色性”对对流层的吸收谱带进行了归属. [7]环戊烯酮与环戊酮是等电子的化合物，它与富烯反应生成1：1的[8 + 2]环加合物。产物构型与最初形成的环加合物（6 + 4）有很大不同。通过动力学和分子轨道计算研究了反应机理。发现[8 + 2]产物的内型是由内禀反应配位过程中的次级轨道相互作用产生的。3.在极性溶剂中，通过硫代羰基化反应合成了热稳定的[7]轮硫酮。产物经IR、UV-可见光谱、~ 1H、~ <13>1C、~ 1 <14>N NMR等表征。4.在温和条件下，8，8-二氰基七富烯与环戊二烯阴离子反应，得到两个不常见的四环笼状分子。使用各种现代NMR光谱技术和氘标记实验的结构进行了阐明。相当紧张的分子的容易形成归因于亲核加成，然后质子化和分子内的Diels-Alder反应与正常的电子需求。MNDO-MO计算表明了一种可能的机制. [7] annulenetransS-氧化物已被合成为稳定的暗红色针状物（mp 68 ℃），产率很高。通过X射线衍射和~ <13>1C，~ 1 <17>O，~ 1 <33>S核磁共振谱研究了硫的结构和化学行为，发现该化合物是硫醚电荷反转（umpoulung）的第一个例子。2-氨基[7]轮烯亚胺以高产率方便地合成，并以纯品形式分离。

项目成果

Takahisa Machiguchi: "Tropothione S-Oxide:The First Example of Sulfine Charge Reversion(Umpolung)" J.Am.Chem.Soc.116. 407-408 (1994)

Takahisa Machiguchi：“Tropothione S-Oxide：亚硫电荷反转的第一个例子（Umpolung）”J.Am.Chem.Soc.116。

T.Machiguchi: "A Simple Synthesis of Pure 2-Aminotroponimine, the Nitrogen Analogue of Tropolone" Chem.Lett.1821-1822 (1992)

T.Machiguchi：“纯 2-氨基托苯胺（托酚酮的氮类似物）的简单合成”Chem.Lett.1821-1822 (1992)

Takahisa Machiguchi: "Tropothione Undergoes Cycloaddition in a Way Different from Tropone:A Comparative Study of Their Reactivities on Cycloaddition to Fulvene" Journal of the American Chemical Society. 115. 11536-11541 (1993)

Takahisa Machiguchi：“托磷酸硫酮以不同于托酮酮的方式进行环加成：它们对富烯环加成反应性的比较研究”美国化学会杂志。

Takahisa Machiguchi: "A Simple Synthesis of Pure 2-Aminotroponimine,the Nitrogen Analogue of Tropolone" Chem.Lett.1821-1822 (1992)

Takahisa Machiguchi：“纯 2-氨基托苯胺（托酚酮的氮类似物）的简单合成”Chem.Lett.1821-1822 (1992)

T.Machiguchi: "Tropothione S-Oxide : The First Example of a Sulfine Charge Reversion(Umpolung)" J.Am.Chem.Soc.116. 407-408 (1994)

T.Machiguchi：“Tropothione S-Oxide：亚硫电荷反转的第一个例子（Umpolung）”J.Am.Chem.Soc.116。