The Chemistry of Novel[7]Annulene Compounds

我们发现了以下结果：1。对角硫酮的吸收带是用一种新方法“磁圆二色性”来分配的。环硫酮与托酮呈价等电子，与氟烯协同反应生成1:1[8 + 2]环加合物。产物构型与托苯酮和富勒烯之间最初形成的[6 + 4]环加合物有很大的不同。通过动力学和分子轨道计算对反应机理进行了研究。得到的[8 + 2]产物的内端构型是在本征反应座标过程中由二级轨道相互作用产生的。通过在极性溶剂中直接将相应的tropones进行硫代羰基化，合成了热稳定的[7]环硫酮。通过红外光谱、紫外可见光谱和^1H、^<13>C、^<14>N核磁共振光谱对产物进行表征。8,8 -二氰七氟烯与环戊二烯阴离子在温和条件下反应得到两个不常见的四环笼状分子。利用各种现代核磁共振光谱技术和氘标记实验对其结构进行了阐明。相当张力分子的容易形成归因于亲核加成，随后是质子化和具有正常电子需求的分子内Diels-Alder反应。MNDO-MO计算提出了一种可能的机制。[7]环硫酮s -氧化物以高收率合成了稳定的深红色针状物（mp68 - C）。通过x射线分析和^<13>C, ^<17>O, ^<33>S核磁共振光谱研究了硫的结构和化学行为，发现该化合物是亚砜电荷还原（umpoulung）的第一个例子。2-氨基b[7]环胺是一种合成方便、产率高、分离纯度高的化合物。

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.