The Chemistry of Novel[7]Annulene Compounds

结果表明：1.用“磁性圆二色谱”新方法对硫代硫酮的吸收带进行了指认。2.[7]与托洛酮等电子的环硫酮与富烯发生配位反应，生成1：1[8+2]环加合物。产物构型与最初在托酮和富烯之间形成的[6+4]环加成物有很大不同。通过分子轨道计算，对反应机理进行了动力学研究。得到的[8+2]产物的内切形式来源于本征反应配位过程中的二次轨道相互作用。3.通过相应的热带酮在极性溶剂中的直接硫代羰化反应合成了热稳定性较好的[7]环硫酮。产物用红外光谱、紫外-可见光谱和~1H，^&lt；13&gt；C，^&lt；14&gt；N核磁共振光谱进行了表征。4.8，8-二氰基七碳富烯与环戊二烯阴离子的反应在温和的条件下提供了两个特殊的四环笼形分子。这些化合物的结构通过各种现代核磁共振波谱技术和氚标记实验得到了证实。相当紧张的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。5.[7]高产率地合成了稳定的暗红色针状物(MP 68ﾟC)。用X-射线分析和核磁共振谱研究了硫的结构和化学性质，发现该化合物是亚硫基电荷反转(Umpoulung)2-氨基[7]轮亚胺的第一个例子。

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.