Study on Synthesis and Properties of Novel pi System Compounds

我们发现了以下结果：1.一种新的、易于亲核开环的托洛酮肟对甲苯磺酸盐，用于立体选择性地合成全顺式三烯。该反应是获得共轭三烯的有效方法。2.以硫代硫酮和S_2Cl2为原料，合成了硫代硫酮。通过与DMAD的反应，发现了一种前所未有的[10pi+2pi]型环加成产物。3.成功地合成了硫代硫酮的类似物硫代硫酮，并对其进行了光谱表征。硫代硫酮的物理性质与托洛酮的物理性质形成鲜明对比。比较了硫代硫酮和托洛酮的电偶极矩。在偶极矩和从头计算的基础上，对硫代硫酮和托洛酮的电荷分离进行了理论和实验研究。4.对硫代硫酮和托洛酮的HgCl2络合物进行了理论和实验研究。红外光谱数据与振动分析得到的理论数据进行了比较。Tropone与HgCl2以单一络合物的形式相连。自从1920年Staudinger发现二苯基酮-环戊二烯反应以来，二烯在酮类反应中的不识别一直是有机化学中的一个重要问题。我们发现，乙烯酮可以识别共轭双烯。烯酮是一种亲双烯化合物，不是用于众所周知的[2+2]环加成反应，而是通过其C=O键进行[4+2](Diels-Alder)反应。

We have found the following results,1.A novel and supriginly facilc nucleophilic ring opening of tropone oxime tosylate to produce all-cisoid trienes stereoselectively. The reaction is usuful method to obtain conjugated trienes.2.Tropothione S-sulfife is synthesized from tropone hydrazone with S_2Cl_2. The S-sulfide is detected as an unprecedented [10pi+2pi] -type cycloadduct with DMAD.3.We have suceeded in synthesis, isolation, and spectral characterization of tropothione, the sulfur analogue of tropone. The physical properties of tropothione are in sharp contrast to those of tropone. The electric dipole moment of tropothione and tropone hase been compared. The charge separation of tropothione and tropone is evaluated on the basis of the dipole moment and ab initio calculations.4.HgCl_2 complexes of tropothione and tropone are studied both experimentally and theoritically. IR spectroscopic data of these complexes are compared with theoritical ones derived from vidrational analyzes. Tropone is linked with HgCl_2 in the form of a sigmacomplex. But, tropothione give pi complex.5.Non-recognition for dienes in ketene reactions has long been an important problem in organic chemistry since the diphenylkefene-cyclopentadiene reaction was found by Staudinger in 1920. We have discoverd that the ketene recognizes conjugated dienes. The ketene is a dienophile not for well-known [2+2] cycloadditions but [4+2] (Diels-Alder) reactions across its C=O bond.