Study on Synthesis and Properties of Novel pi System Compounds

我们发现了以下结果：1。一种新颖的、极其容易的亲核开环的托苯酮肟甲酯，以立体选择性地产生全顺烷三烯。该反应是制备共轭三烯的有效方法。以邻苯二酮腙为原料，用S_2Cl_2合成了s -硫化对流层硫酮。硫代硫化物是一种前所未有的[10pi+2pi]型环加合物。我们已经成功地合成，分离和光谱表征的对流层硫酮，硫类似物。tropothione的物理性质与tropone的物理性质截然不同。比较了对硫酮和对硫酮的电偶极矩。根据偶极矩和从头计算，评价了对硫酮和对硫酮的电荷分离。从实验和理论两方面研究了斜硫酮和斜硫酮的HgCl_2配合物。并将这些配合物的红外光谱数据与理论分析结果进行了比较。Tropone以sigmaccomplexes的形式与HgCl_2连接。但是，对角硫酮给出配合物。自1920年Staudinger发现二苯基乙烯-环戊二烯反应以来，在烯烃反应中对二烯的不识别一直是有机化学中的一个重要问题。我们发现烯酮可以识别共轭二烯。烯酮是一种亲二亲化合物，不是在众所周知的[2+2]环加成反应中，而是在它的C=O键上发生[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.