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Study on Synthesis and Properties of Novel pi System Compounds

新型π系化合物的合成及性能研究

基本信息

批准号：
07640709
负责人：
MACHIGUCHI Takahisa
金额：
$ 1.41万
依托单位：
Saitama University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1997
项目状态：
已结题

项目摘要

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.

结果表明：1.甲酮肟对甲苯磺酸酯的亲核开环反应，立体选择性地生成全顺式三烯。该反应是合成共轭三烯的常用方法。2.以硫代二氯化硫为起始原料，合成了硫代托品酮。用DMAD检测到S-硫化物是一种前所未有的[10 π +2 π]型环加合物。3.我们成功地合成了托品酮的硫类似物托品酮。对流环酮的物理性质与环酮的物理性质形成鲜明对比。比较了对流层和托品的电偶极矩。根据偶极矩和从头计算方法，计算了庚三烯和庚三酮的电荷分离。4.对庚三烯和庚三酮的HgCl_2配合物进行了理论和实验研究。配合物的红外光谱数据与理论计算值进行了比较。Troponin与HgCl_2以σ复合物的形式连接。5.自1920年Staudinger发现二苯基乙烯酮-环戊二烯反应以来，二烯烃的不识别一直是有机化学中的一个重要问题。我们已经证实乙烯酮识别共轭二烯。乙烯酮是一种亲双烯体，不是用于众所周知的[2 + 2]环加成反应，而是通过其C = O键的[4 + 2]（Diels-Alder）反应。