Study on Synthesis and Properties of Novel pi System Compounds

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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.