| Research Abstract |
The formation of a carbon-carbon triple bond from a carbon-carbon double bond is a fundament-tally important process in synthetic organic chemistry. The orthodox method of formation of the acetylenic bond is elimination of a stable substance from a more saturated structure. A novel and facile method for direct C*C acetylenic bond formation from the C*C double bond by treatment with potassium t-butoxide (t-BuOK) in N,N-dimethylformamide in the air has been found in a 9,10-bis (4'-substituted styryl) anthracene series, in 4-substituted 4'-nitrostilbene series, and in 1- (p-nitrophenyl)-4- (p-substituted phenyl)-1,3-butadiene series ; its scope and limitations have been examined and the ESR spectrum of the reaction against 4-diethylamino-4'-nitrostilbene was measured to identify an anion radical species expected for explanation of the mechanism of the dehydrogenation reaction, in collaboration with Dr.Kunihiko Tajima of Ehime University. In many cases, interestingly, the use of a large excess of t-BuOK brought about succeeding hydroxylation into the ortho-position of a nitro group on the benzene nucleus. The simple hydroxylation is useful to the synthesis of substituted arylethyny l-2-nitrophenols, which are expected for non-linear optical materials with the corresponding non-hydroxy compounds. These ultraviolet-visible and fluorescence spectral properties were measured and discussed with the related compounds. Application of these reactions to prepare functional substances (functional dyes, substrates for the measurement of enzyme activity such as phonorates and so on) is now being studied.
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