A NOVEL DIRECT CONVERSION REACTION OF THE C=C BOND INTO C*C BOND AND ITS APPLICATION TO THE SYNTHESIS OF FUNCTIONAL SUBSTANCES

碳碳双键形成碳碳三键是合成有机化学中一个非常重要的过程。乙炔键形成的正统方法是从较饱和的结构中除去稳定的物质。在空气中的N，N-二甲基甲酰胺中，用t-丁氧化钾（t-BuOK）在9,10-二（4′-取代苯基）蒽系、4-取代4′-硝基苯乙烯系和1-（对硝基苯基）-4-（对取代苯基）-1,3-丁二烯系中，发现了由C*C双键直接生成C*C乙炔键的新方法；与爱媛大学的田岛国彦博士合作，研究了它的范围和局限性，并测量了与4-二乙胺-4'-硝基苯乙烯反应的ESR谱，以确定一种阴离子自由基，有望解释脱氢反应的机理。有趣的是，在许多情况下，大量过量的t-BuOK的使用会导致苯核上硝基的邻位羟基化。简单的羟基化反应有助于取代芳乙基- 1 -2-硝基苯酚的合成，这些取代芳乙基- 1 -2-硝基苯酚具有相应的非羟基化合物，有望用于非线性光学材料。测定了其紫外可见光谱和荧光光谱性质，并与相关化合物进行了讨论。目前正在研究将这些反应应用于制备功能物质（功能染料、酶活性测定底物，如膦酸盐等）。

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.