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有机合成中一个非常重要的过程。形成炔键的传统方法是从更饱和的结构中消除一种稳定的物质。在9，10-双（4-甲基-1，4-二氧杂环丁烷-1-基）-1，4-二氧杂环丁烷-1-酮（9，10-bis）中，发现了一种在空气中用叔丁醇钾（t-BuOK）在N，N-二甲基甲酰胺中直接从C*C双键形成C*C炔键的新方法（4 '-取代的苯乙烯基）蒽系列、4-取代的4'-硝基芪系列和1-（对硝基苯基）-4-（对位取代苯基）-1，3-丁二烯系列;它的范围和局限性已被审查和ESR谱的反应对4-二乙氨基-4 '-与Ehime大学的KunihikoTajima博士合作，测量硝基芪以鉴定预期用于解释脱氢反应机理的阴离子自由基种类。在许多情况下，有趣的是，使用大量过量的t-BuOK导致随后羟基化到苯核上硝基的邻位。这种简单的羟基化反应可用于合成取代芳基乙炔基1 -2-硝基苯酚类化合物，这些化合物与相应的非羟基化合物一起可望用于非线性光学材料。测定了这些化合物的紫外-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性物质（功能性染料、用于测量酶活性的底物，如酚酸盐等）。

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.