Phenol Vinylation process and application of polyCo-vinyphend.

乙烯烯是一类重要的化学物质，尤其是聚合物。由于直接合成乙烯基芳香族化合物的方法尚不清楚，因此在实验室和工业中都采用了逐步转化的方法制备乙烯基芳香族化合物。我们最近发现了一种用乙烯乙烯化苯酚的新方法，并在此基础上开发新的工业技术。以下是研究得到的结果。1)详细考察了苯酚乙烯化反应的范围。虽然产物相对不稳定，但该方法可以应用于具有供电子基团的酚的乙烯化反应。羟基斯蒂烯的制备步骤较短。具有吸电子基团的苯酚，如氰基、硝基或三氟甲基，它们的反应性比母体苯酚低，也可以乙烯化。2)建立了一种将苯酚转化为2,6-二乙烯基苯酚的方法。虽然产物的结构很简单，但大多数是未在化学文摘中报道的新化合物。3)研究了以Gacl_3为促进剂由芳烃合成（β -硅基乙烯基）芳烃的方法。产物经脱硅反应转化为乙烯烯。机理研究揭示了有机镓中间体的形成。这些研究使我们进入了有机镓化学的一个新领域。4)研究了几个涉及乙炔活化的C-C键形成反应。我们发现，氨水可以促进乙炔、烯烃和一氧化碳合成环戊烯酮的Pauson-Khand反应。新型多聚抗生素也被开发出来。

Vinylarenes are an important class of chemicals especially for polymers. Since synthetic method directly to vinylate aromatic compounds is not known, step-wise transformation has been employed for their preparation in the laboratory and in industry. We recently found a new method to vinylate phenols with ethyne, and the present study was undertaken to develop new industrial technology based on this reaction. Followings are the results obtained by the study.1) Scope of the phenol vinylation reaction was examined in detail. The methodology could be applied to vinylation of phenols possessing electron-donating groups, although products are relatively unstable. Hydroxystirenes were prepared in short steps. Phenols possessing electron-withdrawing groups such as cyano, nitro, or trifluoromethyl groups, which were less reactive than the parent phenol, could also be vinylated.2) A method to convert phenols to 2,6-divinylphenols were developed. Although the structure of the products are very simple, most of them were new compounds not reported in the Chem.Abstr.3) A method to synthesize (beta-silylvinyl) arenes from aromatic hydrocarbons was developed utilizing Gacl_3 as the promoter. The products were converted to vinylarenes by desilylation. The mechanistic studies revealed the formation of organogallium intermediates. These studies led us to a new field of organogallium chemistry.4) Several C-C bond formation reactions involving acetylene activation were developed. We found that the Pauson-Khand reaction which combines acetylene, olefin and carbon monoxide to give cyclopentenones could be promoted by aqueous ammonia. Novel polyyne antibiotics were also developed.