Phenol Vinylation process and application of polyCo-vinyphend.

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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.