Chemistry of phenoxo complexes. VI. Reactions of phenoxocopper(I) complexes with carbon tetrachloride

Abstract

The reactions of several substituted cuprous phenoxides with CCl4 in acetonitrile were examined. Phenoxides without ortho-substituents usually gave high yields of tetraarylorthocarbonates. It is shown that the latter are also produced catalytically from sodium phenoxides and CCl4 in the presence of small amounts of cuprous chloride. Cuprous phenoxides with ortho-chloro substituents, in the absence of facile hydrogen transfer agents, gave stable mixed oxidation state complexes of approximate composition: Cu2ICuIICl2(OAr)2. In the presence of facile hydrogen atom transfer agents, such as free phenol or ascorbic acid, both the phenoxides without ortho-substituents and the ortho-chlorinated phenoxides gave moderate yields of triarylorthoformates. Some reactions of tritertbutylphenol and tritertbutylphenoxyl with copper complexes are described. The mechanisms of the various reactions are interpreted in terms of homo- and cross-coupling between phenoxyl and •CCl3 radicals.