Reaction of Arylmercuric Chlorides with Sodium Naphthalenide

Article abstract of DOI:10.1021/jo00122a017

Reactions of sodium naphthalenide (Na(+)Np(.-)) with arylmercuric chlorides, ArHgCl, Ar = phenyl (1a), o-anisyl (1b), p-anisyl (1c), p-tolyl (1d), p-nitrophenyl (1e), and o-(allyloxy)phenyl (1f), were carried out.The products were mainly diarylmercurials (Ar2Hg, 3) and smaller amounts of arene (ArH, 2).The yield of 3 was smaller and the yield of 2 greater when reactant ratios Np(.-)/ArHgCl were 2:1 rather that 1:1, resulting, it is proposed, from further reaction of Ar2Hg with the excessive amount of Np(.-).Reactions of Np(.-) with 3b-d gave quantitative yields of 2b-d.Reactions of 1f with Np(.-) gave not only 2f and 3f (mainly) but also small amounts of 3-methyl-2,3-dihydrobenzofuran (7), attributable to formation and cyclization of the o-(allyloxy)phenyl radical in a minor reaction pathway, and phenol (8), attributable to reaction of first-formed 2f with Np(.-).Reaction of Np(.-) with allyl 2-bromophenyl ether (9) in 1:1 and 2:1 ratios gave analogous results, namely 2f (mainly), 7, and 8.The results do not support an aryl radical (Ar.) route in conversions of ArHgCl to Ar2Hg, but one in which the Ar-Hg bond is not broken.Good material balances were obtained with all reactions except that with 1e.