Reaction with mercurated nitrophenols

Reaction with mercurated nitrophenols McMurray and Trentham (1969) and Stefanini et al. (1972) have described the synthesis of several mercurated nitrophenols (Table 3.2). The spectra of these organomercurials show large changes in the visible region when thiols displace more weakly bound ligands from 

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Nitromersol/777-j5 , y (4) and mercurophen [52486-78-9] (5) are prepared by the same mercuration reaction as phenyhnercuric acetate, only 4-nitro-(9-cresol and o-nitrophenol are used, respectively, iastead of benzene. The second step is reaction with sodium hydroxide to form the anhydride or sodium salt, respectively. 

Benzene and some of its derivatives react with solutions of mercuric nitrate in concentrated nitric acid to give nitrophenols. These reactions, known as oxynitrations may proceed by mercuration followed by nitroso-demercuration the resulting nitroso compound becomes a diazonium compound and then a phenol, which is nitrated. ... 

Swain and Eddy have queried the wide applicability of the S l and Sif2 mechanisms and favored a push-pull termolecular process for the reaction of pyridine with methyl bromide in benzene solution for example, they have suggested that the effects observed on the addition of methanol, phenol, p-nitrophenol, and mercuric bromide to the reaction mixture can be explained by an intermediate of type 168. ... 

The catalytic action of mercuric nitrate in the nitration of anthraquinone with nitric acid was observed in 1906 by Holdermann [122], Soon after that, Wolffen-stein and Boters [123] observed the specific influence that mercuric nitrate exercised on the formation of the products of nitration of benzene. They showed that at a certain concentration of nitric acid, mostly nitrophenols were formed ( oxy-nitration reaction). 

Fulminates other than those of Hg and Ag (and also complex Na[Au(CNO)2] from AuCls [110]) cannot be prepared directly by reaction of the metal with nitric acid and subsequently with ethanol like MF or SF [15, 33]. Several reasons exist that make direct formation of other fulminates impossible. Wohler and Martin reported that solubility of most fulminates in the reaction mixture is a reason why only MF and SF can form directly. Most other fulminates are soluble and unstable in the reaction mixture, in which they decompose [57]. Another reason is that the fulminic acid too readily forms complex salts and therefore simple fulminates cannot be isolated [35]. A catalytic effect of noble metals (Hg, Ag) on some of the reaction steps of fulminate formation was reported by Krauz. He mentioned the analogy of the catalytic effect of mercuric ions on hydrocarbons that are oxidized to the relevant nitrophenols in dilute nitric acid [35]. 

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