Subject from organomercurials

Entry 5 is an example of the use of fra-(trimethylsilyl)silane as the chain carrier. Entries 6 to 11 show additions of radicals from organomercury reagents to substituted alkenes. In general, the stereochemistry of these reactions is determined by reactant conformation and steric approach control. In Entry 9, for example, addition is from the exo face of the norbornyl ring. Entry 12 is an example of addition of an acyl radical from a selenide. These reactions are subject to competition from decarbonylation, but the relatively slow decarbonylation of aroyl radicals (see Part A, Table 11.3) favors addition in this case. 

But the diazo method still had its grip on me. Which metals, apart from mercury, could be subjected to the method To answer this, many years were to pass because simultaneously I was working on other problems of interest to me. Eventually, the method of synthesis was extensively developed for aromatic derivatives of such elements as Hg, Tl, (Ge), Sn, (Pb), As, Sb, Bi. For the metals in parentheses the method was shown to just work, while for the others it is an excellent preparative procedure. In Table I the best versions are exemplified. At the same time, I and the first generation of my disciples, and also other scientists, applied the method to various organomercurials substituted at the aromatic nucleus (19-21), and to the naphthalene (22), triphenylmethane (23), and pyridine (24) series. 

Inorganic mercury was also isolated as methyl mercury upon reaction with tetra-methyl tin ° The initial extracts were subjected to thiosulfate clean-up, and mercury was isolated as the bromide derivative. The method yielded good agreement between gas-chromatographic and atomic absorption spectrometric data. Twenty-four samples were analyzed daily on a routine basis. Organomercurials could also be determined and the differences from inorganic mercury could be detected by these gas-chromatographic methods ... 

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