Ozonolysis of organomercurials

Procedure. Product-Determining Studies. In a typical productdetermining run 10 mmoles of organomercurial were dissolved in ca. 50 ml of CH2C12 and placed in the reaction vessel. After the vessel was cooled to the proper temperature, the 03-02 flow was started. In all cases an immediate white precipitate appeared. This precipitation was constant throughout the entire ozonolysis procedure and in fact was used as an endpoint determinant in certain cases. 

Ozonolysis of the s-alkylmercuric halides and the di-s-alkylmercurials produced the coresponding ketone. Although some carbon-carbon cleavage occurred, it was generally less than with the reaction of the primary organomercurials (see Reactions 13 and 14, Table I). In partial contrast to the results of Bockemuller and Pfeuffer (Reaction II), the ozonation of diisopropylmercury yielded acetic acid in addition to acetone (Reaction 14, Table I). 

The inorganic products of the ozonolysis reactions were determined for three different organomercurials. Ozonolysis of two dialykylmer-curials produced a mixture of mercuric chloride, mercurous chloride, and mercuric oxide (Reactions 3 and 14, Table I) while one alkylmercuric halide gave only mercuric and mercurous chlorides (Reaction 13, Table I). A known mixture of the three salts was tested for its stability to the reaction conditions. The salts were ozonized as a solution/mixture with methylene chloride. Powder x-ray diffraction showed no difference in the mercury salt mixture after a 2-hour ozonation at 10°C. 

Reaction Stoichiometry. The results of the stoichiometry study (see Table II) were varied but did suggest a 1 1 ozone mercurial ratio for the cleavage of a carbon-mercury bond. Several problems were evident in such a study. Since mostly only the highest oxidation states for carbon were observed in the products of partial ozonation of 1°, 2°, and 3° organomercurials, it could be assumed that ozonolysis of the C—Hg bond involved the slowest step in the total reaction sequence. Hence, some... 

Product Studies. Table I outlines the organic and inorganic products of the ozonolysis reactions. The ozonolysis products of n-alkylmercuric halides and di-n-alkylmercurials were a mixture of carboxylic acids which had a carbon chain equal to or shorter than the alkyl group of the parent organomercurial. 

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