Mercuration peroxy

Hitherto it has been assumed that the bond graph is bipartite, i.e. bonds only occur between a cation and an anion with no cation-cation or anion-anion bonds present. While the majority of inorganic compounds have bipartite bond graphs, there are a few, such as mercurous and peroxy compounds, that contain homoionic bonds. It is easy to see that there can be no electric flux linking two cations or two anions, so the ionic model predicts that no bond will exist between them. 

Fused cyclohexyl-1,2-dioxepines 141 and 142 were synthesised by the reaction of a peroxy hemiketal 140 onto a tethered a,(3-unsaturated ester. The reaction proceeded best when promoted by mercuric acetate <07T10407>. 

The reaction of propene and other olefins with mercuric salts of some strong oxy acids was shown to give acrolein and analogous carbonyl compounds. This reaction proceeds through a 1 1 adduct which in aqueous solution is probably of the form CH3CH(OH)CH2Hg+x. Inclusion compounds of diperoxy-carboxylic anhydrides with urea have been prepared as peroxy-acid precursors. The inclusion compounds are not shock or heat sensitive. 

Markownikoff addition. 2-Methylpent-l-ene allowed to react with tertAmiyl hydroperoxide and mercuric acetate with initial cooling and shaking, after 2 hrs. the volatiles removed by distillation in vacuo, and the residue digested repeatedly with coned, aq. NaCl -> l-diloromercuri-2-tert-butylperoxy-2-methylpentane. Y 19%. F. e., also hydroperoxymercuration with H2 2 s. E. Schmitz, A. Riedie, and O. Brede, J. pr. 312, 30 (1970) a-alkoxyketones from enolesters s. ibid. 312, 43 peroxy- and methoxy-mercuration of a,i -unsatd. ketones and esters s. A. J. Bloodworth and R. J. Bunce, Soc. (C) 1971, 1453. 

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