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Please login to access the full content or check if you have access via Variation 1: Synthesis from Mercury(II) Carboxylates of Aliphatic Acids

DOI: 10.1055/sos-SD-035-00487

Härtinger, S.; Härtinger, M.Science of Synthesis, (200735572.

In a modification of the Hunsdiecker reaction, a mixture of mercury(II) oxide and a carboxylic acid,[‌2‌,‌51‌,‌59‌,‌62‌,‌63‌] or the isolated mercury(II) carboxylate,[‌2‌] is reacted with iodine. This procedure is more convenient as it avoids the tedious preparation and desiccation of high-purity silver(I) salts. Primary, secondary, and tertiary aliphatic carboxylic acids form mercury(II) carboxylates 14 using a slurry of excess mercury(II) oxide in the red or yellow form in an inert solvent (Scheme 5).[‌64‌] Addition of iodine and heating of the mixture results in iododecarboxylation of an intermediate acyl hypoiodite leading to iodoalkanes 15. The reaction proceeds in the dark; however, irradiation of the reaction mixture with a tungsten lamp has been shown to accelerate the liberation of carbon dioxide.[‌62‌,‌65‌] Other oxides, such as lead(II) oxide, red lead oxide (Pb3O4), silver(I) oxide, or cadmium(I) oxide[‌64‌] have been tried as a replacement for mercury(II) oxide, although, in general much lower yields are obtained. A related iododecarboxylation can be achieved with oxalic acid monoesters of bridgehead alkanes.[‌66‌]

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