Science of Synthesis

Härtinger, S.; Härtinger, M., Science of Synthesis, (2007) 35, 572.

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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‌Meeeeeeeeee 8‌

M8	Meeeeeeeeee	Meeeee (%)	Mee
	MMe8, eeee, eeeeee, 8 e	88	[‌88‌]
	eeeeeeeeeee, eeee, eeeeee, 8 e	88	[‌88‌]
	MMe8, eν	e.e.e	[‌88‌]
	eeeeeeeeeee, ee, eeeeee	e.e.	[‌88‌]
Me	MMe8, eν, eeeeee, 88 eee	88	[‌8‌]

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References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) 8/8, 888.
• 8.Meeeee-Meee, (8888) 8/8e, 888.
• 8.Meeeee-Meee, (8888) M 88e8, 888.