Cyclohexene

Mercury(II) acetate

t-Butyl hydroperoxide

Perchloric acid (60%)

Potassium bromide

t-Butyl hydroperoxide solution

MgSO₄ (8 g) was added to a mixture of t-butyl hydroperoxide (10 g, 70%, 78 mmol) and CH₂Cl₂ (40 cm³) and the mixture stirred for 10 m. The drying agent was filtered and washed with CH₂Cl₂ (10 cm³) to give a solution of anhydrous t-butyl hydroperoxide.

 

Perchloric acid solution

A mixture of perchloric acid (2.0 g, 65%, 13 mmol) and CH₂Cl₂ (20 cm³) was magnetically stirred and cooled in ice. Acetic anhydride was slowly added until a homogeneous solution formed.

 

To mercury(II) acetate (6.4 g, 20 mmol) was added the t-butyl hydroperoxide solution followed by the perchloric acid solution. With magnetic stirring, cyclohexene (1.8 g, 22 mmol) dissolved in CH₂Cl₂ (10 cm³) was added. Most of the mercury(II) acetate rapidly dissolved except for some lumps which dissolved after 15 m. Water (100 cm³) was added and the organic phase separated and stirred with a solution of potassium bromide (5 g) in water (15 cm³) for 0.5 h. Water (100 cm³) was added, the organic phase separated, dried (MgSO₄), and evaporated to give a white solid (9.9 g) after drying at 0.01 mm. Crystallisation from petrol (40/60, 75 cm³) gave bromo-(2-t-butylperoxycyclohexyl)mercury as white needles (7.32 g, 81%).

δ_C (CDCl₃) 24.56t, 26.58q (3C), 28.28t, 31.63t [J(¹⁹⁹Hg-¹³C) 305 Hz], 32.75t [J(¹⁹⁹Hg-¹³C) 756 Hz], 57.32d, 80.89s, 85.73d [J(¹⁹⁹Hg-¹³C) 112 Hz].

 

δ_Hg (CDCl₃) –1199.6.

Bloodworth AJ and Courtneidge JL, J. Chem. Soc., Perkin Trans. 1, 1981, 3258-3264

DOI: 10.1039/P19810003258