Hydrogen Peroxide → Suberic acid

Participants

Reaction Steps

To a mixture of [Mn2O3(Me3-TACN)4] (PF6)2.H2O (8.1 mg, 10 μmol, 0.1 mol %) and 2,6-dichlorobenzoic acid (57.3 mg, 0.30 mmol, 3.0 mol %) in CH3CN (7 ml) was added H2O2 (30 μl of a 50% aq. solution, 0.53 mmol) at room temperature and the resulting mixture was stirred for 20 min. Subsequently cyclooctene (1.16 g, 10 mmol) was added together with CH3CN (2 ml) and water (1 ml). H2O2 (2.83 ml of a 50% aq. solution, 50 mmol, 5.0 equiv.) was then added at room temperature using a syringe pump (0.07 ml/h). New batches of [Mn2O3(Me3-TACN)2] (PF6)2.H2O (8.1 mg, 10 μmol, 0.1 mol % per batch) were added to the reaction mixture 17, 25 and 40.5 hours after the addition of H2O2 had commenced. When the addition of H2O2 was completed, the mixture was stirred for additional 1 hour. Water (10 ml) and Et2O (10 ml) were added and the pH of the aqueous layer was set to pH >9 by adding some saturated NaHCO3 (aq.). The organic layer was separated and the aqueous layer was washed with Et2O (3×15 ml). The pH of the aqueous layer was subsequently set to pH <2 with some 10% HCl (aq.) and was extracted with Et2O (3×20 ml). The combined organic extracts were dried over anhydrous Na2SO4. The solvents were removed in vacuo yielding 868 mg of a solid with a purity of circa 95% (determined by 1H NMR), 47% yield of suberic acid. 1H NMR (400 MHz, acetone-d6) δ 1.34-1.39 (m, 4H), 1.56-1.63 (m, 4H), 2.28 (t, J=7.4, 4H). N.B. NMR showed other compounds as well, including 2,6-dichlorobenzoic acid.

Provenance & Evidence