Sulfuric Acid → Ethyl 2,2-di(tertiary-amylperoxy)-1-cyclohexanecarboxylate

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Ethyl 2,2-di(tertiary-amylperoxy)-1-cyclohexanecarboxylate was prepared by the addition of 92.64% TAHP (tertiary amyl hydroperoxide) (42.16 g, 0.3750 mol) to 95% ethyl 2-oxo-1-cyclohexanecarboxylate (17.92 g, 0.1000 mol) at room temperature in a three necked 250-mL round bottomed flask equipped with a thermometer and mechanical stirrer. The solution was cooled to −10° C. via a dry ice-acetone bath and 78% sulfuric acid (15.09, 0.1200 mol) was added dropwise to the solution with the temperature at −10° C. Upon completion of the addition of sulfuric acid, the solution was allowed to reach 5° C. where it was maintained by an ice-water bath for three hours with mechanical stirring. The reaction was transferred to a separatory funnel and the lower acidic aqueous layer separated and discarded. The organic layer was then washed with saturated NaCl solution until the aqueous washings had a pH of 4.5 or greater. The organic layer was then dried over MgSO4, filtered through a Buchner funnel and analyzed for purity by gas chromatography (53% by area). Purification by chromatography (silica gel, 95:5 petroleum ether/diethyl ether) afforded a liquid product: 13C NMR (75 MHz, CDCl3) δ 171.8 (C═O), 106.0 (O—C—O, cyclic), 81.1 (C—(CH3)2CH2), 81.0 (C(CH3)2CH2), 59.6 (O—CH2CH3), 44.0 (CH, cyclic), 3.16 (CH3—CH2—C), 31.5 (CH3CH2—C), 26.0 (CH2, cyclic), 23.6 (C(CH3)2, (2x)), 21.8 (CH2, cyclic), 22.0 (CH2, cyclic), 13.8 ((O—CH2CH3) (2X)), 8.0 ((CCH2CH3) (2x)); IR (neat) ν 1736, 1364, 1220, 872 cm−1.

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