tert-Butyl hydroperoxide → Oxiranemethanol, 3-(4-nitrophenyl)-, trans-(-)-

Participants

Reaction Conditions

Reaction Steps

A flame-dried 50 ml three-necked flask was fitted with a thermometer and a dropping funnel, flushed with nitrogen, and charged with a mixture of powdered, activated 3 Å molecular sieves (0.45 g) and dry CH2Cl2 (15 ml). After cooling to −5° C., L-(+)-diethyl tartrate (92.8 mg, 0.45 mmol) and Ti(O-i-Pr)4 (88.5 ul, 0.30 mmol) were added sequentially. The mixture was cooled to −20° C. in a CCl4 dry ice bath, (E)-3-(4-nitrophenyl)-2-propenol 4 (1.074 g, 6 mmol) (dissolved in dry methylene chloride (15 ml) and dried with 3Å molecular sieves for 10-15 min prior to addition) was added and the mixture was stirred for 10 minutes. A 7.0 M solution of t-butylhydroperoxide (TBHP) in CH2Cl2 (1.72 ml, 12 mmol) was added, taking care to maintain the temperature around −20° C. After stirring, at −20° C. for 2 hrs, the cold (−20° C.) reaction mixture was quenched with a 10% aqueous solution of sodium hydroxide saturated with sodium chloride (0.48 ml). Ether in the amount of 10% of the total volume of the reaction mixture was added, the cold bath removed and the stirred mixture allowed to warm to 10° C. Stirring was maintained for an additional 10 minutes at 10° C., whereupon anhydrous MgSO4 (0.48 g,) and Celite® (0.06 g) were added. After a final 15 min. of stirring, the mixture was allowed to settle and the clear solution was filtered through a pad of Celite® and washed with ethyl ether. Concentration of the ether solution gave the crude product containing TBHP, which was dissolved in a minimum amount of ethyl acetate, filtered through a small pad of silica gel, and recrystallized from CH2Cl2-hexanes to yield compound 5, (2S, 3S)-3-(4-nitrophenyl) oxiranemethanol (1.13 g, 97%) as light yellow needles: mp 100-101° C. (literature value: 98-99° C.); Rf=0.62 (5% CH3OH—CH2Cl2); 1H NMR (300 MHz, CDCl3) δ: 8.22 (d, aromatic, 2H, J=8.7 Hz), 7.45 (d, aromatic, 2H, J=8.7 Hz), 4.10 (m, 2H) 3.89 (m, 1H), 3.20 (m, 1H), 1.74 (m, 1H); 13C NMR (CDCl3): d 147.88(C), 144.35(C), 126.41(CH), 123.82(CH), 62.94(CH), 60.62(CH2), 54.30(CH). Anal. Calcd for C9H9NO4: C, 55.38; H, 4.65; N, 7.18. Found: C, 55-65; H, 4.54; N, 7.17.

Provenance & Evidence