tert-Butyl hydroperoxide → HCID 10856043, compound

Temperature

-20 °C

To a 1L 3-neck round-bottom flask equipped with a mechanical stirrer, thermocouple and nitrogen inlet was added CH2C12 (350 mL), dried 4 Å molecular sieves (30 g) and L-(+)-diethyl tartrate (7.62 g, 0.037 mol). The resulting mixture was cooled to -20° C. and treated with Ti(O-i-Pr)4 (9.2 mL, 0.031 mol), followed by the addition of t-butylhydroperoxide (4.0 M in CH2Cl2, 182 mL, 0.78 mol) at a rate to maintain the temperature 2 -20° C. Upon complete addition, the reaction mixture was stirred for another 30 min, and then treated with a solution of the allylic alcohol (15) (50 g, 0.31 mol) in CH2C12 (30 mL) at a rate to maintain the temperature at -20° C. The reaction was stirred at the same temperature for 5 h, then filtered into a solution of ferrous sulfate heptahydrate (132 g) and tartaric acid (40 g) in water (400 mL) at 0° C. The mixture was stirred for 20 min, then transferred to a separatory funnel and extracted with t-BuOMe (2×200 mL). The combined organic phase was stirred with 30% NaOH solution containing NaCi, for 1 h at 0° C. The layers were again separated, and the aqueous phase extracted with t-BuOMe. The combined organic phase was washed with brine, dried over MgSO4 and concentrated to yield the title compound (52.8 g) as an amber oil.

1. additionthermocouple and nitrogen inlet was added CH2C12 (350 mL)
2. temperatureto maintain the temperature 2 -20° C
3. additionUpon complete addition
4. temperatureto maintain the temperature at -20° C
5. stirringThe reaction was stirred at the same temperature for 5 h
6. filtrationfiltered into a solution of ferrous sulfate heptahydrate (132 g) and tartaric acid (40 g) in water (400 mL) at 0° C
7. stirringThe mixture was stirred for 20 min
8. customtransferred to a separatory funnel
9. extractionextracted with t-BuOMe (2×200 mL)
10. stirringThe combined organic phase was stirred with 30% NaOH solution
11. additioncontaining NaCi
12. waitfor 1 h at 0° C
13. customThe layers were again separated
14. extractionthe aqueous phase extracted with t-BuOMe
15. washThe combined organic phase was washed with brine
16. dry with materialdried over MgSO4
17. concentrationconcentrated

ORD record

ord-835b21d45c2a4eafafcc47661635ffa1

Source dataset

uspto-grants-2000_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06020512