tert-Butyl hydroperoxide → HCID 10856043, Verbindung

Temperatur

-20 °C

To a 1 L 3-neck round-bottom flask equipped with a mechanical stirrer, thermocouple and nitrogen inlet was added CH2Cl2 (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 CH2Cl2 (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 NaCl, 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. customTo a 1 L 3-neck round-bottom flask equipped with a mechanical stirrer
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 NaCl
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-Eintrag

ord-333d6d4567d642bfaf9d6633fc717b8c

Quelldatensatz

uspto-grants-2000_10

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US06133457