tert-Butyl hydroperoxide → HCID 9815529, compound

Temperature

-20 °C

To a slurry of 5.0 g of powdered 4A molecular sieves in 400 ml of dry CH2Cl2 was added 2.09 g (8.42 mmole) of Ti(Oi-Pr)4 and 2.76 g (11.8 mmole) of L(+)diisopropyl tartrate at 0° C. under argon. The mixture was allowed to stir for 10 min, cooled to -20° C., and 22.5 ml of 3.8 M tert-butyl hydroperoxide in isooctane is added slowly at -20° C. The catalyst was allowed to "age" for 30 min. A solution of 7.50 g (42.1 mmole) of Z-4-(benzyloxy)-2-buten-1-ol in 15 ml of CH2Cl2 was dried over 3A molecular sieves for 15 min and then added to the mixture at -20° C. over 10 min. The mixture was allowed to stand in a refrigerator at 2° C. for 8 days. The reaction mixture was removed from the refrigerator and 40 ml of H2O was added with stirring. After stirring for 30 min, 15 ml of 30% NaOH in saturated brine was added and the mixture was allowed to stir 60 min longer. The organic layer was separated and the aqueous layer washed twice with 50 ml of CH2Cl2. The organic layers were combined, dried over MgSO4, filtered and evaporated to afford a milky, pale yellow oil. Distillation yielded 4.80 g of a clear viscous oil, bp 132-5° C. (0.2 mm Hg). 1H NMR, δ 7.4-7.2 (m, 5), 4.58 (dd, 2, J=12, 20 Hz), 3.7 (m, 4), 3.27 (ddd, 2, J=5, 10, 15 Hz), 1.98 (t, 1, J=6 Hz). Mass Spectra; EI; M+, Calc. 194.0942, Found 194.0929.

1. waitThe catalyst was allowed to "age" for 30 min
2. additionadded to the mixture at -20° C. over 10 min
3. waitto stand in a refrigerator at 2° C. for 8 days
4. customThe reaction mixture was removed from the refrigerator and 40 ml of H2O
5. additionwas added
6. stirringwith stirring
7. stirringAfter stirring for 30 min
8. addition15 ml of 30% NaOH in saturated brine was added
9. stirringto stir 60 min longer
10. customThe organic layer was separated
11. washthe aqueous layer washed twice with 50 ml of CH2Cl2
12. dry with materialdried over MgSO4
13. filtrationfiltered
14. customevaporated
15. customto afford a milky, pale yellow oil
16. distillationDistillation

ORD record

ord-13fb952a63114dae9a9c37a73f8b83b6

Source dataset

uspto-grants-2000_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06153589