tert-Butyl hydroperoxide → HCID 86594449, compound

HRID 1797417Notes

Reaction equation

HRID 1797417 reaction equation
[CH3:1][Si:2]([CH3:25])([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C@@H:3]1[C@@H:7]([CH2:8][O:9][CH2:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[C:6]([CH2:17][OH:18])=[CH:5][CH2:4]1.CC([O:30]O)(C)C>C(Cl)Cl.CC(C)[O-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(N(C(C)C)CCC1C2C(=CC=CC=2)NC=1)C>[CH3:1][Si:2]([CH3:25])([C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1)[CH:3]1[CH2:4][CH:5]2[C:6]([CH2:17][OH:18])([O:30]2)[CH:7]1[CH2:8][O:9][CH2:10][C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1

Participants

6

Reactant 2

HCID 6410tert-Butyl hydroperoxide2×HCID 59434260HCID 59434260, compound

Product 1

HCID 86594449HCID 86594449, compoundYield 162.8%

Reagents, catalysts & solvents 3

HCID 11026Titanium isopropoxideCatalystHCID 26903N,N-DiisopropyltryptamineCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
-30 °C

Procedure

To an oven dried, 1-L 3-necked round bottomed flask equipped with a mechanical stirrer, a temperature probe, and an argon line was charged activated molecular sieves (35 g) and DCM (160 mL) under an atmosphere of argon. The solution was cooled to about −30° C. DIPT (2.34 g, 0.01 moles) followed by titanium (IV) isopropoxide (2.36 mL, 0.008 moles) was added to the reaction mixture. The reaction mixture was stirred at −30° C. for about 20 minutes. Crude 76 (42 g, ˜0.1 moles) in DCM (40 mL) was added to the reaction mixture and stirred for about 30 minutes. TBHP (40 mL, 0.2 moles) was added to the reaction mixture at −30° C. After complete addition of TBHP, the reaction mixture was stirred at −30° C. for about 5 hours to complete the reaction. The excess peroxide was quenched with aqueous sodium bisulfite (20 g). The mixture was filtered through a Buchner Funnel with a pad of diatomaceous earth (Hyflo Celite®). The filtrate was washed with saturated NaHCO3, solution (100 mL) and brine (100 mL). The organic layer was concentrated in vacuo to give the crude title compound (60 g, >100% material balance) as an oil.

Workup

  1. customTo an oven dried
  2. custom1-L 3-necked round bottomed flask equipped with a mechanical stirrer
  3. additiona temperature probe, and an argon line was charged
  4. additionwas added to the reaction mixture
  5. stirringstirred for about 30 minutes
  6. stirringthe reaction mixture was stirred at −30° C. for about 5 hours
  7. customthe reaction
  8. customThe excess peroxide was quenched with aqueous sodium bisulfite (20 g)
  9. filtrationThe mixture was filtered through a Buchner Funnel with a pad of diatomaceous earth (Hyflo Celite®)
  10. washThe filtrate was washed with saturated NaHCO3, solution (100 mL) and brine (100 mL)
  11. concentrationThe organic layer was concentrated in vacuo

Sources & evidence

ORD record
ord-f5998119177845abaf9f74fe47a4bcda
Source dataset
uspto-grants-2006_04
Patent number
US07034152B2

Reaction notes

Loading…