tert-Butyl hydroperoxide → Acetic acid 1-(4-bromo-3-methoxy-5,5-dimethyl-8-oxo-5,6,7,8-tetrahydro-naphthalen-2-yl)-ethyl ester

HRID 2180595Notes

Reaction equation

HRID 2180595 reaction equation
[C:1]([O:5]O)([CH3:4])([CH3:3])C.[Br:7][C:8]1[C:17]2[C:16]([CH3:19])([CH3:18])[CH2:15]CCC=2[CH:11]=[C:10]([CH:20]([O:22][C:23](=[O:25])[CH3:24])[CH3:21])[C:9]=1[O:26][CH3:27]>ClCCl.[O-2].[Cr+6].[O-2].[O-2]>[Br:7][C:8]1[C:17]2[C:16]([CH3:18])([CH3:19])[CH2:15][CH2:4][C:1](=[O:5])[C:3]=2[CH:11]=[C:10]([CH:20]([O:22][C:23](=[O:25])[CH3:24])[CH3:21])[C:9]=1[O:26][CH3:27]

Participants

5

Reactant 2

HCID 6410tert-Butyl hydroperoxideHCID 69731470Acetic acid 1-(4-bromo-3-methoxy-5,5-dimethyl-5,6,7,8-tetrahydro-naphthalen-2-yl)-ethyl ester

Product 1

HCID 69730619Acetic acid 1-(4-bromo-3-methoxy-5,5-dimethyl-8-oxo-5,6,7,8-tetrahydro-naphthalen-2-yl)-ethyl ester

Reagents, catalysts & solvents 2

HCID 10219390chromium (VI) trioxideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a suspension of chromium (VI) oxide (160 mg, 1.6 mmol) in dichloromethane (40 mL) at 0° C. was added tert-butyl hydroperoxide (13 mL, 96 mmol). After stirring at room temperature for 5 min, a solution of acetic acid 1-(4-bromo-3-methoxy-5,5-dimethyl-5,6,7,8-tetrahydro-naphthalen-2-yl)-ethyl ester (Compound A-97, 11.4 g, 32 mmol) in dichloromethane (10 mL) was added. The mixture was stirred at room temperature for 6 days and then quenched with 10% sodium bisulfite.). Organic phase was washed with 10% sodium bisulfite and brine, dried (Na2SO4), filtered and concentrated in vacuo. Recrystallization from ethyl acetate and flash column chromatography of the mother liquid (silica gel, 10% ethyl acetate in hexane) afforded the title compound as a yellow solid.

Workup

  1. stirringThe mixture was stirred at room temperature for 6 days
  2. customquenched with 10% sodium bisulfite
  3. washOrganic phase was washed with 10% sodium bisulfite and brine
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customRecrystallization from ethyl acetate and flash column chromatography of the mother liquid (silica gel, 10% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-d932314b7ca44f6d9f946f8bac0e72b3
Source dataset
uspto-grants-2005_05
Patent number
US06887896B1

Reaction notes

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