tert-Butyl hydroperoxide → HCID 178495889, compound

HRID 1760770Notes

Reaction equation

HRID 1760770 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([N:9]2[C:13](=[O:14])[C@@:12]([CH3:27])([CH2:15][C:16]3[CH:21]=[CH:20][C:19]([O:22][C:23]([F:26])([F:25])[F:24])=[CH:18][CH:17]=3)[NH:11][C:10]2=S)[CH:5]=[C:6]([Cl:8])[CH:7]=1.[CH3:29][O:30][CH:31]([O:34][CH3:35])[CH2:32][NH2:33].C(OO)(C)(C)C.OS([O-])=O.[Na+]>CO>[Cl:1][C:2]1[CH:3]=[C:4]([N:9]2[C:13](=[O:14])[C@@:12]([CH3:27])([CH2:15][C:16]3[CH:21]=[CH:20][C:19]([O:22][C:23]([F:26])([F:25])[F:24])=[CH:18][CH:17]=3)[NH:11]/[C:10]/2=[N:33]\[CH2:32][CH:31]([O:34][CH3:35])[O:30][CH3:29])[CH:5]=[C:6]([Cl:8])[CH:7]=1

Participants

6

Reactant 4

HCID 6410tert-Butyl hydroperoxideHCID 89728Aminoacetaldehyde dimethyl acetalHCID 23665763Sodium BisulfiteHCID 59979230HCID 59979230, compound

Product 1

HCID 178495889HCID 178495889, compoundYield 100.6%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of the above thiohydantoin (4.47 g, 9.95 mmol) and aminoacetaldehyde dimethylacetal (6.50 mL, 59.7 mmol) in 20 mL of MeOH was added 7.69 mL (59.7 mmol, 70% in water) of t-butyl hydroperoxide solution, dropwise over 25 min. During the addition and for about 1 h after, the internal temperature of the mixture was kept below 20° C. with an ice water bath. The mixture was stirred at room temperature for 86 h, and 25 mL of saturated NaHSO3 solution was added slowly dropwise, maintaining the internal temperature below 20° C. with an ice water bath. The resulting cloudy white mixture was concentrated. To the residue was added EtOAc, and this mixture was concentrated again. The oily residue was partitioned between EtOAc and water, and the aqueous phase was separated and extracted with EtOAc. The combined organic layers were washed with water and brine, dried over Na2SO4, filtered and concentrated to give 5.21 g of (R)-3-(3,5-dichloro-phenyl)-2-[(E)-2,2-dimethoxy-ethylimino]-5-methyl-5-(4-trifluoromethoxy-benzyl)-imidazolidin-4-one as a thick yellow oil.

Workup

  1. additionDuring the addition
  2. waitfor about 1 h after, the internal temperature of the mixture was kept below 20° C. with an ice water bath
  3. temperaturemaintaining the internal temperature below 20° C. with an ice water bath
  4. concentrationThe resulting cloudy white mixture was concentrated
  5. additionTo the residue was added EtOAc
  6. concentrationthis mixture was concentrated again
  7. customThe oily residue was partitioned between EtOAc and water
  8. customthe aqueous phase was separated
  9. extractionextracted with EtOAc
  10. washThe combined organic layers were washed with water and brine
  11. dry with materialdried over Na2SO4
  12. filtrationfiltered
  13. concentrationconcentrated

Sources & evidence

ORD record
ord-9ca172b3781f4160ba45a5bb42a783dc
Source dataset
uspto-grants-2005_01
Patent number
US06844360B2

Reaction notes

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