Sodium Thiosulfate Pentahydrate → Tert-butyl 3-bromo-5-formylbenzoate

HRID 1257525Notes

Reaction equation

HRID 1257525 reaction equation
[Br-].[K+].CC1(C)N([O])C(C)(C)CCC1.[Br:14][C:15]1[CH:16]=[C:17]([CH:25]=[C:26]([CH2:28][OH:29])[CH:27]=1)[C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19].Cl[O-].[Na+].O.O.O.O.O.S([O-])([O-])(=O)=S.[Na+].[Na+]>C(=O)(O)[O-].[Na+].O.ClCCl>[Br:14][C:15]1[CH:16]=[C:17]([CH:25]=[C:26]([CH:28]=[O:29])[CH:27]=1)[C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19]

Participants

9

Reactant 5

HCID 61475Sodium Thiosulfate PentahydrateHCID 253877Potassium BromideHCID 2724126TempoHCID 23665760Sodium HypochloriteHCID 58096191Tert-butyl 3-bromo-5-(hydroxymethyl)benzoate

Product 1

HCID 58095966Tert-butyl 3-bromo-5-formylbenzoate

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 6344DichloromethaneSolventHCID 516892Sodium BicarbonateSolvent

Procedure

To a suspension of potassium bromide (249.3 g, 2.095 mol), 2,2,6,6-tetramethylpiperidine 1-oxyl (3.27 g, 20.93 mmol) in saturated aqueous sodium bicarbonate (960 mL) and water (240 mL) were added tert-butyl 3-bromo-5-(hydroxymethyl)benzoate (119.7 g, 417 mmol) and dichloromethane (1200 mL). The mixture was cooled to <5° C. and sodium hypochlorite (850 mL, 12.53 mol) was added dropwise in 4 portions until the reaction completed. A solution of sodium thiosulfate pentahydrate (72 g) in water (250 mL) was added and the reaction mixture was warmed to ambient temperature. The organic layer was separated and the aqueous layer was extracted with dichloromethane (2×). The combined organic extracts were washed with brine, dried over magnesium sulfate, filtered and concentrated (119.0 g).

Workup

  1. temperatureThe mixture was cooled to <5° C.
  2. customThe organic layer was separated
  3. extractionthe aqueous layer was extracted with dichloromethane (2×)
  4. washThe combined organic extracts were washed with brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated (119.0 g)

Sources & evidence

ORD record
ord-d48244ab4a1e49c7bf7736ebdd649576
Source dataset
uspto-grants-2013_06
Patent number
US08461185B2

Reaction notes

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