Triacetoxyperiodinane → 3-Bromo-4-iodobenzaldehyde

HRID 1258005Notes

Reaction equation

HRID 1258005 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH2:9][OH:10])[CH:5]=[CH:6][C:7]=1[I:8].C([O-])(O)=O.[Na+].[Na+].[Br-].CC1(C)N([O])C(C)(C)CCC1.[O-]Cl.[Na+].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O>C(Cl)Cl.O.CCCCCCC.CCOC(C)=O>[Br:1][C:2]1[CH:3]=[C:4]([CH:5]=[CH:6][C:7]=1[I:8])[CH:9]=[O:10]

Participants

10

Reactant 6

HCID 159087TriacetoxyperiodinaneHCID 253881Sodium BromideHCID 516892Sodium BicarbonateHCID 2724126TempoHCID 166410803-Bromo-4-iodobenzenemethanolHCID 23665760Sodium Hypochlorite

Product 1

HCID 140498083-Bromo-4-iodobenzaldehydeYield 87.7%

Reagents, catalysts & solvents 3

HCID 8857Ethyl AcetateSolventHCID 8900HeptaneSolventHCID 21908982Water methylene chlorideSolvent

Conditions

Temperature
0 °C

Procedure

A solution of (3-bromo-4-iodophenyl)methanol (3.1 g, 9.9 mmol) in CH2Cl2/water (2:1, 225 mL) was treated with NaHCO3 (915 mg, 10.9 mmol), NaBr (1060 mg, 10.2 mmol) and TEMPO free radical (40 mg, 0.2 mmol). The resulting mixture was cooled to 0° C. and NaOCl solution (0.8 mL, 10% aq.) was added dropwise. The reaction mixture was left to come to room temperature while stirring. TLC 25:75 EtOAc:heptane after 30 minutes showed approximately 50% conversion to less polar spot. Sequence repeated using same equivalent of reagents. TLC still showed unreacted starting material. The reaction mixture was separated and the organic phase was treated with 1.0× Dess-Martin periodinane (2.1 g, 4.9 mmol) while stirring. TLC after 10 minutes showed complete conversion to less polar spot. The organic phase was washed with saturated NaHCO3, dried over Na2SO4, filtered and evaporated to give an orange solid. The crude material was chromatographed (80 g Redi-Sep column) eluting from 100% heptane to 50:50 EtOAc/heptane to give the intermediate (2.7 g, 87%) as a white solid. 1HNMR (CDCl3) δ ppm: 9.94 (1H), 8.10 (2H), 7.50 (1H).

Workup

  1. waitThe reaction mixture was left
  2. customto come to room temperature
  3. customThe reaction mixture was separated
  4. stirringwhile stirring
  5. washThe organic phase was washed with saturated NaHCO3
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. customevaporated
  9. customto give an orange solid
  10. customThe crude material was chromatographed (80 g Redi-Sep column)
  11. washeluting from 100% heptane to 50:50 EtOAc/heptane

Sources & evidence

ORD record
ord-944f78f3cede4d76be8780bcbb401bc8
Source dataset
uspto-grants-2013_06
Patent number
US08466115B2

Reaction notes

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