Triphenylphosphine → Methyl 3-bromo-5-formyl-4-methylbenzoate

HRID 337657Notes

Reaction equation

HRID 337657 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:9]=[C:10](/[CH:13]=C/COC)[C:11]=1[CH3:12])[C:5]([O:7][CH3:8])=[O:6].[O:18]=[O+][O-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>ClCCl>[Br:1][C:2]1[CH:3]=[C:4]([CH:9]=[C:10]([CH:13]=[O:18])[C:11]=1[CH3:12])[C:5]([O:7][CH3:8])=[O:6]

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 24823OzoneHCID 67062162Methyl 3-bromo-5-[(1E)-3-methoxy-1-propen-1-yl]-4-methylbenzoate

Product 1

HCID 86651684Methyl 3-bromo-5-formyl-4-methylbenzoate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a dichloromethane (0.16 M) solution of methyl 3-bromo-5-[(1E)-3-methoxy-1-propen-1-yl]-4-methylbenzoate (1 eq., Amine 88, Step 1) was bubbled at −78° C. with freshly generated ozone until a persistent blue color was observed. The reaction vessel was then thoroughly purged with nitrogen before triphenylphosphine (1.1 eq.) was added. The resulting mixture was slowly warmed to RT over 6 h. The volatiles were then removed in vacuo and the resulting residue was suspended in a 1:1 (v/v) mixture of hexanes and ether. The insolubles were removed via filtration through a pad of silica gel. Concentration of the filtrate thus obtained in vacuo afforded a white solid. Further purification of the crude product by way of flash chromatography (SiO2, Hex→1:1 (v/v) Hex:EtOAc) afforded the title compound as a white solid.

Workup

  1. additionwas added
  2. customThe volatiles were then removed in vacuo
  3. additionthe resulting residue was suspended in a 1:1 (v/v) mixture of hexanes and ether
  4. customThe insolubles were removed via filtration through a pad of silica gel
  5. customConcentration of the filtrate thus obtained in vacuo
  6. customafforded a white solid
  7. customFurther purification of the crude product by way of flash chromatography (SiO2, Hex→1:1 (v/v) Hex:EtOAc)

Sources & evidence

ORD record
ord-6b6adf71b1cf4840bdeb1270b54e6925
Source dataset
uspto-grants-2014_11
Patent number
US08889714B2

Reaction notes

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