Dimethylformamide dimethyl acetal → 2-Nitro-5-phenoxybenzaldehyde

HRID 2088774Notes

Reaction equation

HRID 2088774 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([O:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[CH:6][C:5]=1[CH3:17])([O-:3])=[O:2].C[O:19]C(OC)N(C)C>CN(C=O)C>[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([O:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[CH:6][C:5]=1[CH:17]=[O:19])([O-:3])=[O:2]

Participants

4

Reactant 2

HCID 78373Dimethylformamide dimethyl acetalHCID 27284182-Nitro-5-phenoxytoluene

Product 1

HCID 442030822-Nitro-5-phenoxybenzaldehyde

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A mixture of 2-nitro-5-phenoxytoluene (57.3 g, 0.25 mol) prepared in Step A above and dimethylformamide dimethyl acetal (43.1 mL, 0.324 mol) in DMF (259 mL) was heated overnight at 140° C. The mixture was cooled to room temperature, and the solvent was evaporated in vacuo. The residue was dissolved in THF (500 mL) and transferred to a 3 L 3-neck flask equipped with an overhead stirrer. The mixture was diluted with 500 mL of water, and NalO4 (160 g, 0.75 mol) was added in portions (slight exotherm). The mixture was stirred overnight at room temperature. The solids were filtered and washed well with EtOAc. The filtrate was washed 3× with saturated aqueous NaHCO3 solution, and then dried (MgSO4). The solution was filtered and the solvent was evaporated in vacuo. The crude product was chromatographed (10-40% CH2Cl2:hexane) to yield 2-nitro-5-phenoxy-benzaldehyde as a yellow crystalline solid.

Workup

  1. customthe solvent was evaporated in vacuo
  2. dissolutionThe residue was dissolved in THF (500 mL)
  3. customequipped with an overhead stirrer
  4. additionThe mixture was diluted with 500 mL of water, and NalO4 (160 g, 0.75 mol)
  5. additionwas added in portions (slight exotherm)
  6. filtrationThe solids were filtered
  7. washwashed well with EtOAc
  8. washThe filtrate was washed 3× with saturated aqueous NaHCO3 solution
  9. dry with materialdried (MgSO4)
  10. filtrationThe solution was filtered
  11. customthe solvent was evaporated in vacuo
  12. customThe crude product was chromatographed (10-40% CH2Cl2:hexane)

Sources & evidence

ORD record
ord-de70d73f6a9e49a19fc33aafff6bf892
Source dataset
uspto-grants-2013_05
Patent number
US08436006B2

Reaction notes

Loading…