Acetic Acid → 3-Bromo-5-(3-pyridyloxy)benzaldehyde

HRID 725029Notes

Reaction equation

HRID 725029 reaction equation
C([Li])(CC)C.Br[C:7]1[CH:8]=[C:9]([CH:17]=[C:18]([Br:20])[CH:19]=1)[O:10][C:11]1[CH:12]=[N:13][CH:14]=[CH:15][CH:16]=1.CN(C)[CH:23]=[O:24].C(O)(=O)C>CCCCCC.CCOCC>[Br:20][C:18]1[CH:19]=[C:7]([CH:8]=[C:9]([O:10][C:11]2[CH:12]=[N:13][CH:14]=[CH:15][CH:16]=2)[CH:17]=1)[CH:23]=[O:24]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 6228DimethylformamideHCID 106877623-(3,5-Dibromophenoxy)pyridineHCID 178418400CID 53628100

Product 1

HCID 105645133-Bromo-5-(3-pyridyloxy)benzaldehydeYield 64.7%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent

Procedure

A 1.3M solution of s-butyllithium in hexane (9.2 ml) was added dropwise to a stirred solution of 3-(3,5-dibromophenoxy)pyridine (Preparation 6; 3.29 g) in dry ether (100 ml) at -78° C., and the resulting mixture was stirred at this temperature for 15 minutes. N,N-dimethylformamide (2.2 g) was then added dropwise and this mixture stirred at the same temperature for 1 hour. Glacial acetic acid (1.6 ml) was next added and the reaction solution was allowed to warm to room temperature, washed sequentially with saturated aqueous sodium bicarbonate solution and water, then dried (MgSO4). Evaporation under vacuum of the solvent gave an oil which was chromatographed on silica gel. Elution with dichloromethane first gave impurity which was followed by pure product. The product fractions were combined and evaporated under vacuum to give the title compound as an oil (1.80 g); δ (CDCl3): 7.36-7.43(4H,m), 7.76(1H,s), 8.45-8.50(2H,m), 9.90(1H,s). Found: C, 51.76; H, 2.89; N, 5.04. C12 H8BrNO2 requires C, 51.82; H, 2.90; N, 5.04%.

Workup

  1. stirringthis mixture stirred at the same temperature for 1 hour
  2. washwashed sequentially with saturated aqueous sodium bicarbonate solution and water
  3. dry with materialdried (MgSO4)
  4. customEvaporation under vacuum of the solvent
  5. customgave an oil which
  6. customwas chromatographed on silica gel
  7. washElution with dichloromethane first gave impurity which
  8. customevaporated under vacuum

Sources & evidence

ORD record
ord-541f83db7b2c45e6868998169f265673
Source dataset
uspto-grants-1998_01
Patent number
US05705523

Reaction notes

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