Dimethylformamide → 3-Bromopyridine-4-carboxaldehyde

HRID 7160Notes

Reaction equation

HRID 7160 reaction equation
CN(CCN(C)C)C.[Li+].CC([N-]C(C)C)C.[Br:17][C:18]1[CH:19]=[N:20][CH:21]=[CH:22][CH:23]=1.CN([CH:27]=[O:28])C>CCOCC>[Br:17][C:18]1[CH:19]=[N:20][CH:21]=[CH:22][C:23]=1[CH:27]=[O:28]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 122863-BromopyridineHCID 2724682Lithium diisopropylamide

Product 1

HCID 27629973-Bromopyridine-4-carboxaldehydeYield 51%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a solution of TMEDA (1.91 mL, 12.7 mmol) and LDA (12.7 mmol) in ether (50 mL) at −78° C. was added 3-bromo-pyridine (1.22 mL, 12.7 mmol). After 60 minutes at −78° C., DMF (1.08 mL, 13.9 mmol) was added, and the mixture allowed to warm to room temperature. After 1 hour at room temperature the reaction was quenched with saturated aqueous NaHCO3 (100 mL), extracted with CH2Cl2 (4×15 mL), dried (MgSO4), filtered and concentrated in vacuo to give the crude oil. Purification by column chromatography on silica gel (Hexanes: EtOAc 4:1) afforded the title compound as a crystalline solid (1.2 g, 51%). 1H NMR (CDCl3) 7.70 (d, 1H, J=4.8 Hz), 8.71 (d, 1H, J=4.8 Hz), 8.91 (s, 1H), 10.36 (s, 1H).

Workup

  1. customAfter 1 hour at room temperature the reaction was quenched with saturated aqueous NaHCO3 (100 mL)
  2. extractionextracted with CH2Cl2 (4×15 mL)
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customto give the crude oil
  7. customPurification by column chromatography on silica gel (Hexanes: EtOAc 4:1)

Sources & evidence

ORD record
ord-75f811fe78684dafa9ebd08ab40247d8
Source dataset
uspto-grants-2006_08
Patent number
US07084155B2

Reaction notes

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