Dimethyl Sulfoxide → 5-Bromo-α,α-dimethyl-3-pyridineacetaldehyde

HRID 1521586Notes

Reaction equation

HRID 1521586 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[Br:11][C:12]1[CH:13]=[C:14]([C:18]([CH3:22])([CH3:21])[CH2:19][OH:20])[CH:15]=[N:16][CH:17]=1.C(N(CC)CC)C>ClCCl>[Br:11][C:12]1[CH:13]=[C:14]([C:18]([CH3:22])([CH3:21])[CH:19]=[O:20])[CH:15]=[N:16][CH:17]=1

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 70977234HCID 70977234, compound

Product 1

HCID 891554725-Bromo-α,α-dimethyl-3-pyridineacetaldehyde

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent4×

Procedure

A solution of oxalyl chloride in dichloromethane (2.0 M, 0.869 mL, 1.74 mmol) was diluted with dichloromethane (2 mL) and then a solution of dimethylsulfoxide (0.250 mL, 3.50 mmol) in dichloromethane (1 mL) was added at −78° C. After stirring for 15 minutes, a solution of the title compound from Example 53 Step E (0.200 g, 0.869 mmol) in dichloromethane (3 mL) was added. The resulting reaction stirred for 30 minutes before triethylamine (0.600 mL, 4.35 mmol) was added. The reaction warmed to room temperature slowly and stirred overnight. It was quenched with the addition of water and then extracted with dichloromethane. The combined organics were washed with saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered and concentrated under reduced pressure. Purification by flash chromatography on silica gel (25-100% ethyl acetate in hexanes) provided the title compound: LCMS m/z 229.87 [M+2H]+; 1H NMR (500 MHz, CDCl3) δ 9.53 (s, 1H), 8.61 (s, 1H), 8.47 (s, 1H), 7.73 (s, 1H), 1.51 (s, 6H).

Workup

  1. customThe resulting reaction
  2. additionwas added
  3. stirringstirred overnight
  4. customIt was quenched with the addition of water
  5. extractionextracted with dichloromethane
  6. washThe combined organics were washed with saturated aqueous sodium chloride solution
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customPurification by flash chromatography on silica gel (25-100% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-a16701fbe02348d1ae2b5f272641fe9c
Source dataset
uspto-grants-2015_07
Patent number
US09073929B2

Reaction notes

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